Commission of the European Communities

nuclear science
and technology
A historical examination of concrete

Commission of the European Communities

ar scienc
chnolo
A historical examination of concrete

L. G. Mallinson, I. LI. Davies

Taylor-Woodrow Construction Ltd
Taywood House
345 Ruislip Rd
Southall, Middlesex UB1 2QX
United Kingdom

Final report

This work has been carried out under cost-sharing contract

No 432-84-7 WASUK with the European Atomic Energy Community
in the framework of its R&D programme on
'Management and storage of radioactive waste',
Sheet 7 'Storage and disposal in geological formations'

iiri'

i-

'

Directorate-General
Science, Research and Development

1987

felJR 10937 FN

IP.

Published by the
COMMISSION OF THE EUROPEAN COMMUNITIES
Directorate-General
Telecommunications, Information Industries and Innovation
Btiment Jean Monnet
LUXEMBOURG

LEGAL NOTICE
Neither the Commission of the European Communities nor any person acting on
behalf of the Commission is responsible for the use which might be made of the
following information

Cataloguing data can be found at the end of this publication

Luxembourg, Office for Official Publications of the European Communities, 1987

ISBN 92-825-6963-2

Catalogue number: CD-NA-10937-EN-C

ECSC-EEC-EAEC, Brussels Luxembourg, 1987
Printed in Belgium

SUMMARY
The requirement that concrete in nuclear waste repositories be stable physically
and chemically for hundreds, if not thousands, of years has initiated studies of
ancient and old concretes.
The history of cement and concrete is described. The oldest known concrete, from
Yugoslavia, is ca. 7,500 years old.
Concrete was used in many ancient
civilisations, including those of Egypt, Greece and Rome.
Ancient concretes were usually based upon lime, but sometimes gypsum was used.
Pure lime concretes hardened by atmospheric carbonation but the Ancients, in
particular the Romans, also employed hydraulic limes and discovered pozzolanas to
make superior concretes which, upon hardening, contained complex cementitious
hydrates including calcium-silicate-hydrate (CSH), the principal binding element
in Portland cement concrete.
Portland cement was not invented until 1824 or later and consists principally of
calcium silicates formed by clinkerisation of a mixture of limestone and clay in
carefully measured proportions.
The cement sets hydraulically to form,
principally, calcium hydroxide and CSH, the latter being an amorphous or
semi-amorphous substance of variable composition.
The published literature relating to the analysis of old and ancient cements and
concretes is reviewed.
A suite of samples spanning the history of concrete has been obtained. A variety
of physical and chemical, techniques have been employed to characterise these
samples.
Ancient concretes have survived
follows:
(a)
(b)
(c)
(d)
(e)
(f)

for many

reasons, which can be summarised

as

careful selection and preparation of materials;

high standard of workmanship and quality control;
stability of cementitious compounds, viz. calcite, CSH;
dense microstructures, created by good compaction (including polishing),
thus preventing the ingress of deleterious agents;
environmental factors, which may include a kind climate and absence of
interference by man;
lack of steel reinforcement.

The durability of early, reinforced concretes has been linked to:

(a)
(b)

high cement contents, at least partly necessitated

performance cements;
high standard of workmanship and quality control.

by

the

use

of

low

These factors are off-set by the negative effects of the relatively poor
compaction obtained without mechanical vibration and defects in aggregate
grading.

Ill

CONTENTS
Page No.
1.

INTRODUCTION

2.

CONCLUSIONS

3.

RECOMMENDATIONS FOR FURTHER STUDY

11

4.

THE HISTORY OF CEMENT AND CONCRETE

14

5.

ANALYTICAL STUDIES OF ANCIENT CEMENT-BASED MATERIALS

45

6.

ANALYTICAL STUDIES OF OLD, PORTLAND CEMENT-BASED MATERIALS

52

7.

RECENT STUDIES INVOLVING MODERN ANALYTICAL TECHNIQUES

61

8.

ANALYTICAL TECHNIQUES

67

9.

SAMPLES COLLECTED

76

10. RESULTS

141

11. REFERENCES

189

12. APPENDICES

201

INTRODUCTION
The potential use of concrete in nuclear waste repositories places stringent
requirements upon this material; it must be chemically and physically stable
in the very long term.

At a meeting in November 1982, organised by Taywood

Engineering on the subject of the use of concrete as an engineered barrier

in active waste repositories, data was presented by R.D. Browne on a 2500
year old concrete from Rhodes.
As a result of the interest generated by this report a project, jointly
funded by the Department of the Environment, the Commission of the European
Communities and Taylor Woodrow, was designed to examine the properties of
old and ancient concretes.
The objectives of the study are as follows:1.

To conduct a review of the literature dealing with the history of

cement and concrete, particularly that involving physical and chemical
examinations of old and ancient materials.

2.

To establish contact with those individuals and bodies interested in,

and involved with, the study of archeological concrete.

3.

To

obtain

suite

of

samples

representative

of

the

history

of

concrete.
4.

To

characterise

attention

to

the

be

samples

paid

to

physically

the

and

determination

chemically,
of

particular

calcium-silicate-

hydrate.
5.

To provide an assessment of those factors which have contributed to

the durability and serviceability of the sample concretes.

After an initial phase during which the project was publicised and several
samples donated, a meeting of interested parties decided that, within the
confines of the budget, the best approach to sample examination would be to
concentrate

on just

Ancient Greek

two of

concrete

the collected

samples, that

is a sample of

from Camiros, Rhodes, c.500 B.C. and a sample of

concrete from the United Kinqdon's first, multi-storey, reinforced concrete

framed building, Weaver's Mill, Swansea, 1897-8.

The ages of these samples

approximate to the reguirements for the length of confinement of low level

radioactive waste, i.e. hundreds of years, and for intermediate and high
level wastes, i.e. many thousands of years.
Other samples were examined in less detail, although samples from Britain's
first,
1899

reinforced

was

concrete, marine

subjected

complement

to

data on the

similar

identical

samples

concrete

of

ancient

study

latter and

concretes of almost

structure, Woolston
as

for

Weaver's

enable comparisons

age.

Quay,
Mill

Southampton,
in order

to

to be made of two

The very small size of some of the

precluded

the

examination

of bulk

physical

Research Establishment

obtained

properties such as permeability.

Mid-way

through

the project

the Building

deep cores from the concrete core of Hadrian's Wall.

examined solely at the BRE.

These samples were

Other samples were examined at Taylor Woodrow

Research Laboratories, Southall; Blue Circle Research Division, Greenhithe;

Imperial

College

of

Science

and

Technology,

Department

of Metallurgy

Materials Science and the Building Research Station, Garston.

-2-

CONCLUSIONS
2.1

Ancient Concretes
2.1.1

Greek (Camiros Water Tank)

The Ancient Greek sample examined was a fully carbonated lime
concrete.

No CSH was found nor any evidence of the use of

volcanic earth as a pozzolana.

Although the concrete is well

compacted by comparison with other ancient concretes and the

matrix, at the microscopic level, is quite dense in places,
nevertheless

the concrete

is highly

porous and cracked

and

would be expected to be highly permeable to water and gases.

The material is weak and crumbly.

These findings are contrary

to those of Efstathiadis (7).

It may be that the sample, which came from a region near the
top of

the

different

tank, examined

area

from

that

in this study was from quite a

of

Efstathiadis

and

was

never

intended by the Ancient Greeks to be of special quality and

needing to be water-tight.

Perhaps this area has weathered

badly or been damaged, for instance by tourists; damage during

sample extraction cannot be discounted.

Problems with this concrete may have been the reason why the
tank was put out of use around the 3rd centry BC, as mentioned
by Efstathiadis.

The concrete may have survived because it

has not been subjected to any severe environmental stresses.

2.1.2

Reading Abbey
This sample is a fully carbonated lime concrete.
of CSH was found.

No evidence

The matrix is quite porous, but little

cracking is present and the samples examined were quite hard.

The structure itself is now, however, badly weathered and the
concrete is extremely soft and crumbly in places; a renovation
programme is underway.

It seems likely that the durability of

this concrete is linked to:

a)

Low

environmental

stresses.

The

sheltered, river-valley position.

Abbey

occupies

Acid rain may provide

an additional, 20th century, deterioration mechanism.

b)

Massive

construction.

The walls are massive and

essentially non-load-bearing; a low strength concrete,

thick

enough

to withstand

continued

environmental

attrition, will suffice in this situation.

2.1.3

Hadrian's Wall
Recent

work

by

the

Building

Research

Establishment

has

established the presence of CSH in deep cores from the Roman

Wall.

The method of formation of the CSH is a matter of

speculation but a preliminary conclusion that can be reached

is that it seems likely that the CSH of the type found is
stable for at least 1800 years.
2.1.4

Durability of Ancient Mortars and Concretes

The results of this and other researches indicate that factors
contributing

to the durability

of ancient mortars are as

follows:
a)

Selection and Preparation of Materials

The

Greeks

and

the

Romans

chose

their

materials

carefully; Vitruvius (3) emphasises the importance of

this.

There is evidence that aggregates were washed and

graded (6,7).
b)

Workmanship and Quality Control

It has been stated (9) that the Romans had little or no
scientific understanding of their cement and concrete.
The writings of Vitruvius (3), however, do at least show
that the reasons behind the behaviour of materials were
being discussed.
that

the

basis

Rather, it is a commonly held opinion

for

the

excellent

quality

of

Roman

concretes and concrete construction was the workmanship

-4-

and quality control exercised upon materials designed as

a

result

of

engineering.

vast
One

very

experience
important

in

constructional

contribution

to this

experience was the writings of Vitruvius (3) and there is

evidence that his instructions were followed throughout
the Roman Empire (5,9).

c)

Chemical Stability of Cement and Concrete

It has been shown that the cementitious phases present in
concrete, viz. calcite, CSH, can be stable for periods of
thousands of years under varying exposure conditions.

d)

Microstructural Factors
The microstructure of a concrete, especially that of the
surface, plays a crucial role as regards durability in
determining

the progress of deleterious

reactions that

may occur due to the ingress of aggressive agents.

ancient

concretes

that

have

been

examined

have

Many
dense

microstructures which have arisen from the intergrowth of

calcite crystals formed as a result of the carbonation of
slaked lime and from compaction, including polishing.

In

some cases oils have been added to reduce shrinkage and

improve

compaction.

The

fine

microstructures

have

produced strong materials and have enabled watertightness

to be achieved in those structures exposed to water.

The

hardening process of lime mortars has been attributed not

only to carbonation and drying but also to the periodic
dissolution
(14),

so

and
that

reprecipitation
a

concrete

of

may

calcium

improve

its

carbonate
physical

properties with age.

e)

Environmental Factors
Consideration of environmental factors has perhaps been
neglected by some researchers.
interference by man.
structures

have

It is probable that many ancient

survived

-5-

This includes mechanical

because

they

have

been

left

alone, hence the mere existence of an antique concrete

should

not

Ancient

be

concretes

conditions
polluted,
rain,

taken

for

have

many

industrial

must

now

structures.

as proof

survived

centuries.
atmosphere

present

It

positive

has been

noted

excellence.

the

local

weather

The

20th

century,

and

new

of

particularly

threat

to

(16) that

acid

ancient

modern

lime

mortars may not be durable because the hardening process

requires moist air free of sulphur dioxide.

f)

Lack of Reinforcement
The major

problem

with

modern,

reinforced

concrete

is

corrosion of the reinforcing steel, due to a variety of

causes.
which

In many cases it is the condition of the steel

governs

ancient

the

durability

concretes

reinforcement

do

as

not

of

the

contain

means

of

concrete.

steel,

Since

corrosion

deterioration

is

of
not

applicable, neither is the reguirement of a concrete to

protect

the steel.

carbonated

Ancient

(pH'U9.4)

concretes which

cannot

maintain

reguired to protect steel (pH>ll).

the

are fully
environnent

Care must therefore

be exercised in comparing the durabilities of ancient and

modern

concretes

such

that

eguitable

criteria

are

applied.

2.2

Old, Portland Cement Based Materials

The information gained
has

been

samples

greater
were

than

obtained

in this study from Portland cement concretes

that
which

from

ancient

enabled

concretes

a wider

because

larger

range of tests to be

applied.
2.2.1

Weaver's Mill (1897-8) and Woolston Quay (1899)

(a)

Calcium Silicate Hydrate (C5H)

The CSH phases in both concretes did not appear to have
suffered

any degradation.

6-

The average composition

was

different in the two cases (Ca/Si =1.5 for Weavers Mill,

= 2.1 for Woolston Quay) and this may indicate that a
different state of hydration has been reached in the two
concretes.

It has been postulated that the proportion of

calcium in CSH increases with a decrease in the water/

cement

ratio;

the

analyses,

together

with

other

observations, indicate that Woolston Quay concrete was

made with a dry mix.
(b) Unhydrated Cement
Both

concretes

contained

unhydrated

cement

grains.

Hydration is therefore incomplete after a period of 85

years; since its progress has not been followed from the
initial mixing it cannot be stated whether hydration has
stopped

or

is

continuing

surrounding

anhydrous

barrier

further

to

at

cement

a certain
grains

hydration

of

has

those

rate.

CSH

acted

as a

grains.

The

reserve of unhydrated cement allows further curing, with

conseguent

strength

gain

and

the

possibility

of

autogenous healing of cracks.

(c) Cement Grain Size
Cement

particle sizes

in both concretes have a wide

distribution, with grains of 100 jjm or more in diameter,

about

ten

times

that

of a modern

OPC.

Since the

hydration of cement is essentially a surface reaction,

the old cements would be slower setting than a modern OPC
and

the

larger

grains

might

be

expected

to hydrate

incompletely, leaving anhydrous cores.

(d) Cement Composition
Both

cements

are

deficient

saturation factors.

in

lime, with

low

lime

The potential compound compositions

indicate that they were high belite, low alite cements.

Such

cements would

strength.

-7-

be slow setting, with

low early

(e)

Cement Content
The

cement

contents

particularly
cement

that

content

of

both

of Woolston

in

concretes

Quay,

are

high,

with an estimated

excess of 600 kgm~3.

The probable

reasons for this are that (1) using cements of moderate

performance necessitates high cement contents to produce
adeguate strength, (2) the two structures were the first
of

their

kind

in

the

U.K.,

therefore

Hennebigue

and

Mouchel would be anxious to produce a good product, with

a guality concrete that would stand the test of time and
act as an advertisement

for the company

(which was the

case).

Durability was a concern of Mouchel and Partners

(107),

so

that

Woolston

Quay

concrete

was

probably

designed with the aggressive, marine environment in mind.

The high cement contents could be used without the risk
of thermal cracking because the high belite cements, with
larger particle sizes, set more slowly, with a lower heat
of

hydration

than

modern,

high

performance

ordinary

Portland cements.

Alkali-aggregate reaction can be a problem if high cement

contents

are

used.

This has not

been

the

case

with

either concrete.
(f)

Carbonation
Carbonation depths in both concretes are at the lowest
limit of the depth range which can be predicted for 85
year

old

provides

concrete.
a

large

The

high

cement

of

alkaline

reserve

content,

which

material,

is

principally responsible for this.

(g)

Permeability
The water permeabilities of the two concretes are very
different;

that

of Woolston

Quay

is very

low whereas

Weaver's Mill has a coefficient of permeability some five

orders of magnitude greater and is highly permeable.

The

measured porosities of the two concretes are very similar

-8-

and it is postulated that those channels responsible for

the high permeability of Weaver's Mill concrete possess
diameters

outside

porosimeter.

the

measuring

range

of

the

mercury

These channels have arisen because of the

gap grading of the fine aggregate and poor compaction.

The permeability of Woolston Quay concrete is lower than
that

expected

would

result

from

the pore

size

from pore blocking

distribution.

This

due to further

cement

hydration during the permeability test.

The low permeability of Woolston Quay concrete is highly
appropriate for its marine situation.
without

the

compaction.

use

of

Weaver's

modern,
Mill

unsuitable for marine use.

the

only

part

of

the

It was achieved

mechanical

concrete

methods

would

be

of

highly

At its demolition, however,

Mill

showing

distress was

that

subjected to running water (58).

h)

Chloride Content
Some areas of Woolston Quay were showing distress due to
reinforcement corrosion when the structure was inspected
in

1963

(108),

although

it

should

be noted

that

the

structure was found to be in perfect condition 21 years

after construction (107).

The levels of chloride found

in one sample of concrete were above the activation level

commonly accepted for the corrosion of reinforcing steel
(105), and it must be concluded that chloride ions had
penetrated to the steel in certain areas of the structure
and had induced corrosion.

2.2.2

Cement Barrel (1848)

A microstructural examination of the 137 year old cement paste
from the

'Ship on Shore' public house at Sheerness revealed

similarities between it and Weaver's Mill and Woolston Quay

cements.

A wide

particle

size distribution

was found and

grains larger than 100 fjm had not completely hydrated.

cement had a high belite, low alite composition.

-9-

The

2.2.3

The Durability of Old, Reinforced Concretes

The principal conclusion

from the study of two, very early,

reinforced

that

concretes

is

they

derived

their

desirable

properties leading to their good durability largely from their

high cement contents.

To some extent this was due to the

moderate performance of the early

cements, which were slow

setting^ with low early strength,due to their high belite, low

alite content and a wide particle size distribution, which
necessitated
modern,

a higher cement content than is necessary with

high

performance

reguired strength.
were concerned
the

early

cements

in

order

to achieve

the

A further factor is that the constructors

to see that guality concrete was produced in

days

of

reinforced

concrete,

about

building establishment was highly suspicious. .

-10-

which

the

RECOMMENDATIONS FOR FURTHER STUDY

3.1

Ancient Concretes
3.1.1

Sampling
Systematic sampling of ancient concretes should be undertaken,
paying particular attention to quality and environment.

Those

samples which may have survived simply because they have been
left alone in a kind
particular

environment

reference

underground

to

the

should

disposal

be avoided.

of

nuclear

With

waste

in

repositories, attempts should be made to sample

concretes from foundations and other underground structures.

3.1.2

Sample Size
Attempts should be made to obtain large samples in order that
a

wide

range

of

testing

can

be

carried

out.

This

is

particularly relevant for physical testing, e.g. permeability,

diffusion

and

strength

measurements, which

requires

large

samples and provides valuable information about bulk concrete

behaviour.

3.1.3

Sample Location
Attempts

should

be

made

surface and the bulk.

from different

to

obtain

samples

from

both

the

A number of samples should be taken

parts of a structure

in order that they be

representative.
3.1.4

Pozzolanic Concretes
Concretes made with pozzolanas and hydraulic limes should be
examined

as the nearest

relatives of modern concrete.

The

behaviour of calcium-silicate-hydrate (CSH) with time can then

be assessed.

- 11-

3.1.5

Hadrian's Wall

Initial studies of deep cores from Hadrian's wall have shown

the presence of CSH formed by a mechanism as yet undetermined.
Further

studies should

be carried

out on these samples and

attempts made to get more samples from other areas.

Other

parts of the Wall contain mortar which has proved to be less

durable than that so far examined; samples of these mortars
could provide illuminating comparisons.
5.2

Old, Portland Cement Concretes

3.2.1

Hennebique Structures

Many

of

today

the

and

early

are

ferro-concrete

testaments

to

structures

their

still

durability.

survive

They

are,

however, increasingly beinq knocked down as they outlive their

usefulness.
obtain

Advantage should be taken of each demolition to

samples.

Selected

Hennebique

buildings

could

be

subjected t non-destructive examinations.

3.2.2

Microstructure

Detailed electron microscopy, coupled with X-ray narcoanalysis

and

image

information
proportions

analysis,

is

regarding
of

unhydrated

cements, particularly

necessary
the

in

order

distribution

and

the amount

hydrated

and

phases

to

obtain

relative
present

of alite vs. belite.

in
The

cement particle size distribution should also be obtained.

3.2.3

Pore Size Distribution

Measurement of large pores and voidage, outside the range of

the porosimeter used in this study, should be undertaken to
ascertain the effect of such pores on the transport properties
of the concretes.

12-

.2.4

Steel
Examination
times

would

of
be

the
of

steel

reinforcement

interest

in

order

employed
to

in

determine

former
if

the

composition or microstructure has changed since then and to

ascertain what effect, if any, such changes might have on the
durability of reinforced concrete.

13

THE HISTORY OF CEMENT AND CONCRETE

4.1

Introduction
Cement and concrete are usually thought of as being modern materials
and normally of little interest to most people.

Yet concrete has its

origins in antiquity and, had it not been for the fall of the Roman
Empire and the subsequent Dark Ages, Portland cement and reinforced
concrete would doubtless be centuries old; perhaps the same could be
said for much of today's technology.
Publications detailing the history of cement and concrete are limited
in number, but perhaps the best, overall view is given in 'Highlights
In the History of Concrete' by C.C. Stanley (47). A valuable book by
Francis (48), an ancestor of one of Britain's pioneer cement makers,
sets out in great detail the history of the Roman cement industry and
the birth and early history of the Portland cement industry.

An

interesting insight is provided into the lives of the early pioneers

and their commercial transactions.

Davey

(49) in

'A History of

Building Materials' describes a wide range of cementitious materials

used from ancient times up to the present day.

Lea (1) includes many

historical details in his comprehensive book 'The Chemistry of Cement

and Concrete'. Spackman (50) reviews the work of a very large number
of authors in his book
published in 1929.

'Some Writers on Lime and Cement

,'

Finally, two good reviews on the history and

properties of Portland cement have been published in Transactions of

the Newcomen Society by Halstead (51) and Skempton (19).
4.2

The Oldest Known Concrete

The oldest known concrete (47, 52) has been excavated from the banks
of the river Danube at Lepenski Vir in Yugoslavia.

It dates from

about 5600 BC and is reported to be a lime concrete made from red

lime, sand, gravel and water.

The concrete, approx. 250 mm thick,

formed the floors of fishermens' huts.

this

find

limestone

is a matter
and

By how far concrete pre-dates

of speculation.

its subsequent

slaking

and

The effects of burning

hardening

in

air were

doubtless discovered around camp fires, but its use in making concrete
necessitates the formation of at least semi-permanent settlements.

-14-

4.3

Ancient Egypt
The next known period
Ancient Egypt.

of cement-making

is early dynastic

Gypsum mortar was employed

times in

in the Great Pyramid at

Giza, c. 2500 BC and in the tombs of Saqqara.

Outcrops of rock gypsum are common throughout the Middle East.

The

gypsum would be broken up and burnt in a primitive kiln, perhaps just

a hollow in the side of a hill.

Only moderate temperatures need be

achieved - between 130 and 170C - to dehydrate gypsum to form the

hemihydrate, which

then

presence of calcium

sets

rapidly

carbonate

on

mixing

with

water.

The

in Egyptian mortars and plasters has

perhaps misled some authors into believing that lime concrete was made
by burning

limestone.

Fuel

in Egypt, however, has always been in

short supply and very much larger amounts would be needed to achieve
the

higher

limestone

temperatures

than

to dehydrate

(ca.

900C)

gypsum,

required

so that

to

decarbonate

the calcium

carbonate

observed is much more likely to be an unaltered, original impurity in

the gypsum.
area

dry

In any case, gypsum mortar has proved very durable, in an

enough

construction

with

such

that

mud

impunity.

bricks

Stanley

could
(47)

be

shows

used
the

in

building

first

known

illustration of concrete work, an Ancient Egyptian mural from Thebes,

of about 1950 BC.

The Egyptians used their cement either as a mortar

between blocks of stone - and this would enable the blocks to be slid
more easily into place - or as a render, or stucco, to dress brick or
masonry walls.

The achievement of the Ancient Egyptians, and certainly the Stone Age
Yugoslavs, must not be underestimated.

We naturally stand in awe of

Roman constructions and their advanced concrete technology, yet it has

been noted (53) that when in 5 BC Herodotus gazed upon the pyramids,
they were more ancient to him than he is to us.
4.4

The Ancient Greeks

The concrete technology of the Egyptians spread to the Greeks and the
Romans, who developed it extensively.

During the Minoan period (c.

1500 BC) lime stucco was being applied to buildings as a coating for
rubble masonry, as at Vasiliki

(49), where an analysis of the two

- 15

inches of render covering sun-dried bricks and loose rubble showed

about 40% soluble silica and alumina, as well as calcium carbonate.
It is not known whether clay was added to a burnt lime or was
originaly present in an impure limestone.

Later examples contained

rather more lime, up to 95% present as calcium carbonate, but again it

is not known whether this represents an original limestone composition
or one with subsequent addition of powdered limestone, as was used by
the Greeks and Romans.

High quality, polished mortar renderings have

been found, for instance at Malia (11). The Greeks subsequently made
much use of renders, both for ornamental buildings and hydraulic
structures.

The Doric temples often had to be built from locally

available, soft limestone when suitable marble was unavailable.

thin coating of stucco was then used to cover the porous limestone,
filling in the crevices and making the surface smooth, providing also
a base for colouring.
employed.

Often marble dust was added to the mixture

In one hydraulic structure, the cistern at Megara (c. 500

BC), a single layer was used (11).

layers, varying

Malinowski (11) considered such

in thickness between

aggregate concrete.

10 and 60 mm, to be fine

The Greeks also used lime mortars as a binding

material between stone and brick and this building method has since
become universal.
4.5

The Romans
It seems very

likely that the Romans learned the art of making

concrete from the Greeks.

According to Stanley (47), Roman concrete

dating back to 300 BC has been found.

It is thought (49) that the

earliest uses of concrete were in foundations; examples are the podia

of the temples of Concord and Castor, 121 and 117 BC respectively.
Concrete, from

the Latin

concretus, meaning

condensed, solid or

composed of diverse parts, was termed opus caementitium

and was

used a great deal to fill the cores of walls faced with stone blocks.
In the core layers of caementa, consisting of broken stones and
tiles, were filled with lime mortar.

When the stone block facing was

replaced with a facing of small stone, as in the 1st and 2nd centuries
BC,

this work

timber

was known

formwork

during

as opus

incertum

construction.

and
Opus

usually

required

reticulatum

was

similar, but consisted of squared pieces of stone set with their sides
at 45 to the horizontal, ie.
reticulate
- 16-

diamond

fashion, thus forming a

pattern, a system in use from the 1st century BC until the 2nd century
AD.

Opus testaceum

consisted

of a concrete wall faced with brick

and was used from the 1st century BC until the end of the Western
Empire.

Finally,

opus

mixtum

contained

mixture

bricks and was used from the 3rd century AD onwards.

concrete in almost
today.
Ordinary

of

stones

and

The Romans used

every kind of construction, very much as we do

To be able to do this they had to develop special materials.

lime

concrete

and

mortar

lacked

the

setting

properties,

strength and durability necessary for marine structures and would be

too heavy for the mass concrete domes and vaults that were built.

To

solve the first problem, the Romans developed the use of pozzolanic
lime concrete, probably inherited from the Greeks, and, to solve the
second, they made lightweight

concrete and experimented

with metal

reinforcement.

4.5.1

Pozzolana
Vitruvius (3) refers to pozzolana as: 'a kind of powder which
from natural causes produces astonishing results.

It is found

in the neighourhood of Baiae and in the country belonging to

the towns round Mount Vesuvius.

This substance, when mixed

with lime and rubble, not only lends strength to buildings of

other kinds, but even when piers of it are constructed in the
sea, they set hard under water.' Vitruvius then goes on to say
why he thinks this happens.

It was around
guarried

the second

the

pink,

century BC that

sand-like

material

the Romans first

form

Pozzuoli,

locality from which the term pozzolana is derived.

the

It was not

sand, as they first thought, but a volcanic earth containing

compounds of silica and alumina which, when mixed with lime
and

water

at

ordinary

cementitious compounds.

temperatures,

will

form

stable,

Thus no longer was calcium carbonate

the sole binding agent, as in a set non-hydraulic lime, but

also

calcium

silicate

and

aluminate

hydrates, producing

stronger, more durable material which, furthermore, would set

under water.
water;

good

Pozzolanic concrete has good resistance to sea

example

is given

by Davey

(49) of an opus

reticulatum wall, near Naples and exposed to the sea, where

17

the tufa blocks of the wall have been considerably eroded, yet
the pozzolanic mortar has endured.

According to Stanley (47)

the first major use to which pozzolanic lime concrete was put
was in the theatre at Pompeii, built

in 75 BC.

Throughout

Europe the Romans used pozzolana wherever it could be found.

Thus

the

waterworks

of

Gaul, which

supplied

water

to the

fortifications near Cologne and were constructed in the reigns

of the emperors Trajan (98 - 117 AD) and Hadrian ( 1 1 7 - 138
AD) contained trass, a volcanic material similar to pozzolana,
from the Eifel, Moselle, Nette and Brohl valleys.

In Britain,

where

found,

the

tiles

and

Romans

no

natural

resorted

pozzolanic
to

the

deposits

use

of

could

crushed

be

bricks,

pottery, which produced a mortar with similar characteristics

and was even preferred
crushed

tile

in some instances.

pozzolanic

lime

concrete

agueduct Agua Marcia near Rome, c.

An example of a

is

144 BC.

that

from

the

Malinowski (11)

has pointed put that in some important Roman constructions,

even hydraulic and marine ones, pozzolana was not used and yet
the lime concrete

performed

satisfactorily.

He guotes the

examples of the harbour at Caesarea and the Cloaca Maxima in

Rome.

4.5.2

Roman Attempts to Reinforce Concrete

As the design of their structures became more ambitious, the

inventive Roman engineers attempted, for the first time ever,
to reinforce concrete using bronze strips and rods.
(47) guotes the Colosseum
was

tried.

degrees

of

The

attempts

thermal

Stanley

(80 AD) as a structure where this

failed

expansion

because

between

of

the

different

bronze

and

concrete.

This failure to improve the tensile strength of concrete had a

major conseguence for Roman architecture : buildings had to be
designed to carry their loads in compression; this resulted in
walls sometimes several metres thick.

A Roman building stood

by virtue of the tough, monolithic gualities of the concrete.

Vaulting of brick or masonry, as employed in Medieval times,
could not be used as such vaults would have pushed out their
supporting walls.

So a concrete vault covered space like a

lid and where brick arches occur, such as in the Basilica of

18

Constantine and the Thermae of Caracalla and Diocletian, these

have been found to be merely superficial, just a few inches in
concrete walls two metres thick.

Such arches are thought to

have played more of a part during construction, before the

concrete had set.
4.5.3

Roman Lightweight Concrete

One approach

adopted

to alleviate the problems of always

having to use massive construction was to use to lightweight

concrete.

Two methods were tried : to begin with earthenware

jars were cast into walls, but later the use of lightweight
aggregate was adopted.

Crushed pumice, a porous volcanic

rock, served the purpose well and could also provide better
insulation.

Lightweight concrete was used in some of the

arches of the Colosseum, the dome of the Pantheon (47) and in

the vaulting of the theatre of Taormina (11).
4.5.4

Roman Precast Concrete

The Romans may have been the first users of precast concrete
during the reign of Caligula (37-41 AD) when, in Naples, a
breakwater was built of concrete blocks which had been allowed
to harden before use.

4.5.5

Hadrian's Wall
One of the largest Roman constructions was built in Britain Hadrian's Wall.

Built during the second century A.D, the Wall

extended from the Solway Firth to the Tyne and was some 120 km
long.

In places the Wall stood over 4m high and was built in

the opus incertum style, with stone facing a core of lime

concrete.

The

concrete

has

proved

to be of varying

durability, today being very soft and crumbly in some places

but very hard in others. Nevertheless, the Wall has stood for
nearly

two

thousand

natural environments.

years

in one

of Britain's harshest,

With 80 milecastles and 16 forts one

can only imagine the awe with which the natives must have
viewed this work, a psychological as well as physical barrier,

-19-

and evidence of an intellectual and technical superiority to

be denied Western man for many centuries after the Romans left
these

shores;

concrete

for,

technology

as

with

almost

much

else,

disappeared

the

with

knowledge

of

the end of the

Roman Empire.
4.5.6

Vitruvius

It could be argued that the most important facet of the Roman

achievement in building technology was that the passing-on of
the knowledge of construction and the choice of materials was
not left to chance, to be handed down by word of mouth, but
was actually written down.
thought by Howard

The works of Vitruvius (3, 54),

(54) to have been written at the time of

either Augustus or Nero, comprised a manual for building which

was in use for nearly two millennia.

There is much evidence

(11,

by

49)

that

the

rules

selection, proportioning,

laid

down

mixing

and

Vitruvius

compaction

for

the

of concrete

were followed throughout the Roman Empire, one example being

mortars found at the Park Street villa, near St. Albans (49).
There is evidence too, that aggregates were selectively graded
for a particular job (49).

4.6

The Fall of the Roman Empire - The Loss of Concrete Technology

After the fall of the Roman Empire what concrete work there was seems
to have been only involved the use of non-hydraulic lime.
the Saxons used
about 700 A.D.

In Britain

concrete and primitive concrete mixers dating from

have been reported (47).

After the Norman invasion,

there was a resurgence in the number of works involving concrete, yet

these still

tended

only to use concrete

in a relatively

fashion, for foundations and as the cores of walls.

primitive

An example of the

latter type is Reading Abbey, built about 1130, where the concrete
core still stands, though the stone facing has gone.

Major Norman

construction works, i.e. castles and cathedrals, often used concrete.

It appears that

little use was made of, and there was virtually no

progress with, concrete

until

effort came to be directed

the

17th

and

18th

towards rediscovering

20

centuries.
the secret

Much
of the

Romans and experiments with pozzolanas

hydraulic

limes

began,

and attempts

particularly

in

to manufacture

France.

Such

early

experimenters were Belidor, Loriot, Chaptal, Saussure, De Morveau and

Vicat (51).
for the

George Semple used an hydraulic lime mixed with gravel

foundations

of the Essex Bridge over

the River Liffey

in

Dublin in 1753 (49).

4.7

John Smeaton - The Eddystone Lighthouse

It

was

Leeds

advance.

engineer, John

Smeaton, who

In 1756 he was commissioned

Lighthouse.

made

the

next

major

to build the third Eddystone

The two previous structures had proved inadeguate, being

of timber construction, and Smeaton was determined to build his new

Lighthouse

out of stone and cement.

For this purpose he needed a

cement that would be strong and would set hard under water reasonably
guickly so as not to be washed away by the sea.

No such cement was

available in 1756, so Smeaton set about a series of experiments to

find one.

On the continent

considerable use was being made of a

pozzolana known as Dutch tarras or trass; a 2 : 1 mixture by volume of

slaked

lime to Dutch tarras being used for structures subjected to

water.

The tarras was in fact dug up in Germany and transported to

Holland where it was mixed with an hydraulic, blue, argillaceous lime

and prepared to become 'tarras mortar'.

Smeaton visited Holland and

initially opted for a mixture containing egual parts of lime and Dutch
tarras.
that

After a series of experiments, however, he eventually decided

the cement

with

the best

gualities was one resulting

mixture of egual parts of siliceous

formation

at

Aberthaw

in

South

Civita Vecchia, a consignment

imported
built

by

a Plymouth

in 1759

and

limestone, from the blue

Wales, and

Italian

pozzolana

lias
from

of which had just been speculatively

merchant.

remained

from a

The lighthouse

in place

until

was

subseguently

1876 when, due to its

weakening structure, it was dismantled and re-erected on Plymouth Hoe,

where it can still be seen today.
base

of

Smeaton's

Lighthouse

Even more remarkably, the concrete

still

stands

on

Eddystone

rock, a

monument to the durability of a material which Stanley (47) thought to

be the
Empire.

first

good

quality

cement

since the downfall of the Roman

Smeaton is believed to be the first English engineer to have

employed pozzolana.

Perhaps the most important information to have

come out of Smeaton's experiments was his discovery

21-

that hydraulic

limes always contained

considerable

quantities of clay.

however,

was

to

that

Smeaton

unable

appreciate

or

It seems,

develop

finding, probably due to his lack of chemical knowledge.

this

Similarly

there is no evidence that John Gilbert, a contemporary of Smeaton's,

who, in association with James Brindley, was building for the Duke of
Bridgewater, appreciated the reasons why he was able to produce a good
hydraulic

lime

by

burning

Sutton

lime, which

contained

nearly

20

clay.

4.8

Bergmann
An amusing chapter (50) in the history of cement research was written
by Tobern Bergmann (1735-1784) a Swede who was Professor of Chemistry
and Mineralogy at the University of Upsala from 1777 till 1784.

In

his study of hydraulic limes he analysed a powerfully hydraulic lime,

from Lena in Sweden, which was found to contain 90S calcium carbonate,
6% clay and 43 manganese oxide.

Out of the two available choices,

Bergmann unfortunately opted for the manganese component as that being

responsible for the hydraulic properties of the lime.
a lock constructed

In consequence,

in Sweden with mortar composed of pure lime and

manganese oxide proved to be a complete failure.

4.9

The Work of Louis Vicat

The term

'hydraulic

lime' was not

used by Smeaton and his English

contempories; they used the words 'water lime' for lime which would
harden under water.
Vicat

The term 'hydraulic lime' was introduced by Louis

(1786-1861), an eminent

French engineer who spent a lifetime

researching into cement and never lost his enthusiasm for it.
importantly,

accounts

investigated

the

of his

properties

researches
of

hydraulic

are very complete.

limes and

found

inferior ones could be improved upon by adding clay.

limes in order of their hydraulicity.
of clays and

showed

how

fine, soft

Most
Vicat

that

the

He classified

He investigated the properties

clays could

be converted

into

pozzolanas upon calcination.

He had found, by 1851, that overburned

cement

of

heated

to

the

extremely hard product.

point

semi-fusion, would

set

to form

an

He analysed English Portland cement, which,

by the 1850s, was being imported into France.

-22-

4.10

The Industrial Revolution

The end of the eighteenth century and the beqinning of the nineteenth
saw considerable changes taking place in Britain and, more than ever,
good, hydraulic
with

its

reguirements

responsible
1774,

cements were required.

but

which

for

great

The

industrial

enqineerinq

revolution,

works, was

primarily

also of importance was the London Buildinq Act of

all

but

prohibited

the

use

of

external

timber

on

buildings, stipulating that ornaments to the front of buildings were

to be of brick, stone, burnt clay, artificial stone, stucco, lead or
iron.

4.11

Roman Cement
The next advance, in response to the demand for a superior, hydraulic
cement, was made in the best tradition of English discoveries, as a
result of an accidental find by a vicar.
Northfleet,

Kent

collected

some

stones

The Rev. Games Parker of

he

found

layinq

abundance at the base of cliffs on the Isle of Sheppey.

about

in

Havinq thrown

one of these stones upon the fire, it subsequently rolled out and was
found

to

be

thoroughly

calcined.

After

some

experimentation

he

developed a hydraulic cement which proved to be guick setting, stronq

and durable.
cement,

at

On 27th July 1796 Parker was qranted a patent for his

first

called

'Parkers

universally known as 'Roman cement'.

cement',

but

later

becominq

This name is rather confusinq to

us and was referred to as 'most improperly and absurdly termed' by

Pasley in 1838 (33), but probably was so called by Parker because he
fancied he had discovered the secret of the cement made by the Romans.
It is therefore somewhat ironic that the Romans constructed the walls
of the baths at Chelmsford from blocks of a very similar stone from
the Essex foreshore and bonded them toqether with a lime mortar, never
realisinq that by burninq such stones they could produce a hydraulic
cement.

The

'nodules

arqillaceous

of

clay',

limestone

as

and

Parker
were

stone, rock stones or noddles.

clay beds, havinq

been washed

result of sea erosion.

called

variously

them,

consisted

of

an

termed

septaria,

cement

They were derived from the Tertiary

out of the London clay cliffs as a

Larqe numbers were to be found at Sheppey,

23-

South

Benfleet,

Leigh,

Southend,

Shoebury,

Frinton, Walton-on-the-Naze, Dovercourt

Mersea

Island,

and Harwich.

Clacton,

By the 1840's

the cement stone reaching London came from five or six different areas
and therefore varied in composition.

Skempton (19) quotes a typical

analysis as:

Si0 2

CaO

A1 2 0 3

Fe 2 0 3

MgO

25%

543

9%

8%

2%

According to Parker's patent, the stones were first broken into small
fragments and then burnt in a kiln nearly sufficient to vitrify them.
This
(

would

result

-C2S),

strength

of

composition

which
the

as

the

would

cement.
lying

compositions.
Portland

in

be

cements

and

largely

Halstead

between

Roman

cements

formation

which,

potential belite content.

42

of

responsible

(51) gives

and

62% for

contained
competing

-dicalcium

excess
for

for

the

the

silicate
ultimate

theoretical

varying

cement

silica

C2S

stone

compared

lime, would

reduce

to
the

Because the cements contained more alumina

and iron oxide than Portland cements they set quickly in some 5 to 20
minutes.

With'

some of the higher lime containing stones, it might

have been possible to produce a Portland cement, but this was unlikely
to occur because the firing temperature would normally be too low.

If

clinkering did occur due to accidental over-burning then tri-calcium

silicate

(C3S) would

be formed, but the Roman cement

manufacturers

tried to avoid clinkering because the clinkers were more difficult to

grind and also because the cements produced would be poor if the clay
content was high.

This latter point became more relevant after 1810,

when Parker's patent lapsed, and stones from Harwich, containing more
clay than those from Sheppey were increasingly used.

Harwich became

the centre of the Roman cement industry; over a million tons of stones
were removed from the foreshore between 1812 and 1845 and, after a law
was

passed

prohibiting

stone

removal

from

within

50

feet

of

the

cliff8, it was for some years dredged from the sea.

Roman cement was often made up from a mixture of stones according to

the price of the product;
those

from

Harwich.

Sheppey

Other

stones were more expensive

natural

-24-

cements

were

than

'Atkinson's',

'Mulqrave', 'Whitby', 'Yorkshire', all of which came from stones from

the Upper Lias strata near Whitby and good quality

'Medina' cement,

which came from the Solent.

4.11.1

Uses of Roman Cement - The Thames Tunnel

The main uses of Roman cement were as mortar for brickwork and
stucco on the wall of houses.

It was, however,

put to a

major use by Marc Isambard Brunei in his construction of the

Thames Tunnel, for which he was knighted.

Begun in 1825 the

tunnel, between Rotherhithe and Wapping - a distance of some

1,200 ft, was the world's first under a navigable river.

It

was Brunei's intention to build the tunnel out of brick and he

carried

out many

experiments

to find a suitable mortar, a

prime reguirement being speed of setting to minimise leakage.

He found

that only

Roman cement

could do the job.

During

construction the contents of each cask of cement were tested

before use.
lapse

The tunnel was finally completed in 1842, with a

of some seven

recognised

as

one

years
of

due to money

the

greatest

problems.

achievements

It was
of

the

nineteenth century and represented the first use of cement on

a large scale in modern times.

4.12

The Search

for Artificial, Hydraulic

Cements and the Invention of

Portland Cement
Stimulated by the success of Roman cement and Vicat's synthesis of a
hydraulic lime in 1818, attempts were made to synthesise an artificial
Roman cement.

James Frost, who consulted Vicat, was successful in

manufacturing a patent cement in 1822, as was Edgar Dobbs in 1811.

4.12.1

Joseph Aspdin
It is said

(47) that in 1813 Joseph Aspdin, a young Leeds

bricklayer,

purchased

Smeaton's

book

'A Narrative

of The

Eddystone Lighthouse' containing an account of his researches.

Aspdin's efforts to synthesise an artificial, hydraulic cement
culminated with the granting of patent No.

5022, on the 21st

October

called

1824, for

material

-25

which

he

'Portland

cement'.

Aspdin called his product thus because he fancied it

resembled Portland stone in colour and doubtless also because

he wanted it to be associated with a natural material renowned
for its looks and durability.
There

has

been

much

debate

as

to

whether

Joseph

Aspdin

invented Portland cement as we know it or merely devised the

name of a primitive, hydraulic
refined

and

developed

lime which

by others.

was

Halstead

subsequently

(51) considered

this and listed the requirements for a material to be regarded

as a Portland cement as:

1.

It must largely be composed of calcium silicates, with

little free lime; this requires a lime-silica ratio of
about

2.

3:1.

The temperature

at which

the raw materials are burnt

must be sufficient to allow the lime and silica to react

nearly to completeness.

A minimum temperature for this

would be 1300C.
3.

After burning the product is ground and kept dry; water

is not added to slake it.

Halstead concluded that there was insufficient evidence either

from

knowledge

specimens

of

of

Aspdin's

Aspdin

manufacturing

cement,

which

were

process

or

from

unknown

to

him.

Blezard (42), however, has since examined a specimen of mortar

attributed

to

Joseph

cement', finding
evidence

of

material

has

Aspdin

and

termed

it

some silica-rich calcium

higher-temperature

calcium

been, nevertheless, the

'proto-Portland

silicates, but no
silicates.

only

sample

This

of early

Joseph Aspdin cement so far located and examined.

Certainly,

in Joseph Aspdin's patent

feature of

of 1824 the essential

raising the kiln temperature high enough to produce clinkering

is not

mentioned.

mixture

into suitable

similar

to a lime kiln

expelled'.
greater

Rather

Aspdin's

he says that

lumps

calcine

till the carbonic

words

than 900C, but what

we do not know.

and

certainly

'I break
them

in a furnace

acid

imply

the said

final temperature

is entirely
temperature
was reached

Joseph Aspdin's first cement works was at

26-

Kirkgate in Wakefield, from whence Blezard's sample is thought

to have originated.

He was forced to move in 1838 when his

works were demolished to make way for the Manchester and Leeds
Railway, establishing new works not far away.

In 1841 he took

his son James into partnership; Joseph retired in 1844 and in

1848 James Aspdin moved the works to Ings road, not very far
away.

In 1877 Reid (55), in his book 'The Science And Art of

The Manufacture of Portland Cement', mentions an Aspdin kiln,

presumably

one at the Ings Road site, although this is not

specified.

He comments that 'during the last ten years but

little effort has been exerted in the direction of the kiln.

The original pattern first introduced by Aspdin still prevails
in

all

its

variety

of

form

and

modifications, yet

it

is

curious that none of those imitations reach the excellence of

the one at the parent cement manufactory at Wakefield.

The

chimney or dome of that kiln is of unusual height, and much

resembles a glass furnace in appearance.
while

affording

cement

'

excellent

This extreme height

facilities

for

burning

the

By 1877 the necessity of clinkering certainly

was understood and is specifically mentioned by Reid as the

most important kiln operation so that, from his comments, it
seems reasonable to assume that clinker had been produced at
Joseph Aspdin & Son's works for some time.
also notes that the manufacturing

In his book Reid

process at Wakefield

was

still surrounded with an 'air of ignorant exclusiveness' and

that Aspdin had stressed to him the importance and necessity
of obtaining a high kiln temperature.

Francis (48) entirely discounts the above argument, implying

that Reid's writings had misled other writers to believe that
the Aspdins had made the essential developments in Portland
cement in the twenty years after 1824.

He argues that Reid

had been deluded on his visit to Wakefield in the 1870's into

believing
cement

that

works

he
and

had

seen

that,

in

certainly erected post- 1848.

27

Joseph
reality,

Aspdin's
Reid

original

had

seen

1825
plant

4.12.2

Portland Cement and The Thames Tunnel

Further

controversy

also

surrounds what

first major use of Portland cement.

may

have

been

the

Joseph Aspdin's younger

son, William, claimed in 1848, 1849 and again in 1854 that his
father's cement had been used to fill a breach

in Brunei's

Thames Tunnel in 1828, when it was still

incomplete.

would

cement

be only

three years after Portland

began in Wakefield.

This

production

Two major breaches certainly occurred in

1827 and 1828, with minor ones in 1836 and 1837.

Some three

hundred suggestions on how to repair the breach were received

by Brunei, none of which
cement.

Francis

engineer's

(48)

reports,

mentioned

examined

which

using Aspdin's Portland

Brunei's

quite

clearly

diaries
state

and

the

that

the

breaches were efficaciously filled with clay bags and gravel.

Furthermore,

no

mention

was

ever

made

by

Joseph

or

James

Aspdin of the use of their cement for such an important work,

something they might fully have been expected to do since the
Thames

Tunnel

was

such

story .seems therefore

remarkable

that

the

famous engineering

not

to

claims

have
of

been

project.

true,

William

yet

Aspdin

The
it

were

is
not

challenged, especially when he went into detail in a pamphlet

of 1854, saying that, after testing, Brunei was convinced of
the 'great superiority' of Aspdin's cement over Roman cement,
finding it three times stronger than any other known cement
and purchasing it even though it was about twice as expensive
as Roman cement.

4.12.3

William Aspdin
William Aspdin (1815-1864) left his father Joseph's employ in
1841

and

before

Rotherhithe
entered

on

long
the

was making

south

into partnership

bank
with

patent

Portland

of the Thames.
J.M.

Maude.

cement at
In 1843 he

This period

in

history is significant because it may be that at this time a

true

Portland

cement

was manufactured

for

the

first

time.

Tests on Maude and Aspdin's cement, carried out in October

1843 by the highly reputable firm of Grissel and Peto, showed
that

it was some 1.8

times stronger

28

than

the best

guality

Roman cement; the tests are considered in detail by Skempton

(19).

In order to achieve this strength Aspdin must have been

including clinkered material in his cement.

Such 'overburnt'

material had normally been discarded, being difficult to grind

and

considered

useless; whether

Aspdin, with his limited

knowledge of chemistry, had discovered the value of clinkering

by accident or design is not known.
Aspdin

was

very

The problem is that

secretive; apparently

his

works

were

surrounded by walls twenty feet high, with only one way in.
To deceive others he shrouded the whole operation in mystery,
even going to the extent of personally scattering unknown
powders in the kiln.
Had the Aspdins not been so reluctant to divulge details of
their operation, William, or his father, since William never
claimed to have radically altered his father's specification,
might well have been credited by all with the invention of
true Portland cement.
4.12.4

Isaac Johnson
The man who claimed

himself to be the inventor

of true

Portland cement, and has been given this accreditation by

some, was Isaac Charles Johnson (1811-1911).

Johnson studied

chemistry and physics in his spare time and in 1843 was works
manager to J.B. White and Sons, makers of Roman and Frost's
cement at Swanscombe, Kent.

The results of the tests in 1843

on William Aspdin's cement had created quite a stir because of

the obvious superiority of the new cement. White's approached
Maude and Aspdin in an attempt to come to an agreement to
allow White's to manufacture the cement but, not surprisingly,
no arrangement could be agreed.

Johnson then convinced his

employers that he could discover how to make the cement.

He

obtained a sample of Aspdin's cement and sent the sample for

chemical

analysis

well-known chemist.
furnished

to Dr. Andrew

Ure, M.D., F.R.S., a

Incredibly, the analysis subsequently

to Johnson was incorrect, showing the sample to

contain 45% phosphate of lime.

Thinking, therefore, that the

main ingredient was bone ash Johnson made up mixtures of bone

-29-

ash, chalk and clay, but the products proved to be useless.

Undeterred, he analysed Isle of Sheppey and Harwich cement
stones and proceeded to experiment with mixtures of chalk and
clay.
By accident he overburned some material and it
clinkered. Thinking, following what he had heard Pasley say,
that the material would be useless, he nevertheless powdered
it and added water to this alongside some lightly-burned
material. The latter set and hardened quickly, but the former
did not seem as though it would harden and, furthermore,
produced no heat. Heat generation was considered by Pasley to
be essential in an artificial cement. On examination of his
powdered clinker mixture several day later, however, he found
that it had set much harder than the lightly-burned mix and,
furthermore, the colour was a pleasing grey. After further
experimentation the mixture found to give the best results
consisted of five parts of chalk and two parts of Medway clay
and on this basis White's went into production, eventually
advertising their product as 'Portland cement of best
quality'.
Skempton (19) considered the fact that White's
adopted the name Portland cement for their new cement to be
decisive in confirming that the Aspdins, and not Johnson, had
invented Portland cement.
This was a time when patent
cements, with their different names, proliferated and Portland
cement certainly had not yet gained an unassailable reputation
in its field. As Skempton convincingly argues, if Johnson had
genuinely invented a brand new cement the one name he would
certainly not have used for it would be Portland, which was by
this time irrevocably associated with Joseph and James Aspdin
in Wakefield and William Aspdin in Rotherhithe.
4.12.5

Chemical Composition of Early Portland Cements

Skempton reports that the mixture
White's in 1845 contained about
expected to make a cement with
compositional analysis of White's
given as:
Si0 2
225!

CaO
59%

A1 2 0 3
6%

30

of raw materials adopted by

26% clay, which would be
ca. 5Q% CaO.
An average
cement for 1849 to 1852 is

Fe 2 03
5%

MgO
1%

By about 1862, when about a dozen firms were manufacturing

Portland cement in Britain, a typical analysis is given as:
SiO-2
23a

CaO
60S

A1 2 0 3
1%

Fe 2 0 3
4

MgO
1%

and might be expected to contain ca. 55% belite and 10%

alite.
4.12.6

The First Major Use of Portland Cement

A major success for White's and the first (accurately
documented) use of Portland cement on a large scale was in the
construction of the main breakwater of Cherbourg harbour.
Engineers with the Administration of the Ponts et Chausses in
France tested White's cement, along with others, in 1847. The
engineers selected White's cement along with Medina cement,
the latter being a Roman cement.
The Medina cement was
considered to be too fast in setting and the Portland cement
too slow, therefore a mixture was used; in each concrete block
occupying 20m^, 4 tons of Portland cement and l tons of
Medina cement were used, about 2000 blocks being made between
1848 and 1853.
Thus several thousand tons of White's Portland cement were
exported to France and the success of the Cherbourg breakwater
opened the doors for numerous other maritime contracts for
White's in France. By 1850 Portland cement still had not been
used on any large scale in Britain; its three principal uses
were as mortar for brickwork, as blocks of moulded concrete
for maritime constructions and as an external stucco.

4.12.7 Portland Hall

For someone whose name was surrounded with success in the
manufacture of Portland cement, William Aspdin had a cheguered
career.
His works moved to Northfleet in 1846, under a
different partnership which was declared bankrupt in 1847. A
fresh partnership, Robins Aspdin & Co., began trading in 1848.

-31-

Tests carried out in 1848 indicate that, on average, Robins

and Aspdin's

cement was stronger

than White's but was more

variable; White's was preferred for engineering works.

In

1850

William

Aspdin

conceived

an

ambitious

advertise the uses of Portland cement.

project

to

Portland Hall was to

be a large mansion, completely faced in Portland cement stucco

and

with

extensive

ornaments.

grounds

containing

The Hall was

concrete

to be built

near

statues and

Gravesend,

yet

Aspdin was already short of money and with outstanding debts.

Work began in 1850, but by 1852 costs had risen to 40,000 or
the eguivalent of 2 million today (47).

The outer structure

was complete but the interior unfinished when work stopped;

the money had run out, despite Aspdin's desperate efforts to
find funds by one way or another.

The Hall was put up for

sale and later by auction but no buyer came forward and the
house

lay

empty

for

five

years

before,

by

order

of

the

bankruptcy court, it was mostly pulled down, except for part

which

was

converted

into

private

house.

Now

all

that

remains is part of the boundary wall, the subject of recent

research (44, 45, 46 and this work).

4.12.8

William Aspdin's Later Years

William

Aspdin

left

Northfleet

in

1852

and,

in

another

partnership, began manufacturing cement in Gateshead, close to

the river Tyne, building one of the largest cement works in
the world at the time.

According to Francis (48), Aspdin's

claims from 1848 onwards became more and more unbelievable.

In 1853-4 he produced
appears

to be

a pamphlet

'largely

in which

fictitious'

(48).

the

information

His claim

about

Portland cement being use to repair Brunei's Thames Tunnel has

already

been

mentioned.

Aspdin

also

maintained

that

Sir

Robert Peel, the Prime Minister, had at one time become so

concerned

that

the manufacture

of Roman cement

was

leading

rapidly to the exhaustion of cement stone on the Sheppey and

Harwich coasts that he was considering imposing a tax on its
use.

Hearing of this matter, Aspdin made representations to

the Prime Minister, assuring him that Portland cement was a

32-

vastly

superior

product

manufactured, whereupon
tax.

and

was

the P.M.

being

dropped

extensively

his plans for the

In consequence of havinq qained Sir Robert's approval,

many firms beqan to imitate the manufacture of Portland cement

but only produced 'a spurious and worthless article'.

Francis

(48) maintains that this claim has no foundation in fact and

he notes that neither Brunei nor Peel were alive when

the

pamphlet was published.

It

was

not

lonq

before

Aspdin's

company

in Gateshead

bankrupt, the court proceedings continuing into 1857.

Johnson
again

took
in

over

October

the abandoned
1856.

works, production

Aspdin

partnership manufacturinq

briefly

set

was

Isaac

starting

up

another

cement in Newcastle, but it seems

that his creditors were fast catchinq up with him and, under
advice,

he

emiqrated

to

Germany

in

1857, where

he

began

manufacturing cement again, eventually founding an important

works at Lagerdorf.

He died in 1864, at the early age of 48,

as a result of a fall in the street but the monuments to the

energy, perseverance and inventiveness of this great man stand
around us everywhere today.

4.12.9

Developments in Germany
Developments

in

cement

technology

continued

latter half of the nineteenth century.

washing

and

mixing

process

through

of

the

improved

process were to be made.

raw

kiln

in

the

Improvements in the

materials,
design

apace

and

in
in

the
the

burning
grinding

A lot of this improvement took place

in Germany, where production first began at Stettin in 1855.

In

1871

Rudolf

Dyckerhoff,

who

had

studied

chemistry

at

University, introduced a system of chemical analysis which led

to a very much decreased variation in the final product.

Of

nine different German cements made in 1876, their CaO content

varied only from 59 to 62%; modern cement would be expected to
exhibit
increased

similar

scatter

(19).

Kiln

temperatures

were

to ca. 1400 C and were more uniform as a result

of improved kiln design and management.

33

Accordingly
higher

the

lime

content

proportion

of

could

calcium

be increased

silicates,

so that a

particularly

tricalcium silicate, would be achieved and hence the strengths

of

cements

improved.

Skempton

(19) states that, by 1880,

German cements probably contained about 2585 C3S and 4585 C2S.
This could not be significantly improved upon until the advent
of rotary kilns.

By 1965, typical C3S and C2S contents were

458! and 258! respectively and by 1980 the mean C3S content of
ordinary Portland cement was 538! (30).

4.12.10 Grinding of Cement

Improvements

in

grinding

technigues

were

brought

about

in

response to the harder clinkers being produced as CaO contents

increased

and

also

because

of

the

realisation

that

large

cement particles possessed little cementive value (26), since

the hydration of cement is essentially a surface reaction.

By

1875 the leading producers' cement contained not more than 1585
which was retained on a sieve with 900 meshes per cm^, this
was cut to 885 by 1880 and 3 to 4% by 1887 (19).

4.12.11 The Development of Rotary Kilns

The high price of Portland cement - about ten times the cost
today

(47) - delayed progress in its use; it would only be

reduced

by

cutting

burning

process

fuel

was

and

labour

necessary.

In

costs.
1877

continuous

Thomas

Crampton

patented two rotary kiln systems for cement burning, but made
it clear that he expected others to develop it.

This did not

immediately come about since good profits were being made in

the cement industry at that time.

Frederick Ransome took up

the challenge and patented his own rotary kiln in May 1885.
All the early experiments proved failures.
also

turned his attention

Frederick Stokes

to this matter, but again trials

were relatively unsuccessful, although many developments were

made.

It was the Americans who were to make a success of this

British idea, they had even more of an incentive since high

labour

costs

in

the

U.S.A.

relatively unprofitable.

made

static

kiln

operations

A major advantage was the ability to

34-

use oil as a fuel, too expensive in Britain, which provided a

much better means of kiln temperature control.

Powdered coal

was also sucessfully developed for use as a fuel.

and H.J.

Seaman had by 1898 developed

E.H. Hurry

the first, fully

operational, rotary kiln process which soon reached Britain

and, within a few years, nearly all the cement works in this
country operated one or more rotary kilns.
4.13

Reinforced Concrete
A very detailed description of the birth of reinforced concrete and
its early development is given in a Ph.D. thesis by Cusack, entitled
'Reinforced

Concrete

in Britain

development

of Portland

1897-1908'

cement, that

of

(56).

reinforced

As with the
concrete

is

dominated by the personalities of men of inventiveness, foresight and

dynamism.
Francois

Such people were William Boutland Wilkinson (1819-1902),

Hennebique

(1842-1921)

and

Louis

Gustave

Mouchel

(1852-1908).
4.13.1

The Use of Mass Concrete

Parallel with the. growth of reinforced concrete, but soon to
die out, was the use of mass concrete, sometimes strengthened,
for the entire construction of buildings. Cusack (56) cites a
reference to a house, built in 1817 near Gloucester out of
lime concrete, which may represent the first modern use of
concrete
buildings

for house building.

were

erected

in

Most of these all-concrete

the 1869's

and 70's, several

examples are guoted by Stanley (47).

4.13.2 Use of the Words 'Reinforced Concrete'
The term 'reinforced concrete' did not fall into use until the
early 1900's when it was adopted by journals such as Concrete
and Constructional Engineering as a deliberate attempt to take
away

attention

from

the specialist

systems

construction of reinforced concrete buildings.

used

in the

In particular

the description was employed to discourage usage of the words

-35

'ferro-concrete', introduced by L.G.

Mouchel to describe the

Hennebique system, using which the majority of Britain's early

reinforced concrete structures were built.
4.13.3

W.B. Wilkinson

The man generally credited with the invention of reinforced

concrete is W.B.

Wilkinson.

Since 1841 Wilkinson had been in

business in Newcastle as a manufacturer of artificial paving

stones and as a plasterer.
was

also

one

successful,

of William

reinforced

It can be no coincidence that he

Aspdin's customers

concrete

requires

because, to be

the

use

of

quality, consistent cement and Wilkinson knew this.

Wilkinson obtained patent No.
construction

of

fire-proof

incorporating

dwellings,

warehouses

or

and

other

A network of flat iron rods

ropes was to be embedded

'Portland

In 1854

2293 for 'improvements in the

buildings, or parts of the same'.

or secondhand wire

good

other

cement

in a concrete

of equal

quality'.

Francis (48) believed that Wilkinson may have been the first
to have specified

the use of Portland cement for structural

building but Cusack (56) refutes this.

Although there were a

number of patents in the nineteenth century combining metal

with

concrete

both

they were not

pre- and

post-dating

patent

'in accordance with the principles of modern

reinforced concrete' (48) in which

efficiently

Wilkinson's

arranged

to

'concrete and metal were

assume

complementary

structural

functions' (56). Although Francis (48) thought that Wilkinson

may

have

Brunei,

been
both

influenced
of

whom

in his

ideas by Pasley

reinforced

brick

beams,

and M.I.

Cusack

(56)

thought it more likely that economy was the principal driving

force, as was claimed in Wilkinson's advertisements for his
fireproof floors.

Wilkinson concentrated

the majority

of his business life on

the production of paving stones and apparently did little to

develop his patent, which was unnoticed by the building world
for some thirty years.

But by the time Wilkinson died in 1902

his company had constructed several all-concrete houses, some

of

them

of

reinforced

concrete.

-36

Unfortunately,

fire

destroyed the company records relating to the I860's and 70's

and, as far as we know, the earliest example of Wilkinson's
reinforced concrete was a small cottage, built about 1865,
near Ellison Place, Newcastle.

The two-storey cottage was

reported to be in excellent condition when demolished in 1954

(57).
4.13.4 Other Early Workers
Other workers in Britain and France were developing ideas in
reinforcing concrete.

Scott in 1867 patented a fireproof

floor in which the concrete was said to take compressive, and

the iron, tensile stresses.

Francois Coignet and Joseph

Monier worked upon systems in France. Alexander Payne in 1876

pointed

out to the Royal Institute of British Architects

(RIBA) that iron embedded in concrete could give it tensile

strength.

Thaddeus Hyatt in 1876-7 compared experimentally

the thermal expansions of iron and Portland cement and found

that they were practically identical; it will be remembered
that

the

thermal

expansion

mismatch

between

bronze

and

concrete had been responsible for the failure of reinforcement

attempts in Roman times.

E.L.

Ransome was working upon

reinforced concrete in the U.S.A.

4.13.5

F. Hennebigue
After

Wilkinson's

patent

there

were

no

significant

improvements in reinforced concrete until the introduction of

shear reinforcement in beams, which was patented, in Britain,
in 1892 by F.

Hennebigue. Hennebigue, born in Arras near the

Belgian border, was fifty years old when he first patented his
reinforced concrete, which was to have a major impact on
reinforced concrete construction in Britain.
Hennebigue had been using reinforcement in concrete floors
since 1879. The complete specification for his British patent
was filed in May 1893, in which he claimed the principle of
combining

iron and cement

such that

'the resistance iron

offers to tension is added to that the cement offers to

37

compression'

and the use of anchors or suspension stirrups

not only to support the bar but also to counteract shearing

action in bending; it was this latter specification which was
the important

innovation.

Amazingly, at this point

in the

nineteenth century, Hennebique mentioned that hydraulic lime

concrete could be used as an alternative to Portland cement
concrete

in

his

reinforced

beams;

it

was, however,

never

employed as such in Britain.

4.13.6

Weaver's Mill

The

first

mentioned

use

by

Hennebique

of

his

reinforced

concrete was in a floor, but his first, entirely reinforced

concrete

framed

building

was

erected at Tourcoing in 1895.

was

project

number

2615

on

four-storey

woollen

mill

Weaver's Mill, Swansea(1897-8)

Hennebique's

books

and

was a

landmark in the history of concrete in Britain because it was

the first, entirely reinforced concrete framed, multi-storey
building

to be erected in this country.

Hennebique offered

only 4150 as the price for the building, but it seems that
this may have been a ploy by Hennebique to enable him to get a
foothold

in Britain,

since

a similar

sized

contract

for a

neighbouring granary was built for 15478 not long afterwards.

The contract

for the mill was signed on 20th October 1879.

The design incorporated a new feature, bent or cranked up rods

in beams, the mill being one of the first buildings to be thus
reinforced.

Hennebique was naturally concerned to ensure that

his first major venture in Britain was a success and it is

reported

(56)

construction

of

that

he

Weaver's

took

particular

Mill;

he

was

care

probably

over

the

personally

involved in the working drawings, trained foremen were brought

from France and all the materials, cement, sand, aggregate and
steel are said

to have been brought over from Nantes.

At

least in the case of the aggregate, the French connection has

been

doubted

(58),

but

it

would

certainly

practically and economically feasible to transport

have

been

materials

from France as there was a considerable coal trade between

South Wales and Nantes, so that ships returning to Swansea
could carry the concrete materials as ballast to fill their

38

holds.

The final loadinq tests were carried out on the 1st

August 1898 and the building subsequently handed over for a

final price of 4430.

Despite the fact that a new page had

just been written in the history of construction in Britain,

Weaver's

Mill

architectural

was

ignored

journals;

this

by

British

situation

was

building

and

to continue

as

other reinforced concrete buildings were put up.

4.13.7

L.G. Mouchel
It was at about the time of the preparations for Weaver's Mill
that

Hennebigue

became

associated

with

L.G.

Mouchel, an

enterprising businessman, living in South Wales, who was also

Vice-Consul

in

Wales

for

the French

Government.

Mouchel

became closely involved with Weaver's Mill and, although at

first reluctant, became Hennebique's agent in Britain.

This

was a fortuitous move, because in Mouchel Hennebique had found

the most enthusiastic

and able proponent

of his reinforced

concrete system that he could have wished for.

flair

and

influential

friends

contracts, he was said

magnetic

brought

to possess great

many

Hennebigue's

system

and

the

important

personal charm, a

influence, and was of tireless enerqy

'indomitable perseverance' was noteworthy

promote

in

His business

(56).

His

in his efforts to

journal

Concrete

and

Constructional Engineering in 1908 mentioned his 'ability to

inspire confidence, extraordinary energy, industry, and pains
in matters of detail, organisational skill and singularity of
purpose' (56,59).
days

of

This was just as well, because in the early

reinforced

concrete

the

majority

of

architects,

engineers and builders were both ignorant and sceptical of the

material.

4.13.8

'Ferro-Concrete' Building
Mouchel

established

in Britain

an

organisation

similar

to

Hennebique's own, consisting of regional technical or planning

offices

and

Hennebique

contractors
system.

which
He

were

himself

licensed

to

introduced

use
the

the
term

ferro-concrete to describe the system and advertised it as:

-39-

'Ferro-Concrete:

Indestructible and Absolutely Fireproof.'

Mouchel

obtained

himself

concrete

and

applied

several
them

in

patents
his

in

reinforced

buildings.

In

contradistinction to Hennebique he exclusively specified the

use of good

Portland

cement.

Although specially trained

French workers had assisted in the building of Weaver's Mill,

Mouchel believed that no skill and mental effort were required
in the use of Hennebique's system - or the Mouchel-Hennebique
system, as it came to be called - and that workmen of average
intelligence could be trained in a few days.

Nevertheless the

record was good; unlike other countries, where fatal accidents

occurred, the first serious failure did not occur until 1914
when, in Bradford, a completed, six-storey Hennebique building
collapsed, of an unknown cause. The Mouchel-Hennebique system
proved to be of increasing popularity:

between 1897-9 seven

Hennebique framed buildings were commissioned, in 1908 alone

forty were on order, between 1897-1908 over 130 reinforced
concrete framed buildings were constructed
such landmarks as the Royal Liver
other

structures were

also

(56), including

Building, Liverpool. Many

built on Hennebique's system;

Stanley (47) estimates that by 1910 over 40,000 structures of

various kinds had been completed.
4.13.9

Other Reinforced Concrete Systems

There were systems other than Hennebique's in the early days
of reinforced concrete, though none were applied to anything
like the same extent.

Another French system was that of E.

Coignet and warehouses erected in 1905 at Rainham, Essex may

have been the earliest reinforced concrete framed buildings in
Britain on a system other than Hennebique's (56). Mouchel had
long

legal

battles

with

infringement of patents.

Coignet

representatives

over

Yet another system from France was

that of Considere, but not in use until 1908. From the U.S.A.
came the Kahn system, in about 1904.
4.13.10 The Durability of Reinforced Concrete
The

journal

'Ferro-Concrete'

Hennebique's system would

-40-

claimed,

in

1911,

that

'endure for thousands of years;1

nevertheless

others

did

express

doubts

regarding

the

durability of reinforced concrete. William Dunn in 1909 noted

that the use of reinforced concrete had been restricted in.the
U.K. because of fears about the durability
concrete

and

corrosion

of

the

steel

of reinforced

(60).

The journal

Concrete and Constructional Engineering noted in 1908 (61)

that there was a lack of data on reinforced concrete and that
the

cause

of

laboratory.

this was
Further

the

lack

of an

experiments

to

official

those

of

testing

Hyatt

by

Durand-Claye in 1902 (63) confirmed the similar coefficients

of expansion of iron and concrete and also demonstrated that
steel embedded in concrete did not oxidise.

Along with the

requirements that the concrete and metal adhere sufficiently,

these

were

concrete
4.13.11 The First

the

three

essential conditions

for reinforced

which became widely accepted in the early 1900's.

British

Standard

for

Portland

Cement and Fake

Portland Cements
It was necessary of course, to ensure that the cement and
concrete were of adequate quality.

Mouchel specified only the

use of Portland cement and a maximum aggregate size of ? inch

(ca. 19mm).

Aggregate

grading

is reported

to have been

somewhat of a haphazard process at the turn of the century,

there being one

instance of a supplier advising a purchaser

that lumps in the aggregate should be broken up with a hammer

when received (56). Another problem was the varying quality
of Portland cement; Thomas Potter wrote in 1907 that this had
been the primary cause of concrete failures (65). In response
to the need for a constantly reliable product a sub-committee
of

the

Enqineering

Standards

Committee,

comprising

representatives of the cement industry and other interested

parties, drew up the first British Standard Specification for
Portland

Cement, British

issued in December 1904.

Standard

Specification

No.

12,

The Standard was recommended by the

RIBA in 1907 for reinforced concrete (66).

The problem did

not end there, however, because the unscrupulous dealers in

fake Portland cement recognised no Standards. Natural cements
were being imported from Belgium and sold with misleading

41

names or were deliberately misrepresented as Portland cement,

for instance by marking with
Company's initials.
natural

cement

concrete.

to

the Associated Portland Cement

Ignorance of cement enabled some of the

be

Journals

sold
such

in

good

as

faith

Concrete

for

and

reinforced

Constructional

Engineering carried warnings; the trade was still a problem in

1914.
4.13.12 Water to Cement Ratio
Even with

good

quality

cement, bad concrete could still be

made because of the general ignorance among users and experts

of the effects of the amount of water used.
1918

that

showed

Duff

that

affected

Andrew

Abrams

variation

in

published

water

his

content

the resulting strength

It was not until

of

results

which

a concrete

mix

far more than variations in

other parameters, and recommended using the smallest amount of

water

possible. (67).

Before this time opinions were very

much divided on whether a wet mix or a dry mix was better.

One practical difficulty was the lack of a means of mechanical
vibration,
compact.
had

which

that

It is reported

preferred

fairly wet
Arme'

meant

a very

mixes

could

dry

it

using

seems

be

hard

to

(56,68) that until 1904 Hennebique

mix, but

after

mixture; indeed, his in-house

advocated

Generally,

dry

an

that

'excess

in

of

the early

this time used a

journal

'Le Beton

water'

in

years of

1902.

reinforced

concrete dry mixes were preferred, but later wet and sloppy
mixes were used.
need

to

obviate

This related principally to the recognised

voids

in

the

concrete, but

some

actually

believed that wet mixes were stronger and denser.

however,

Tanner

(69) showed

that

the

largest

In 1909,

increases

in

strength after six and eighteen months occurred in dry mixes

and

later,

confirmed

in 1912, a committee
that

the

strength

of

of the Concrete
concrete

Institute

increased

as

the

amount of water decreased (70).

4.14

The Development of Cement Chemistry

During the days of the development of hydraulic limes, Roman cement

and Portland cement, there was a great lack of understanding of the
-42-

cementation
cement.

process

and

knowledge

of

the chemical

constituents

There was a dearth of scientific, experimental work.

sufficient

knowledge

and

understanding

development

was

of

Without
naturally

limited and important discoveries tended to be made by accident.

Before 1800 there was little progress because of the lack of chemical
knowledge on the part of the experimenters.
which

determined

that

the

presence

of

Smeaton's experiments,

clay

in

limestone

was

essential for it to form an hydraulic lime, were largely ignored by

chemists.
first
step

The comprehensive work of Louis Vicat, who accomplished the

synthesis
forward;

of

he

an

hydraulic

determined

important constituent.

lime

that

the

in

1818,

silica

in

was

an

important

the

clay

was

the

It was in 1856 that Winkler (71) put forward,

for the first time, the modern view that basic silicates are formed in
the cement

making

process and

that, on reaction with water, these

silicates are hydrolysed, forming silicate hydrates and lime.

4.14.1

The Portland Cement Minerals

The identification

of the minerals that constitute Portland

cement was carried out by the French chemist Henri Louis Le

Chatelier, from 1883 onwards (72, 73), and the Swede Alfred
Tornebohm,

working

Chatelier

used

petrography

and

independently,

the

in

mineralogist's

examined

thin

1897

technique

sections

clinker in the optical microscope.

(74,

of

75).
of

Le

optical

Portland

cement

He observed four distinct

kinds of crystals and was able to synthesise these from lime,

silica and alumina.

He also studied the hydration of cement

under the microscope and observed the crystal growth of the

hydrated compounds formed.

Tornebohm repeated Le Chatelier's

experiments and observed the same four distinct constituents,

which he named
observed

alite, belite, celite and

colourless,

between alite grains.

precisely

material

filling

He also
in

space

There followed much debate as to what

the chemical constituents of these minerals were.

Le Chatelier
silicate

glassy

felite.

believed

that alite was essentially

tricalcium

(C3S), and that it was responsible chiefly for the

cementing power of Portland cement, but this was disputed by

others, who believed alite to be a solid solution of calcium

43

silicates and aluminates.

It was not until about 1930 (1)

that it was confirmed, by synthetic, optical and X-ray work,

that alite was C3S, but was usually impure as other oxides are
taken into solid solution.

Belite and felite were found to be

dicalcium silicate (C2S), usually the

(76).

/3 polymorph

Celite turned out to be the interstitial ferrite phase,

a CgAF

- C5AF2

solid

solution, and

the isotropic, glassy

material the aluminate phases tricalcium aluminate (C3A) and

C12A7.

Since the advent of cement chemistry there has been a great

proliferation

of

research

important material.

into

what

is

probably

our

most

Surprisingly little is known, and there

is much argument, about the hydration process and the picture

seems

to

get

more

techniques become.
can

be

said

that

complex

the more

advanced

investigative

Much more research is necessary before it

we

fully

materials.

44

understand

one

of man's

oldest

5.

ANALYTICAL STUDIES OF ANCIENT CEMENT-BASED MATERIALS

Publications describing the results of analytical work on ancient cements,
concretes, mortars and plasters are relatively few and it is only in recent
years that interest in the subject has revived owinq to the proposed use of
concrete as a barrier in the disposal of nuclear waste.
5.1

L.J. Vicat (1837)

Vicat (2) in his work entitled 'A Practical and Scientific Treatise on
Calcareous

Cements,

Artificial

and

Natural',

published

in

1837,

includes observations, including strength measurements, of samples of

various

Roman

mortars

taken

form

the

South

of

France.

He

also

comments that, in his day, it was commonly believed that the Romans
possessed a secret in the fabrication of their mortars, either due to
the choice of materials or their method of application.
that,

if

this

were

true, then

Roman

mortars

Vicat argued

everywhere

would

be

equally hard but was able to show, from the results of his researches,
that this was not the case and guotes Vitruvius (3) as saying that, at
least

in

the

case

of

materials, use

should

be

made

of

whatever

materials were available, even if they left something to be desired.

It

is most

interesting

to note

that, in Vicat's day, people were

concerned at 'the deplorable condition of most of our buildings' and

that most believed that Roman constructions were superior to modern
ones.

Vicat points out, however, that, in comparing buildings, we

should

compare like with like and Roman grand monuments should

compared with modern

constructions.
ruins

was

be

grand monuments and not with lesser, ordinary

He cites Pliny as saying that the main cause of city

inadeguate

cement; surely

this observation

remains

true

today.

5.2

W. Wallace (1865)
Wallace

(2) in 1865 examined

chemically mortars

from 1600 to 3000

years old, comprising Ancient Eqyptian from the Great Pyramid, Ancient
Phoenician from Cyprus, Ancient Greek and Ancient Roman mortars.

Two

samples from the Pyramid of Cheops proved to be mostly gypsum, with

some

calcium

carbonate

samples were studied.

and

silica

also

present.

Two

Phoenician

One, from a temple near Larnaca, was supposed

at the time to be the most ancient mortar in existence and proved to

-45-

be

'exceedingly

lime, sharp

hard and firm', being made from a mixture of burnt

sand

and

gravel.

amount of soluble silica.

This sample

also contained

a small

The other sample was a lime cement joining

underground water pipes and, most interestingly, proved to be coated

with

bitumen.

Both samples were completely

carbonated.

Both

Ancient Greek samples analysed were fully carbonated lime mortars.

was noticed, however, that the mortar

the
It

that had been exposed to the

weather was harder than that taken from a temple situated in a cave.
All four Roman samples examined were pozzolanic limes, were hard and
contained

significant

amounts

of

combined

silica.

Wallace's

conclusions were that, contrary to the opinions of others, free lime

in mortars and plasters eventually became fully carbonated; that, in
cases where the mortar was exposed

to the elements, silicates were

formed, making the mortars harder and that, in underground structures

the

hardening

effect

was

greater.

He

postulated

that

calcium

silicate, formed upon exposure to moisture, increased the binding to

the aggregate.

5.3

N. Davey (1947)
This century, Davey (5, 6) examined petrographically Roman mortars and
concretes excavated

from a villa

at Park

Street, near St. Albans.

After determining the mix proportions, Davey then went on to simulate

Roman concrete made with crushed tile as a pozzolana.

The mortar was

made with a non-hydraulic, pure lime and crushed tile from the Park
Street villa.

A progressive increase in strength was 'demonstrated,

whilst in the same period

(90 days) comparative specimens with lime

and sand achieved no strength when tested under the same conditions.

5.4

Efstathiadis (1978) - The Greek Water Tank at Camiros

The ancient Greek water tank at Camiros on Rhodes was the subject of a
paper of Efstathiadis (7).

The tank was built about 500 BC and put

out of use around the 3rd century BC.

The stone tank was lined with a

lime concrete made with a pozzolana, a volcanic ash possibly from the
island of Santorini or Nisyros.
was

well

grading

graded,
curve

of

the

grading

Fuller.

Research showed that the aggregate

curve

Mix

closely

the

ideal

compressive

strength,

elastic modulus and water permeability were all determined.

The claim

-46-

proportions,

approaching

made by Efstathiadis

that

the compressive strength obtained by the

Greek concrete after 2500 years, ie.

13.2 MPa, is quite satisfactory

for modern, reinforced concrete structures is somewhat optimistic when

compared with modern UK requirements (8).

Experiments were performed

with lime-pozzolanic mixes containing Santorin earth and the strengths

obtained

up

to

years

examined.

The

conclusion

intimated

by

Efstathiadis was that the Ancient Greeks had produced a high quality
product, more

than

adequate

for

the

requirements,

as a result

of

careful selection and preparation of materials, together with a high

quality of workmanship.

5.5

Malinowski (1979)
Malinowski (9) examined in detail a number of mortars used in ancient
structures designed to convey water.
Etruscan-Roman

water

conduit

In the lining of an underground

only traces of calcium

silicates were

found by chemical examination, despite the presence of crushed brick.

The

lining,

however,

had

proved

very

durable

and

possessed

an

insignificant water absorbance in spite of low density and strength.

This was due to surface polishing, as recommended by Vitrivius (3),
and was demonstrated

by scanning

electron

closely knitted carbonation products.

microscopy, which

showed

The unusually hard lining of a

Roman aqueduct in Caesarea, Israel, proved to consist of six layers,

of

varying

tightness

composition

in

polishing.

two

and

qualities.

Once

again,
been

structural

of

the

layers

seemed

to

have

achieved

Although

the

microstructure

of

the material

from

by
the

joints of a stone pressure conduit indicated to Malinowski that an oil

had

been added,

found

by

following

chemical

Vitrvius

analysis.

(3), no traces of oil could be

Experiments with

simulate the sealants were attempted.

exhibited

mortar

and

oils to

Hydrated lime and linseed oil

a shrinkage, rather than the desired expansion, whereas a

mixture of quicklime and linseed oil did expand on exposure to water,

subsequently showing a very small shrinkage on exposure to air.
great

deal

of

sealants was
excellence

of

similarity
achieved.
the

Roman

in properties between
Malinowski's
cement

modern

and

ancient

main conclusion was that the

products

was

based,

not

upon

scientific understanding, but upon centuries' worth of experience.

47

any

5.6

B. Marchese (1980)
Marchese

(10)

used

differential

thermal

analysis

(DTA) and

diffraction (XRD) to examine a 12th century Italian mortar.

X-ray

Although

DTA showed the presence of calcium hydroxide, Ca(0H)2 reflections were

absent

in

XRD

traces.

These

results

led

to the

amorphous Ca(0H)2 was present, in contrast

conclusion

to that observed

that

in OPC

paste, which is highly crystalline.

5.7

R. Malinowski (1982)
Malinowski
findings
method

summarised

from

of

his

concretes

careful

earlier

in

ancient

polishing

of

findings

(9) and

structures

fresh

lime

presented

in 1982

mortar

new

(11).

was

The

stated

as

ocurring as long ago as 7000 BC, with many instances since that time.
The polishing was described as 'essentially a process which grinds the
lime, carbonate or pozzolana of the mortar creating a dense capillary
structure

at

material.

the surface which

increases the impermeability

The carbonation and hydration i.e. the hardening, are also

accelerated

and,

especially

in

mortars

strength and durability improved.

but

also

inhibits the formation

placed

in thin

layers, the

It restrains shrinkage and cracking

of lime sediments on the walls of

cisterns and agueducts due to a better flow of water.

The removal of

such sediments during maintenance work is also easier.'

porous, lightweight
for

of the

increased

entrained air.

aggregate was also considered

durability,

functioning

in

much

The use of

to be responsible
the

same

way

as

Malinowski pointed out that several Roman buildings

had not been built with a pozzolanic concrete, but that lime concrete
had been

employed

which

had proved

to be extremely durable.

Such

structures included the Cloaca Maxima in Rome and agueducts at Eifel,

Germany.
described.

An

example

of

The ability

a concrete

with

of the Romans

gap-graded

to produce

aggregate

large

was

structures

without cracking was put down to sound engineering practice.

5.8

P.M. Roy and C A . Langton (1983)

Roy and Langton (12) produced in 1983 a large report which examined
the properties of ancient mortars and plasters specifically in terms

-48-

of providing

information

repositories.

on durability

for use with nuclear waste

This work also dealt with

the findings of previous

research (13). Materials dating back to ca. 5500 BC, from Greece and
Cyprus, were
durability.

investigated and were chosen because of their proven

Their wide sample spectrum was divided into four classes

: (1) gypsum cements, (2) hydraulic, hydrated lime and hydrated lime
cements,

(3)

hydraulic,

aluminous

and

ferruginous

hydrated

lime

cements (with or without siliceous components), and (4) lime-pozzolana

cements.

Many

technigues of study were employed including

optical

petrography, scanning electron microscopy including energy dispersive

X-ray

analysis,

structure

chemical

analysis,

analysis by means

of

X-ray

diffraction,

trimethylsilylation

silicate

(TMS), electron

probe microanalysis (EPMA), liquid chromotography to identify organic

constituents and thermal analysis.
detailed

analyses

microstructural

was

by

combination

of

both

chemical

and

factors was responsible for the durability of these

ancient materials.
affected

that

The conclusion reached from very

As with modern constructions, the durability is

initial

composition

throughout the entire

and

design and by quality

building process.

control

Most importantly from the

point of view of the survival of chemical compounds over thousands of

years, it was concluded that most of the binding phases of cements,
with

both amorphous

and

sub-crystalline

structure, were chemically

inert under a variety of exposure conditions for at least 3000 years,

leading to the further conclusion that with modern, Portland cement
based

materials,

durability

problems

as

result

of

deleterious

recrystallisation of the cement matrix would not be expected.

5.9

T. Perander and T. Raman (1984)

Perander and Raman (1984) considered ancient Finnish mortars from the
point

of

restoration

view

of

work;

the
it

possible
having

development

been

found

of

that

new

mortars

mortars

for

currently

available in Finland were unsuitable, some even leading to further

structural damage.
were

examined.

Mortars dating from the 12th to the 15th centuries

Optical

microscopic

studies

were

density, porosity and compositional measurements.

between old and modern mortars were found:
porous, pore shapes being indeterminate.

supplemented

by

Clear differences

old mortars were thick and

The presence of round pores

in some samples indicated the possible use of air entraining agents.

-49

All the lime present was totally carbonated, but hydration of the lime
was often incomplete and the lime improperly burnt.

In the aggregate,

a marked variation in granularity was found, with a lack of material

less than 100 j_im.
5.10

J. Papayianni (1984)
Although Papayianni (15) did not study ancient Greek concrete itself,
he in fact examined concretes made with Santorini Earth, measurements
continuing

for

an

eight

year

period

and

comprising

compressive

strength, alkalinity, carbonation depth and porosity determinations.

Santorini Earth was used to replace Portland cement in quantities up
to

30%,

optimum

Santorini

Earth

quantities
improves

being

obtained

at

level

of

20%.

the strength of concrete, but reduces its

alkalinity as a result of the pozzolanic reaction.

Incorporation of

Santorini Earth was found to shift the pore size distribution to that
containing finer pores.

5.11

T. Perander and ,T. Raman (1985)

A large report by Perander and Raman, published in May 1985 (16) is an
expansion

of their previous work

(14).

Fifteen, historic, Finnish

buildings were examined and approximately sixty mortars studied.

Most

of the failures were due to the effects of frost "and moisture.

large

number

Laboratory

of

laboratory

investigation

determination

made

mortars

consisted

of density, porosity

of

were

optical

also

examined.

microscopy

and

by means of water sorption, mix

proportions, soluble salts, frost resistance and compressive strength.

As a result, new mortars were developed and subsequently field trials
conducted.
resistant

Tests
without

showed

buildings

industrial

air-entraining

normally incorporated
historic

that

agents,

limes
although

to improve workability.

showed

that

the

were

not

additives

frost
were

The investigations of

presence of moisture

and

within the masonry was responsible for the majority of failures.

salts
The

durability of the old mortars was laid down to good adhesion, suitable
porosity

and

long-term

hardening

in

favourable weather

conditions.

This hardening was attributed, not just to a carbonation and drying

process, but also to the periodic dissolution and recrystallisation of
carbonates-

However, since the conditions required for this process

-50

consist of moist

air free of sulphur dioxide, an open-pored

mortar

surface and a long time, it was the opinion of the authors that modern
lime mortars are sentenced to a weak durability because of atmospheric
pollution.

One

interesting

observation

as a result

tests was that lime from various sources, ie.

pits, or dry-slaked, proved

-51-

laboratory

pit-slaked, from old

to have no significant

properties of the lime mortar.

of

effect upon the

ANALYTICAL STUDIES OF OLD, PORTLAND CEMENT-BASED MATERIALS

Although

there

concretes,

have

ranging

been
from

many

published

seconds

to

studies

few

years

of

young

old,

cements

there

have

and
been

relatively few studies of old materials, even though countless numbers of

concrete structures have been erected since the turn of the century.
with

the ancient

materials, interest

has been

stimulated

As

by the nuclear

waste disposal programmes and the development of new analytical techniques.

In any historical study of cement and concrete the development of Portland

cement must occupy a central place in the analysis because it is the only
cementitious
evolution.

material

that

has

been

continuously

studied

throughout

its

It is now clear that the changes in cement performance over the

last 150 years or so are due principally to alterations in mineralogicei

composition.

6.1

W. Lerch and C.L. Ford (1948)

A long term study of cement performance in the USA, reported in the
1940's (17) examined the properties of many cements in concrete for a
number of years.

In the experimental brief it was recommended that

'all known laboratory tests for cement and clinker that appear to have
possible significance should be applied.' The performance of concrete
in

buildings,

however,

was

implications discussed.

not

monitored,

Gonnerman

and Lerch

nor

were

durability

(18) were subsequently

able to report on changes in the characteristics of Portland cement

over

the period

water

1904-50.

demand, setting

Data

on chemical

composition,

fineness,

time, tensile strength, compressive strength,

rupture modulus, expansion, heat of hydration and sulphate resistance

were

presented.

American

cements

exhibited

wide

variation

in

composition in 1904. Free lime contents were relatively high, as were

average

C2S

(37%) and

cements; C3S
period

1904

C3A

(13%) contents

compared

(38%) contents being correspondingly

to

1950

the

principal

changes

to

modern

lower.

day

Over the

in composition

(mostly

occuring between 1926 and 1933) were an increase in C3S content to

about

50% and

a decrease

in C2S content

to about

25%.

Fineness,

surface area, water demand and strengths also increased over the same
period; setting times decreased. The main factors responsible for the
increases observed were the increase in C3S content and an increase in

52-

fineness.

Of interest is the fact that some of the cements in 1904

contained

oil

or

grease

that

leaked

from

grinding

machinery,

in

sufficient amounts to give the cements the potential for entraining

significant amounts of air.
6.2

A.W. Skempton (1963)

In

a review

paper

published

in

1963, Skempton

(19) presents

and

interprets chemical compositional, compressive and tensile strength,

fineness and setting time data available from the earliest days of
Portland cement production.

The work lays particular emphasis upon

the results of strength testing and traces the increases in strength,

through

the

experiments

development

of

of James Rendei

superior

in 1847

product,

(23) and

from

including

the

early

the

first

systematic tests on Portland cement by John Grant, who published his

results in 1866 and 1871 (20, 21, 2 2 ) .

According to Skempton, James

Rendei (1799-1856), supervising work at Henry Grissell's Regents Canal

Ironworks

in London

on 10th

and

31st December

1847, produced

the

first, wholly reliable strength data on Portland cement, the actual

sample

being

that

of

J.B.

White

compression machine was employed

square.
London

&

Sons.

A 75

ton

hydraulic

on specimens 18 in. high by 9 in

John Grant (1819-88) was working on the Main Drainage for

for the Metropolitan Board

of Works when he began, for the

first time in history, the systematic testing of cements.

The tests

comprised tension tests on Portland and Roman cements and compression

tests on Portland cements.
techniques,

so

apparent

As he continued to develop and modify his

strengths

increased.

Because

of

Grant's

endeavours, cement manufacturers made efforts to improve the quality

of their products and, by the year 1863, Grant's results showed that
these efforts were meeting with success.

Between the years 1860 and

1865 the 28 day compressive strength of a Grant test specimen, 1:3 by

weight mix, increased from 900 lb/sq in to 1200 lb/sq in.

At about

this time the average chemical analysis of a cement was:

Si0 2

CaO

23S!

60S

AI2O3
1%

Fe 2 03
4SS

<3
IS

and would produce a Portland cement containing about 55% belite and
10 alite.

It was noted that this average composition had not changed

significantly form those reported earlier (1849-1852).

-53-

6.2.1

The Invention of Portland Cement

Skempton also analysed the results of tests on Roman cements
and compared them with contemporary Portland cements.
first

half of the 19th century

the strength

In the

of cement

was

often assessed by mortaring together bricks in the form of a

horizontal cantilever from a wall, each brick being cemented
to the previous one after the cement had set (from 5 to 15
minutes - Roman cement was guick setting).

If 12 bricks could

be built in an hour, the cement was satisfactory.

Another

test was to construct a brick beam and then apply a load to

failure.

By calculation Skempton compared Roman to Portland

cements.

It was found

producing

much

that

superior

in 1843 Maude and Aspdin were

product

to

the

available,

best

guality Roman cement; even the 1:3 mortars made with Portland
cement

were

stronger

than

1:1

Roman

cement

mortars.

On

average the Portland cements produced in the 1840's were about

twice as strong as the best Roman cements.
enough

to

convince

Skempton

that

the

The evidence was

breakthrough

in

the

production of artificial cement had been made by 1843 at the

latest, probably earlier by Joseph Aspdin, but was probably
not due to I.C.

Johnson (1811-1911), whose firm, J.B.

White

and Sons, did not begin full production of a Portland cement

until 1845.

6.2.2

Improvements to Cement Technology in Germany

Subseguent

improvements

in

cement

quality

were

made

by

Germans; German cements in 1885 had strengths double those of

English cements 20 years before and three times those of 1860
and before.

The reasons for this were (1) systematic analysis

of raw materials, (2) the achievement of more uniform, higher

kiln temperatures as a result of improvements in kiln design
and

management

leading

to

and

finer

(3) improvements
cements.

(1842-1917), a chemist
cement

works,

who

and

It

in grinding techniques,
was

Rudolf

son of the founder

introduced

chemical

Dyckerhoff
of a German

analysis

which

subsequently became standard practice throughout Germany.

a

conseguence

chemical

analyses

54

carried

out

As

by Bauschinger

(24) in 1879 showed a variation of only 59 to 62% in CaO

content in 9 different German cements and analysis of 11
cements by Bhme (25) in 1883 gave similar results.

The

higher, more uniform kiln temperatures achieved as a result of

better design enabled a higher CaO content to be used, so that
there was an increase in the amount of alite formed; by about
1880, German cements contained over 62% CaO, with resulting
alite and belite contents of about 25 and 45% respectively.
This increase in alite content was responsible for the early
age strength increases observed in this period.

As a result

of these changes in chemical composition, clinker from the

kiln became harder and hence the grinding stage of the process
became more important.

That the hydration of cement is a

surface phenomenon was beginning to be recognised; Bramwell

(26) in 1866 had discussed the fact that cement particles
retained on a 200 sieve, with 36 meshes to the inch, were
effectively

inert.

By

1875

the

foremost

producers were

manufacturing cement with not more than 15% retained on a 900

meshes per sq.cm sieve, falling to ca. 8% in 1880 and ca. 3%
in 1887.
6.2.3

The First Standards for the Testing of Cement

The first, officially recognised standard for the testing of
cement was issued by the Royal Prussian Minister for Commerce,
Industry and Public Works on 10th November 1878; it specified
fineness, setting time and strength.

The first time chemical

composition was specified was in the French standard of 1885

which stipulated:
SO2 + AI2O3

0.44

Fe 2 0 3

<C

4%

SO3

<C

1%

CaO

55

Skempton's review of 1963 was an important contribution to our

understanding

of

the

history

of

Portland

development of scientific testing.

cement

and

the

Of significance was his

rationalisation of test results, involving many different test

methods

and units, so that

the progress of the quality

artificial cement could be charted.

of

Once again, however, no

data was presented on the long-term performance of cements and

no conclusions as to durability made.

6.3

Brig. 3. Hamilton-Baillie (1980)

Two papers recognising the contribution to concrete technology made by
the Royal Engineers were published by Hamilton-Bailie
32).
of

in 1980 (31,

Nineteenth century papers published in the Professional Papers

the

Royal

lime-pozzolana

Engineers

are

reviewed,

concrete, Roman

cement,

ranging
Scott's

through
cement

lime

and

and Portland

cement.

6.3.1

Col. C.B. Pasley

Colonel Pasley
military
Pasley

(33) was perhaps the best

engineers

involved

was director

in

the

known of all the

history

of

concrete.

of the Royal Engineer Establishment

at

Chatham and performed many experiments on cement, attempting

to make an artificial version of Roman cement.

Although he

met William Aspdin in 1851 at the Great Exhibition, he still

did not approve the use of Portland cement, preferring instead
hydraulic
Portland

lime.

Pasley

cement

concrete

did

not

carry

out

experiments

on

and his disapproval of the use of

this material is said to have slowed down the progress of its

acceptance among other engineers of the day.
fashion,

Pasley's

comprehensive

book

In a similar

(33) is said

discouraged similar publications for some years.

to have

Subsequent

to the Great Exhibition, however, the value of Portland cement

did become recognised, but only in mortar for brickwork and
not for mass concrete.

-56

6.3.2

Cap. H.R.D. Scott

Captain H.R.D. Scott (34) was the first military engineer to
argue for the use of concrete as a substitute for brick and
masonry.

This was based upon strength tests which showed

Portland cement to be superior to hydraulic lime, Roman cement

and

Scott's

large-scale

cement.
use

of

In spite

concrete

of

this, in

the

first

above ground, Newhaven Fort,

constructed in 1866, Scott's cement was used, probably because

it was cheaper and possessed adequate strength.

Subsequently,

however, because of the increase in quality of Portland cement

and also because of Grant's work (20, 21, 22) Portland cement
was used for military and military-related constructions and
it is claimed

that the defences of Cork Harbour probably

represent the first large-scale use by the Royal Engineers of

Portland cement concrete.

In a paper published in 1880 by

Scott and Redgrave (35) it is claimed that William Aspdin made

the

first,

true

Portland

cement

and

accepted

that

the

proportioning of the raw materials could be left to guesswork

based upon experience.
6.4

K. Walz (1976)
A long-term study of strength gain in concrete was carried out by Walz
(27,28).

Concretes made in 1923 from four Portland cements and stored

in the open showed a 50 year strength that was, on average, 2.4 times
the 28 day strength.

Concretes made in 1941 with one Portland cement

and two blended cements and stored in the open showed, after 30 years,
a strenth gain of approximately 2.3 times the 28 day strength for the
Portland

cement

concrete.

concrete

The most

and

important

3.1

times

for

the

blended

cement

conclusions reached were that the

strength gain after 28 days was greater the lower was the compressive
strength at 28 days and also greater the higher the water/cement
ratio.
6.5

A.T. Corish and P.J. Jackson (1982)

Corish and Jackson (29) in 1982 presented an historical review of the
properties of Portland cement, paying particular attention to the
effects

of

mineralogicei

composition
-57-

upon

strength.

Data

on

composition

from

many

sources

over

the

years

1848

to

collated and reasons for changes in composition given.

1980

were

Because this

century has seen a four or five-fold increase in 28 day strengths, it

was Corish and Jackson's opinion that 'many structures which are built
today in concrete would be quite impossible with the low strengths
that

were

available

a generation

or

two

ago.'

Importantly,

with

regard to setting times and strength gain, it was pointed out that
research has shown that slower cements do not catch up with the more
active cements.

6.6

The Concrete Society Working Party Report (1984)

The most important recent document to review the changing properties
of cement over this century and, for the first time to discuss the
implications

for

durability, was

Working Party investigating

the

report

of a Concrete

Society

'Changes in Cement Properties and Their

Effects on Concrete' (30).

6.6.1

Changes in Mineralogical Composition

The principal chemical changes have been in the proportions of
the calcium silicates alite (C3S) and belite (C2S).

Whereas

in the years 1900 to 1910 typical alite and belite proportions

were 25 and 45 respectively, they had changed dramatically
by 1965 to 45 and 25SS and by 1980 in the UK the proportion of
alite

in

cements

mineralogical

lay

changes

in

the

were

region

slight;

45

the

to

64%.

Other

C3A content

falling

from an average of 13 between 1900 and 1910 to about 11.5

(range 7 to 14) in 1960 and 9.7 (range 5 to 14) by 1980.
The C4AF content changed from an average 10 between 1900 and
1910 to 5
content,

(range 2 to 10) in 1982.

now

important

alkali-aggregate
because,
until

firstly,

recently

changed.

reaction,
such

and,

from
proved

data

had

secondly,

the

Changes in alkali
point

more
proved
methods

of

difficult
of

little

of

view

of

to assess
interest

analysis

have

Only post-1960 data were presented, showing a slight

increase in the early 70's, but a fall overall.

58

6.6.2

Changes in Fineness
Changes

in

fineness
assess,

of

Portland

again

due

cement
to

have

changes

also

in

proved

difficult

to

methods

of

analysis.

Available data indicate that there has in fact been

little change in average fineness since pre-war days, although

the older cements did exhibit more variation.
there is no British Standard method

Unfortunately,

for the measurement of

particle size distribution.

6.6.3

Heat of Hydration
Of significant interest with regard to physical properties are
the

data

hydration

demonstrating

large

of

The

cement.

increases
evidence

in

the

indicates

heat
that

of
the

temperature rise of a concrete containing about 300 kg m -' of

cement

in 1934 was approximately the same as one containing

150 kgm"' of cement in 1978.

It was concluded that, in the

years from 1933 to 1980, there had been an increase in maximum

peak temperature rise of ca. 17 and that the time taken to
reach

this

consideration

temperature

had

reduced

by

ca.

of cracking of concrete subsequent

65%.

In

to thermal

stresses during curing, it is therefore apparent that higher

cement contents could be used in concrete during the earlier
part of this century than is the case today.

6.6.4

Strength
Owing to the large amount of available data, the evolution of
strength
though

development

standard

could

be

considered

in

detail,

methods of testing have changed.

even

Over the

years from pre-1950 to 1980 28 day strengths had risen, but

early strengths had risen proportionally more.

Although data

post-28 days was more sparse it was apparent that the greater
the 28 day strength the less the strength increased beyond 28
days.

-59-

6.6.5

Durability
The

implications

of

the

changes

of cement

properties

upon

concrete design and durability were discussed in detail.

Of

particular importance is the realisation that similar concrete

strengths

are

available

to

modern

constructors

with

lower

cement contents and higher water to cement ratios than were

possible before 1950.
today

in

severe

resistance

to

durability

freeze/thaw

solutions, plus also

cracking

from

It is pointed out that this can result

an

problems

damage
increased

plastic

settlement

and

because
attack

of
by

aggressive

risk of bleeding
and

plastic

poorer
and of

shrinkage.

Conversely, however, because of the higher heats of hydration

of modern

cements, too high a cement content increases the

risk of thermal cracking.

Alkali-aggregate reaction may also

be a problem with higher cement contents.

Because of the

higher, early strengths available in modern times, inadequate

curing due to early formwork striking has become a problem.
Inadequate curing leads to a permeable concrete with increases
in

rates

of

carbonation

and

ingress

of

other

deleterious

substances.

In considering the working party report from the point of view

of the durability of historical structures we are left with
the inevitable conclusion that older concretes are likely to
be more durable because they were made with cements of only
moderate performance.

Because lower strengths were developed

by the older cements, lower water to cement ratios and higher

cement contents had to be used; the latter did not present as
much of a problem as would be the case today since the heats
of hydration were lower.
less of their ultimate

Because the older cements developed

strength before 28 days than modern

cements, formwork striking times would be longer and would be

likely to

lead to better curing.

These practices, forced

upon constructors in former times, would be expected to lead

to

relatively

impermeable

concrete

able

to

resist

deterioration processes leading to reinforcement corrosion.

-60-

the

1.

RECENT STUDIES INVOLVING MODERN ANALYTICAL TECHNIQUES

Much of the work so far reviewed, concerning contemporary studies of old
cements

and

concretes

or modern-day

studies, has

involved

some

strength assessment and determination of chemical composition.

us

something

about

the

macroscopic

properties

of

these

form

of

These tell

materials, but

nothing about the microstructure and the nature of the chemical reactions
that are occurring, or have taken place.

Not until recent years has the

full panoply of modern physical and chemical analytical techniques begun to

be applied to the study of ancient and old concretes.

7.1

Trimethylsilylation
Trimethylsilylation
technique

which

can

(TMS)

(36,

determine

anions present in cement.

37)
the

and

subsequent

polymeric

analysis

is a

state of the silicate

Using TMS Sarkar and Roy (38) examined a

laboratory prepared, completely hydrated cement paste, together with a

20 year

old

paste.

Six

anions were

identified

in both pastes :

SO4 4 -, S i 2 0 7 6 - , S3O9 6 -, S30 1 0 8 ", S 4 0 1 3 1 0 - and S505 10 - and it was

found that during a 20 year hydration period only the relative amounts
of these ions changed.

The ions observed were interesting in that no

known crystalline silicates or organic siloxane compounds containing

or

S4.O13

Si50]3l0~ anions are known.

The aim of such studies is,

of course, to understand the nature of the enigmatic CSH gel formed

upon hydration of the calcium silicates present in Portland cement.
Sarkar and Roy put forward a hydration mechanism in which the calcium
silicates

dissociate

in

polymerise, in a similar

water

to

form

SiO^-

ions

which

slowly

fashion to sodium silicate solution which

forms silica gel upon acidification.

Why this process stops at the

pentamer has remained a mystery.

7.2

Analytical Electron Microscopy

Analytical electron microscopy (39) is a technique that has come much
to the fore
years.

in

solid

state chemistry

and allied

fields in recent

It has enabled the elemental analysis to be accurately carried

out of microscopic regions, which can also be studied by diffraction

and imaging techniques.
other

phases

present

In this fashion the composition of CSH and

in

hydrated

-61

cement

paste

can

be

directly

analysed.

Lachowski, Mohan, Taylor, Lawrence and Moore (40) analysed

mature C3S and cement pastes hydrated for periods ranging from one to
thirty years.

The objective was to study the changes in composition

of hydrated phases, mainly CSH, over long periods.

It was found that

the

is

mean

Ca/Si

ratio

of

the

CSH

in

C3S

pastes

substantially

independent of time between 1 day and 30 years, but, in contrast, for

the cement pastes it was found
with time.

that the mean Ca/Si ratio decreased

In cements, however, it was also apparent that the mean

Ca/Si ratio of the CSH was more closely related to the curing time
than to the degree of hydration.

From an historical point of view,

therefore, it would appear that the mean value of the Ca/Si ratio of
the cement

in a concrete can tell us nothing about

the age of the

cement, unless this ratio has been monitored previously.

.3

Electron Probe Microanalysis

An

allied

technigue

to analytical

probe microanalysis (EPMA) (39).

electron

microscopy

is electron

This technigue was used by Rayment

and Majumdar (41) to examine the composition of CSH phases in cement

pastes from eight days to five years old and in concretes ten years
old.

They

found,

in partially

hydrated

cements, two distinct

CSH

compositions present as inner and outer hydrates around elite grains.

However, upon further hydration, when alite is no longer present, a
single CSH composition is found.
composition

may

be

used

The important conclusion is that CSH

as a means

of determining

hydration reached by a cement at a particular age.

the

degree

of

It was also found

that the calcium content of CSH varies inversely with water to cement
ratio; if this remains true for very old cements then it might be
possible to deduce the original w/c ratio.

EPMA was used to examine a 60 year old Portland cement concrete from a
dockyard

(99).

No substantial difference was found between the CSH

composition of this cement and those of cements hydrated for 23 and 10

years, leading to the conclusion that CSH is stable up to at least 60
years, given no external attack.
Examination

of

the 136 year

old cement

paste

from

the barrels of

William Aspdin'8 cement salvaged from the 'Lucky Escape' (100) showed
the presence of both inner and outer calcium silicate hydrates whose

-62

compositions,

apart

from

having

lower

sulphur

content,

were

essentially identical to those found in a five year old OPC paste.

was therefore concluded that inner and outer CSH phases

It

can be stable

for at least 136 years.

7.4

X-Ray Diffraction
Grudemo (43) used X-ray difraction to examine a concrete from the wall
of a concrete tunnel built in 1914.

His aim, specifically from the

point of view of the suitability of concrete for use in the isolation

of nuclear waste, was to determine what, if any, changes had occurred
in

the

cement

structure.

phase,

His

constructional

particularly

statement,

concrete

of

in
a

those

1982,

of

that

reasonably

crystallinity

or

'for

reasons,

modern

natural
type

has

pore

not

yet

reached an age of more than 50 years' is, however, over-conservative

by at least 30 years.

As a technique for looking at the possibility

of the long-term crystallisation of the cement gel, X-ray diffraction

would

seem

to be

an

ideal method,

but, in practice, the analysis

proved difficult since the reflections from CSH are weak and diffuse
and the diffractograms tended to be dominated by aggregate.

Given

these problems with his experimental approach, Grudemo was able to

come to the conclusion that there had been no major changes in the
cement

matrix

growth.

His

silicate

phase,

with

attempts

no

pronounced

to determine

polymerisation

led

tendency

towards

crystal

if there was a progression

to a similar

conclusion

in

that, if this

process was occurring at all, it was very slow and the time to reach
equilibrium would be very great, such that the effects could not be
predicted.

7.5

Studies of Aspdin Cements

Blezard (42) examined both Joseph Aspdin's and William Aspdin's cement
using

reflected

light

microscopy.

He

used

the

mineralogicei

composition of Portland cement to classify stages in its development

as follows:
a)

Proto-Portland cement as produced by Joseph Aspdin;

b)

Meso-Portland cement as produced by William Aspdin;

c)

Normal Portland cement as produced today.

63

The sample of Joseph Aspdin's cement examined was a mortar rendering

(c. 1828-29) from a building near the site of Aspdin's Kirkgate works
in

Wakefield.

The

material

proved

to

be

aggregate containing shale, coke and coal.

temperature
although

calcium

some

silica-rich

proto-Portland
mixture

of

silicates,

alite

calcium

extremely

porous, with

No evidence of the higher

and

belite,

silicates

were

could

be

noted.

found

This

is

cement, defined by Blezard as essentially a calcined

limestone

and

clay,

with

little

evidence

of

CaO-SiQ.2

interaction as the temperature of the burning was too low for compound
synthesis.

Three samples of William Aspdin's cement were examined

: a clinker

from a preserved kiln at Northfleet, a specimen from a cement barrel

salvaged from the 'Lucky Escape' at Sheerness and a specimen from the
boundary wall of Portland Hall, Gravesend.
produced

by William

heterogenerous

Aspdin

material

interaction, producing

was defined

but

with

The meso-Portland cement

by Blezard

definite

as an

evidence

belite with some alite.

of

extremely

CaO -

The clinker

SO2

sample

from the kiln showed evidence of slow cooling, to be expected from a

beehive kiln, in the form

of small belite

crystals.
from

the

A maximum

kiln

temperature

mineralogy

and

microstructure

semi-hydrated
similar

crystals

fringing

of 1325-1350C
of

the

was inferred

samples.

The

cement from the barrel from the 'Lucky Escape' proved

to the kiln sample, again showing heterogeneity

composition,

with

deficient

lime, with

in

alite

similar
a

crystal

character.

lime saturation

The

factor

of mineral
cement

of 78SS.

was

Belite

predominated, with well differentiated aluminate and ferrite phases.

The Portland Hall sample was similar in character to the others, but
proved to be heavily carbonated.

Blezard pointed out that because the William Aspdin clinker was so
heterogeneous it was unneccesary to add a retarder to the cement, this
only becoming necessary with the advent of a more homogeneous product
as produced in a rotary kiln.
7.5.1

Portland Hall
Several

investigators

in

recent

years

have

examined

the

concrete from the boundary wall of William Aspdin's Portland

-64-

Hall,

built

hand-sized
wall.

c.

1850.

Idorn and Thaulow

piece

of

pre-cast

concrete

Contrary

to

the observations

(44) examined

from

the top of the

of Blezard

(42) on a

different sample, this piece proved to be carbonated only to a

depth of about 5 mm, taken to be'an indication of a low water
to cement

ratio, good compaction and curing.

were examined in the optical microscope.

cement-paste
Crystalline

matrix,

calcium

with

an

hydroxide

Thin sections

These showed a dense

estimated

and

w/c

unhydrated

of

and

0.45.

partially

hydrated cement grains were all identified in abundance.

No

sulphated compounds were identified, consistent with it being

unnecessary to add gypsum to early Portland cement.
was

found

seemed

of unhydrated

to have remained

identified
implying

at

long

aluminate

phases, but

unhydrated.

Calcium

distances

continuing

from

its

ionic migration.

No trace

the

ferrite

hydroxide was

supposed

origin,

The cement was coarse

and this was seen as having functioned in such a way as to

provide

a reserve of cement

leading

to continued

secondary

hydration, increasing the strength and density of the concrete

and making the material very durable.

Most interestingly, the

concrete proved to be air-entrained; this was interpreted by

the authors as being by deliberate design, either to improve
workability or durability.

Blezard (45), in a discussion of

Idorn and Thaulow's paper, was of the opinion that the air
entrainment was not deliberate - its benefits not having been
appreciated

and

applied

until

the

1930's

and

that

it

probably had occurred by accident, perhaps from the use of a

mould release agent.
Portland

Hall wall

He also pointed out that his sample of

(42) was heavily carbonated

and that an

examination of the unhydrated phases showed the aluminate was

present.

Figg,

the

provider

of

Blezard's

and

Idorn

and

Thaulow's

sample, has also examined and written about the concrete of

the

boundary

remarkable
wrought

of

discovery

iron

reinforced

wall
rod,

Portland
of

one

concrete.

Hall

(46).

Fleur-de-Lys

He

made

unit

containing

examples

of

of

the

first,

modern

The

rod

proved

to

be

in

excellent

condition, with the cover varying between 15 and 25 mm.

65

the

Of

the decorative units on the top of the wall, Figg noted that
they

are

of

variable

quality,

as

shown

by

the

different

carbonation depths observed by Blezard and Idorn and Thaulow,

and

that

the

Fleurs-de-Lys

circles

are

of

lower

quality

than

the

(Blezard had examined a circle and Idorn and

Thaulow a Fleur-de-Lys).

Figg estimated that, for concrete in

a sheltered, outdoor position, the depth of carbonation would

be expected

to

lie

in

the

range

10-70 mm

for

a 130 year

exposure period, so that the 3-5 mm depth observed by Idorn

and Thaulow and the 2-3 mm observed by Figg in other places
demonstrate

the remarkable quality of the Fleur-de-Lys unit

concrete.

Figg

proven
matrix,

durability
the

thought

that

the principal

lay in the highly

aggregate

being

rather

reason

densified
poor

in

for the

cement

paste

quality.

The

large, unhydrated cement particles remaining were seen as the

residue from an originally well-graded range of cement grains
which led to the high densification, the continuing hydration
of the cement resulting in the hydration products filling the
cement paste volume nearly completely, perhaps aided by the
presence of an air-entraining agent.

-66

ANALYTICAL TECHNIQUES
8.1

X-ray Diffractometry
X-ray diffractometry is an extremely valuable technique for the study
of mixtures of crystalline solids and so can be very useful in the
analysis of heterogeneous materials such as cement and concrete.
X-rays are diffracted by crystalline solids according to Bragg's Law
such that a substance may be identified from the observed reflections.
In the powder method a polycrystalline or powdered solid is placed in
a beam of monochromatic X-rays.

In powdered form a substance will

contain crystals oriented in all possible directions so that there

will always be some crystals with the correct orientation to satisfy
Bragg's Law for any lattice plane spacing, 'd'.

Thus the output from

a diffractometer consists of a set of peaks corresponding to the

various

'd' values

in

the

crystals.

Using

the

d values, the

intensities of the peaks and other information it is possible to:

a)

identify unknown substances;

b)

quantitatively estimate compounds in mixtures;

c)

determine cell parameters;

d)

determine

the chemical composition

of compounds in a solid

solution series.
8.2

Optical Microscopy
Concrete can be examined either in transmitted light or in reflected
light.

Both methods of examination require careful, skilled sample

preparation; for reflected light a plane, polished surface of high

quality is required, whereas for transmitted light a thin, transparent
section of approximately 30 micron thickness is necessary.

Both these

methods allow examination of the relationships between grains to be

studied; crushed grains can be used for transmitted light microscopy,
but their spatial relationships have been destroyed.
In transmitted light minerals can be identified by their shape, size
and by their behaviour under specific lighting conditions, viz. under
plane polarised light and with crossed polars. This type of study was

-67-

pioneered by Le Chatelier and Tornebohm, who were the first to use the
polarising

microscope

to

study

cement

clinkers

and

identify

the

Portland cement minerals.

In reflected light minerals are identified by their shape, size and

reflectance under certain lighting conditions.

Hardness can also be

measured by micro-identation technigues.

Chemical etchants may also be applied to the surface of sections in
order to bring out certain features in minerals as an aid to their
identification.
8.3

Thermal Analysis

Thermal analysis is a technigue which measures the dependence of a

physical property of a substance with temperature.
range

of

physical

properties

which

can

There is a wide

be

studied.

The

thermo-analytical technigues employed in this study are: differential

thermal

analysis

(DTA),

thermogravimetry

(TG)

and

derivative

thermogravimetry (DTG).

8.3.1

Differential Thermal Analysis

is a technigue of recording the

temperature difference between the sample to be studied and an

inert, reference material against either time or temperature
as the two are subjected to identical temperature regimes in
an environment heated or cooled at a controlled rate.

Thus if

the sample evolves heat as a response to being heated within a

certain

temperature

range

then

positive

temperature

difference is recorded; examples of such exothermic events are

oxidation

reactions

and

certain

phase

transitions.

If an

endothermic reaction occurs so that the sample absorbs heat

from its environment then a negative temperature difference is
recorded;

examples of such reactions are dehydroxylations and

decarbonations.

Thus the DTA curve consists of regions of

baseline, where no thermal

reactions are

taking

place, and

sections of positive or negative peaks, where exothermic or

endothermic reactions respectively are taking place.

DTA is

not normally used as a guantitative technigue for practical

-68-

reasons:

the

instrumental

form

of

the

curve

is

and sample factors.

'fingerprint'

identification

affected

by

both

It is useful for the

of

minerals

and

for

semi-quantitative assessment.
8.3.2

Thermogravimetry

is a technique in which the weight of a

substance, in an environment heated or cooled at a controlled

rate, is recorded

as a function

of time or temperature.

Reactions such as oxidations will involve an increase in

weight whereas dehydroxylations or decarbonations occur with a
decrease in sample weight.

Thus the typical TG curve consists

of plateaux, where the sample weight is essentially constant,

and steps, where weight changes are taking place, and which
vary

in

sharpness

involved.
8.3.3

according

to

the

particular

reaction

Unlike DTA, TG is a quantitative technique.

Derivative Thermogravimetry
the TG curve.

records the first derivative of

Although presenting no more information than

TG, DTG is extremely useful as an aid to interpretation of the

TG curve.

The DTG curve consists of a series of positive and

negative peaks which correspond to the temperatures where the

weight is changing most rapidly.

It is superficially similar

to the DTA curve, but the peak temperatures are often slightly
different and the DTG curve cannot record weightless reactions
such as crystalline phase transformations.
8.3.4

Simultaneous DTA, TG and DTG

It

is

possible

to

devise

an

instrument

which

will

simultaneously record the DTA, TG and DTG curves from the same
sample.

Apart from saving the time and effort of having to

record the thermograms of the different techniques separately,

simultaneous curves are an aid to their mutual interpretation,
for example a peak observed by DTA might be confirmed as a
phase transformation if no weight change is observed by TG.
8.4

Water Permeability
Water permeability measurements were carried out in an apparatus as
illustrated in Fig. A9.1. There are two, basic, experimental methods:

69

a) if

the

through

sample

the

is

sample

completely
can

be

penetrated

measured

then

and

the

Darcy's

rate

of

flow

permeability

coefficient calculated, b) if the sample is not completely penetrated

it is split open, the penetration measured and Valena's permeability
coefficient calculated.

Darcy's coefficient

k'

Vx_

(8.1)

Valena's coefficient

k'

2ht

(8.2)

nx^
where

Tests are
diameter

velocity of flow

sample thickness

pressure head

time for penetration

voids fraction

normally

carried

out

cores, but smaller

on

samples

50 mm

long

sections

can be used.

of 100 mm

The samples are

encased in epoxy resin and fixed into the rig.

Water is applied at a

pressure of 10 bar to the face of the sample.

The flow through, or

the sample penetration, at a set time is then measured.

The voids

fraction is calculated from the weight of the sample before and after
testing, the depth of penetration and the sample dimensions.
8.5

Oxygen Diffusion
Test samples, normally core sections 50 mm long by 100 mm diameter,
are

sealed

exposed.

in

circular

steel

rigs

such

that

the

flat

faces

are

Oxygen at a known pressure and flow rate is passed over one

side of the specimen whereas helium gas is purged over the opposite
face at the same pressure and flow rate.

The helium gas stream is

analysed by gas chromatography for oxygen and the steady state flow of
oxygen calculated from the percentage of oxygen in the helium stream,
the flow rate of gas and the temperature and pressure conditions.
time taken for equilibrium
The

diffusion

coefficient

The

to be reached is generally 24-48 hours.

D Q 2 was calculated using Fick's first law

of diffusionj

70

where

8.6

fx

Ci

(8.3)

Co-Ci

diffusion coefficient;

flow rate of the helium stream;

cross sectional area of the sample;

diffusion path length;

Co

oxyqen concentration in the helium stream;

C^

diffused oxyqen concentration.

Core Strength
Core strength was determined by crushing according to BS 1881 (77).
The estimated in-situ cube strength can be calculated if the coring
direction is known; where this was not known the calculation was not
carried out.

8.7

Chemical Analysis
Chemical analyses were carried out according to procedures detailed in
BS 1881 (78).

8.8

Depth of Carbonation
The depth of carbonation of a concrete was determined by spraying a
freshly

cut

surface

with

Phenolphthalein

solution.

Maximum

and

minimum depths were measured.

The depth of carbonation could also be assessed from a thin section by
optical microscopic observation of calcite.
8.9

Scanning Electron Microscopy

The

use

of

electron

microscopy,

in

combination

with

in-situ,

quantitative X-ray microanalysis, has become widespread in the field

of solid

state chemistry

in recent

years and

has proved

to be an

invaluable tool for the elucidation of the microstructure of solids.

There are many, distinct, electron microscopic techniques.
study

scanning

electron

microscopy

71

(SEM),

imaging

with

In this
either

secondary

electrons

energy-dispersive

or back-scattered

X-ray

electrons, and

'microanalysis,

was

combined

employed

on

with

polished

sections of concrete.
In the conventional mode of operation of an SEM low energy, secondary
electrons are used for imaging; such electrons are produced near the
surface of the specimen and, since their intensity is dependent upon
the inclination of the surface to the beam, the surface topography can
be studied.

If, however, back-scattered electrons are used to form

the image then the image is dependent upon atomic number as well as
surface topography

(79).

Electrons are scattered more strongly from

regions of higher, mean atomic number

than other regions and hence

these regions appear brighter in the image; moreover this dependence

is very sensitive.

In the examination of cement the unhydrated grains

appear bright and C3S, C2S and C3A can be distinguished, even though
the differences in mean atomic number are very small; the mean atomic
numbers

being

12.67,

respectively.

All

12.29

the

and

hydrated

12.18
phases

for

C3S,

appear

C2S

darker

and

C3A

than

the

unhydrated ones, calcium hydroxide is light grey, while CSH is darker

and porosity black.

Quantitative analysis of areas of interest discovered in the electron

microscope

can be obtained

X-rays,

emitted

either

by

commonly
Computing

as a result

wavelength

these

simultaneously

by X-ray microanalysis.

days,

dispersive
by

analyse

systems

of electron

apply

an

bombardment,

crystal

energy
all

the

appropriate

are analysed

spectrometers

dispersive

for

Characteristic

elements

from

system

or,

more

which

can

fluorine

corrections.

upwards.

Quantitative

analysis can be obtained from areas less than 1 urn in diameter.

8.10

Mercury Intrusion Porosimetry (MIP)

The measurement of the pore size distribution of concrete samples is
of

importance

permeability
porosimetry

since

and

this

durability

(MIP) provides

distribution
of

the

influences

material.

information

over

the

strength,

Mercury

intrusion

wide

range

of pore

sizes, from 15 pm down to approx. 0.01 urn pore diameter, from pore
sizes just larger than gel pores and including the range for capillary
pores whose size and number vary considerably with water/cement ratio
and maturity.
-72-

MIP is based upon the fact that a non-wettinq liquid, which is one
forminq a contact anqle qreater than 90 with the pore walls,
intrudes open pores only under applied pressure.
For cylindrical
pores the Washburn equation (80) applies:

where

= - 2 y Cos Q
r

P
r
0
9

=
=
=
=

(8.4)

pressure required to intrude a pore;

radius of intruded pore;
surface enerqy of the liquid;
contact anqle between liquid and pore wall;

In the practical situation, eqn. 8.4 is reduced to:

r

75000

(8.5)

At a qiven pressure, P, a volume of mercury is intruded into all

pores of radii not less than r. This volume is equal to the volume
of pores of radius r^ in the sample. By incrementally increasinq
the pressure, the cumulative pore volume distribution can be obtained
for smaller pore radii. The interpretation of the cumulative plot of
intruded pore volume aqainst pore radius may be aided by the
calculation, from the obtained data, of other parameters such as the
differential pore size distribution, the surface area of the pores,
the hydraulic radius of the pore system and the maximum continuous
pore radius (81,82,83).
The differential pore size distribution qives the frequency at each
radius, enablinq the most frequently occurrinq radii to be quickly
recoqnised.
The hydraulic radius, r n , is defined as the ratio of the total
intruded pore volume to the total surface area and attempts to
simplify the pore structure of the sample from one with varyinq radii
to that of a sinqle pore of radius r n with a volume equivalent to
the total pore volume.

-73

The maximum continuous pore radius (MCPR) is defined as the radius at

which the function
Change in Pore Volume
Change in Applied Pressure
reaches a maximum and is thought to represent the minimum diameter of
pores which are continuous throughout the hydrated cement paste.
larger the value the greater will be the permeability (82).

The

Below a

certain pore radius it might be expected that gas and liguid movement
would be so slow as to be negligible in comparison with flow through
larger pores.

Mehta and Manmohan

(84) considered

that pores below

0.132 jjm diameter did not contribute to water permeability and found
good agreement between water permeability and pore parameters greater
than

this

intruded

diameter.

pore

volumes,

It

can

therefore

surface

area

and

be

useful

to

hydraulic

recalculate

radii

for

pore

pastes.

For

diameters greater than 0.132 jjm.

Most

porosimeter

mortars and

research

concretes

has been done using

the relationship

cement

between

pore parameters and

transport properties such as water permeability is less obvious.

This

is thought, for various reasons, to be due to microcracking at the

interface

between

microcracks

could

the

aggregate

invalidate

and

cement

the assumptions

paste

(81).

made when

Such

calculating

pore parameters.
8.11

Sorption

Capillary rise within concrete is the basis of the Taywood Engineering

'Sorption

Test*

(85).

sample

of

concrete

is

placed,

in

the

laboratory, with one surface just in contact with water and the height
or

weight

of

water

absorbed

by

capillary

rise

is

measured.

Measurement of the rate of absorption provides information about the

pore structure of the concrete; if water is absorbed rapidly then the
capillaries are large, if absorption is slow then the capillaries are
small.

Measurement of sorptivity has been found useful in determining

the durability of building materials (86, 87) and concrete (88).

The

depth of penetration is related to pore radius and time as follows:

74

;(^e)
where

d
r
Po
t
\

(8.6)

capillary rise;

pore radius;

atmospheric pressure;

=
s

time;
viscosity.

It is also possible (85) to obtain a measure of porosity by plotting

the height of capillary rise against the weight of water gained per
unit area of sample; the porosity is obtained from:
V

1000 M

(8.7)

A d
where

weight gain;

area of penetration;

depth of penetration.

Volumes obtained during the sorption test can be presented graphically

by relating the volume obsorbed per unit area to time:
V

Sti

(8.8)

sorptivity;

area of penetration;

volume of water absorbed;

A
where

so that a plot of V^ vs t should be a straight line whose slope is

A
the sorptivity.

-75-

9.

SAMPLES COLLECTED
Historical and other information regarding each sample is presented first,
in sections 9.1 to 9.17.

This is followed by reports of visual examinations

of the samples, with selected photographs.

9.1

Ancient Greek Concrete (Camiros) (c. 500 BC) (7) (Fig. 9.1)
Camiros was one of the three ancient cities of Rhodes, the others
being Lindos and Ielysos.
hill.

The city was built on the north side of a

Excavations have revealed an underground water storage tank

near the ruins of the Temple of Athena.

The tank has a capacity of

about 600 m-'. It was put out of use around the 3rd century B.C.
The tank was built of stone lined with concrete.

This concrete has

been the subject of research by Efstathiadis (7).

9.2

Roman Mortar, Bath (1st century A.D.)

A small piece of Roman mortar from the Thermae at Bath.

9.3

Herod's Palace, Masada, Israel (pre-73 A.D.) (115,116)

Masada was the scene of a great tragedy in 73 A.D.

On a sheer

mountain-top, in the desert east of the Dead Sea, the Jews had
constructed a great fortress. This fortress was their last stronghold
in the rebellion against Imperial Rome.
A.D.,

was

put

down

with

devastating

The 'First Revolt', 66-70

results

for

Judaea; Titus

conguered and destroyed Jerusalem, the Temple was demolished.

Masada was beseiged from 72-73 A.D.

For nearly two years the Roman

legionaries laboured to construct a massive earth bank against the

mountain side.

When the crest of the ramp was level with the summit,

the Roman siege engines attacked the helpless fortress.

their awful fate, the Jews committed mass suicide.

Realising

In Rome triumphal

arches were erected to celebrate the victory over Judaea and coins
bearing the inscription

'Judaea Capta' were issued throughout the

Roman Empire.

-76

Fig 9.1

The Water Tank at Camiros, Rhodes

77

9.4

Hadrian's Wall (122 A.D. -

) (117) (Figs. 9.2 to 9.4)

The emperor Hadrian came to power in 117 A.D. and found trouble in
Britain.

He decided to deal effectively with the northern frontier

and, being conservative in nature, chose to improve the existing

frontier on the Tyne-Solway line rather than conquer the whole island
or move forward to the much shorter Forth-Clyde isthmus. The other
frontiers of the empire were usually formed by natural boundaries such
as rivers, seas and deserts, but in Britain there was no such boundary
so Hadrian decided to create an effective barrier by the construction
of a wall, from sea to sea, to divide the Romans from the barbarians.
T h e Wall was planned to be 76 Roman miles long, from Newcastle-on-Tyne
to Bowness-on-Solway.

It was to be a stone wall, 10 Roman feet wide,

for the eastern 45 miles from Newcastle to the River Irthing and a
turf wall, 20 Roman feet wide at its base, for the western 31 miles
from the Irthing to the Solway.

Regularly spaced at intervals of one

Roman mile were to be fortified gateways (which have been termed

milecastles), which provided a way through the Wall with double gates
front and fear. The gap between fortlets was to be broken by two
observation turrets.
The plan was later modified, before completion of the Wall, to include
the construction of new forts along the Wall, those forts behind the
Wall being abandoned.

The new forts were built for whole auxiliary

units and varied in size from over 3 acres to over 9 acres.

Evenly

spaced, their main purpose was to allow unrestricted access for major
forces to the north.

It was also decided to construct an earthwork

(now known as the Vallum) behind the Wall, from Newcastle to Bowness,
the purpose of which was to secure the Wall from the rear. Before it
was completed it was decided to narrow the Wall to between 6 and 8 ft,
probably to speed up the work.
Work on the Wall did not start until 122 or 123 A.D.

The stone wall

consisted of two outer faces of dressed stones with a core of rubble,

usually bonded with mortar but occasionally with clay.

The building

method seems to have been that one or two courses of facing stones
were laid, then the rubble and mortar core poured in, followed by more
courses of stone etc.

Drains were laid through the foundation.

-78-

The

igs 92 and 9.3

Hadrian's Wall, Near Sycamore Gap, Northumberland

-79

Fig 9.4

Hadrian's Wall, Near Sycamore Gap, Northumberland

-80-

stone was quarried locally, as can be seen from inscriptions on rock

faces.

The sources of lime for the concrete have, however, not yet

been found (118).

The height of the Wall, or how it was finished off,

is not known, but it is thought that it was about 15 feet high.

Nearly the whole of the Wall is known to have been built by three
legions of the army of Britain.

The majority of the work was done by

the legionaries themselves; craftsmen of all types skilled in the art

of construction were present

in the legions and the soldiers were

experienced in the construction of military installations.

The date when the Wall was finished is not precisely known.

Certain

parts were not built until 128-38.

An estimate

in 1976 for a similar

concrete was 80 million (117).

wall to be built

in reinforced

The cost of a stone wall would be

truly astronomical.
The

history

of

the

Wall

in Roman

Britain

reoccupation, destruction and rebuilding.

is one

of abandonment,

The samples obtained for

this study came from a section of the Wall rebuilt during the reign of
Septimius Severus, around 200 A.D.

The location

was Sycamore Gap

(O.S. grid reference 762678), about 10 miles west of Hexham.

Wall

is presently

being

excavated

by the National

Trust

Here the
(119) and

areas of the Wall previously hidden by the accumulations of time have

been exposed.

One section of the Wall here has a hard and durable

mortar core; by contrast other sections nearby have mortar which is

soft and crumbly, with a soil-like consistency.

From the area with

the harder core a piece of the core and a piece of unconsolidated

mortar, dropped by a Roman Mason and never incorporated into the Wall,
were
has

9.5

removed.

The Building Research Establishment (see Appendix A4-)

obtained deep core samples from the Wall in this location.

Bulla Regia (1st century A.D. onwards) (131)

A small sample of Roman concrete from Bulla Regia, Tunisia, Northern
Africa.
Kings.

The name of the town shows that it was used by Numidian

34-35 A.D. is the date given to the oldest building.

The town

became a municipium by 110-112 and was elevated to colonial status

by Hadrian.

81

The town survived until Byzantine times.

It is noted for its houses

with luxurious, underground rooms, which would be cool during the very
hot African summers.
9.6

Reading'Abbey (c. 1121) (124, 125) (Figs. 9.5 and 9.6)

Reading Abbey was founded in 1121 by Henry I, a younger son of William
the Conqueror and the third Norman king of England, reigning from
1100-1135.
branch

The first monks belonged to the Order of Cluny, a reformed

of

Benedictine

Benedictine by 1250.

Monasticism,

becoming

regarded

as

fully

The Abbey was built on a gravel spur between the

rivers Kennet and Thames. The Abbey church was completed by 1164 and
the dedication

ceremony

performed

Thomas Becket, in the presence

by the archbishop

of Henry

II.

of

Canterbury,

The church was very

large, only 50 feet shorter than St. Pauls is today, and the other
buildings too were on a large scale.

The Abbey occupied a 30 acre

site and became one of the most important religious establishments in

the country, benefiting greatly from royal patronage.

In the 1530's-the government

dissolution

of Henry VIII carried out the general

of the English monasteries.

The Abbot

of Reading was

tried and found guilty of high treason in 1539 for refusing to accept
the supremacy of Henry VIII as head of the Church of England.

He was

dragged through the streets of Reading and hung, drawn and quartered
in front of the Abbey Church.

Occupation of the Abbey was ended; by

1549 the buildings were being robbed and the lead stripped from the
roofs.

The

building

work

removed

and

Abbey
in
the

became

Reading;
cores

an

official

and

the

facing

stones

mostly

removed.

unofficial

Most

quarry

for

from

the

walls

were

of

the

church

and

cloisters had been razed by 1642, when events during the Civil War
wrought further destruction.

The site also became a source of gravel

from the 17th to the 19th centuries.

Now all that remains of the

Abbey are parts of the walls of the refectory and reredorter.

These

walls have been stripped of their stone to expose the inner cores,
made of concrete, with large pieces of flint aggregate (see figs. 9.5
and 9.6).

These cores have endured for a number of centuries but are

now in need of repair to ensure their survival.

many places soft and crumbly.

-82-

The concrete is in

= A-^tt-- -

iKsrr--

Figs 9o5 and 96

-83

Reading Abbey

Although the concrete cores possess undoubted durability, the walls of

Reading Abbey have been misrepresented in putting forward the case for
concrete.

L.G.

Mouchel

and

Partners

(107),

claiming

'unlimited

durability*

for reinforced concrete in 1921, stated that

'the stone

has long since perished, while the concrete still remains' and Stanley
(47) implies something similar.

Since the stone seems to have been

removed by man, however, statements as to the durability of the stone

vs. the concrete ought to be disregarded.

Coade Stone (1770-1840) (120, 121)

Coade

Stone was

an artificial

preparation have remained

stone

somewhat

of which

the

of a mystery.

composition

and

It is thought to

have been based upon patents taken out by Richard Holt in 1722 for an
artificial stone which was made by casting in moulds and vitrification
by fire to produce a product
stone or marble'.
and

Eleanor

'more durable and harder than natural

Holt sold his business in Lambeth in 1769 to George

Coade,

who,

along

with

their

daughter,

also

called

Eleanor, had been making a similar stone-like material in Lyme Regis.

George

died

'Coade's

in

1770

Lithodipyra

and

it was left

Terra-Cotta

or

to the two women

Artificial

Stone

to ' develop

Manufactory'.

The business flourished, producing decorative works such as coats of

arms,

church

pinnacles,

architects, including
Coade

Stone

statues,

Robert

extensively

vases

Adam,

during

etc.

Many

distinguished

James Wyatt and Dohn Nash, used

the

late

18th

and

19th

centuries.

Captain Bligh (of 'Mutiny on the Bounty' fame) had his tomb decorated
with Coade Stone.
today

and

material.

are

Examples of Coade Stone can be seen in many places

monuments

Noteworthy

Isleworth, West

London.

is

to

the

the

exceptional

western

Designed

gateway

by Robert

durability
to

Adam,

Syon

of

this

House

the gateway

at
was

originally decorated with a material from one of Coades' competitors.

This material weathered badly and some panels were eventually replaced
with

Coade

Stone;

the

latter

has

alongside the decayed imitations.

endured

and

can

be

seen

today

Lions were popular and examples can

be seen at County Hall, London and Syon House; the Lion Yard shopping
precinct in Cambridge boasts a wooden lion which was carved as a model
for the Stone lions now at County Hall.

84

Some Coade Stone figures have proved to be not so durable, but this
has been the fault of their construction, not of the Stone itself.
Pieces of figures were cemented together with iron rods introduced to
reinforced

those parts requiring strengthening.

Some of the joints

have proved to be not so impervious as the Stone itself, the metal has
rusted and damaged the Stone.
Investigations into the nature of Coade Stone were carried out in the
1950's (120).

Pieces of preparative materials were discovered when

the Coades' factory was knocked down to make way for the Festival of
Britain

in 1951.

A clay was found which proved

to be fairly well

crystallised kaolinite with a small proportion of white mica.

microscopic
ground

examination

quartz,

flint

of Coade Stone showed

and

individual stones varied.

glass

in

an

Optical

it to contain finely

amorphous

matrix,

although

Together with the results from an X-ray

examination this suggested that the material might be a meta-kaolin,

produced

by heating

concluded

a kaolin

clay

between 450 and 950C.

It was

that Coade Stone contained as its main ingredients china

clay with a finely ground grog prepared from Coade Stone either mixed
with, or used as an alternative to, sand.

The samples received for this study were from a church pinnacle.
9.8

Joseph Aspdin Render (c. 1843-5)

A piece of render from the 'Wakefield Arms' public house in Wakefield.
This building, according to Stanley (47), is the only known surviving
structure incorporating Joseph Aspdin's Portland cement.
close

to

the

site

of

Aspdin's

cement

works

and

is

It is very
brick-built,

rendered with Portland cement in order to resemble stone.

9.9

Cement Barrel (c. 1848) (Figs. 9.7 and 9.8)

The fascinating and amusing story of this sample is told by Stanley
(47).

In the early days of cement manufacture, cement was sold in

barrels.

William

Aspdin

had

established

his

cement

works

in

Northfleet by 1848 and at about this time a ship loaded with barrels
of Aspdin's cement was making its way down the River Thames when it
unfortunately

ran

aground

off

Sheerness

-85-

on

the

Isle

of

Sheppey.

Figs 9.7 and 9.8 The 'Ship on Shore' Inn, Sheerness

showing the 1848 Cement Barrels

86

Seeing the foundered ship, the local people went out and removed the
cargo, expecting to find whisky in the barrels.

Finding instead that

the barrels contained cement which had by now set, they decided to
take the barrels back to the beach and use them to build a public
house.

The

'Ship on Shore' is still there today.

The barrels

themselves are extensively cracked due to shrinkage of the neat cement

paste.
9.10

Portland Hall (1850-2)

The building of Portland Hall by William Aspdin is described in
Section 4.12.7.

Samples from the boundary wall have been obtained

comprising part of a core from the wall and part of a decorative

Fleur-de-Lys unit from the top of the wall.
9.11

Concrete House (1865)

A piece of unreinforced concrete.

9.12

Railway Terraces, Hull (1877)

Pieces of concrete from houses in Hull.

9.13

Weaver's Mill (1897-8) (Figs. 9.9 and 9.10)

Weaver's

Provender

Mill

was

the

first,

multi-storey,

reinforced concrete-framed building to be erected in the U.K.

entirely
It was

built in 'ferro-concrete', the term, pre-dating 'reinforced concrete',

first

coined

by

L.G.

Mouchel

to

describe

the

Hennebique

(or

Mouchel-Hennebique) system, with which the vast majority of the early

reinforced concrete buildings were constructed.

The forward-looking

directors of Weaver & Co. Ltd., an expanding Swansea flour-milling

company, commissioned their second flour mill in 1897 from the French
firm of Hennebique 4 Le Brun on the advice of L.G. Mouchel, who was
French consul to Swansea and an enthusiast for the new concrete
system, becoming a short time later Hennebique's agent in Britain.
The contract was signed on the 20th October 1897 for the very low
price of 4,150; this may have been a ploy by Hennebique to maximise

-87-

Fig 9.10 Weaver's Mill, Swansea

(Photograph by courtesy of Mr. C.C. Stanley)

88

HENNEBIQUE FERRO-CONCRETE
Fig 9.9

FLOUR M I L L AND GRANARY. SWANSEA.

Built (or Messrs. W E A V E R i Co., L t d .

GENERAL. VIEW

These

buildings,

c o n s t r u c t e d in

Concrete in this c o u n t r y .

1897,

were

OF

BUILDINGS.

the first

buildings

erected

entirely

of

Ferro-

T h e y are founded on a general raft of Ferro-Concrete, laid over a

deep s t r a t u m of sand and r u b b i s h deposited on soft m u d in the e s t u a r y of the River T a w e .

The Flour Mill measures So feet b y 40 feet by 1 1 ; feet high, and its flat roof is c o n v e r t e d into a
reservoir with the c a p a c i t y of 20,000 gallons.

T h e cantilever p o r t i o n at the left h a n d

projects

1+ feet b e y o n d the s u p p o r t s , and carries the total load of 670 tons.

The G r a n a r y

measures 127 feet b y 4S feet 6 inches by 90 feet 3 inches high, the

Tower rising to the height of 130 feet.

The c a p a c i t y of

the Grain

Silos is 33,000

Cleaning

q u a r t e r s of

wheat.
After h a v i n g been 111 use for n
new m a c h i n e r y .

years, one of the Mill floors was c u t t h r o u g h to m a k e room for

The reinforcing s t e e l was t h e n found to be in perfect c o n d i t i o n , w i t h o u t a n y

trace of corrosion.
Architect:

- 89

HENRY C. PORTSMOUTH, M.S.A.

his chances of getting the contract or, as has been suggested (109),
part of a package deal, since neighbouring silos, of a similar size,
were commissioned and erected a short time afterwards for 15,478.
Hennebique

was

determined

contract in Britain.

to

make

success

of

his

first

major

The British architect, H.C. Portsmouth, who was

completely inexperienced in ferro-concrete design, is thought only to

have been responsible for minor details and the drawings were prepared
in

Nantes,

probably

with

Hennebique's

personal

involvement

(109).

Although local labour was used, French foremen were brought over to
supervise

the

work

and

it

is

thought

that

aggregate, cement and steel, were all imported

109,

110, 111).

the

materials

used,

from France (47, 56,

The transport of materials from France would have

been a relatively easy matter because there was a considerable coal

export trade from Swansea to Nantes and returning ships could carry
concrete materials as ballast.

Access to the Mill was easy as ships

could dock alongside the site.

however,

is

still

matter

Whether

for

the materials were French,

enquiry

(58,

this

work);

local

aggregate was available and the British Portland cement industry was
very large and producing a good product.

The Mill was built on a spit of land, formed largely from discarded
ships'

ballast,

completed

by

between

September

examined several times.

two

docks

1898.

on

Since

Swansea
then

waterfront

the

building

and
has

was
been

The Hennebique ferro-concrete handbook (107,

fig. 9.9) mentions that the reinforcing steel was in perfect condition
when a floor was cut through 14 years after completion.
same

time

Clark

(112)

reported

that

the

Mill

was

At about the
in

excellent

condition and noted that the site was both near the sea and chemical
works.

The architect's son, O.S. Portsmouth, maintained that the Mill

was still structurally sound in 1968 (109).

1972

that

the Mill was

standing

threatened with demolition.

empty

but

Stanley (110) reported in

in good

condition, yet

Cusack (109) reported in 1976 that the

Mill was 'probably still sound'; by this time the building had been
listed

for preservation

by the Welsh Office.

Parkinson

(111), in

1981, stated that the mill was 'in poor condition' and noted that some
of the wrought iron beam links had encouraged spelling.

The aggregate

grading was assessed as being very poor, lacking fines and with little

-90

material in the 5-20mm range.

previously

that

different

the

parts

difficulties

In this respect Cusack (109) had noted

aggregate

of

the

experienced

mill

was
and

visibly

uneven

commented

in making

that

in

this

texture
may

that

transporting
maintained
steel,

clinker

found

in

colliers

and

noted

that

yet

the

aggregate

the

high

still

'relatively

might

shell

the concrete was completely

was

reflect

up the aggregate; this would be

ironical, if true, had the aggregate had been imported.

thought

in

Parkinson

have

come

content.

It

from
was

carbonated down to the

impermeable

to

air

and

water',

although no measurements are quoted.

When the building was demolished

in 1984 it was reported that

'the

frame was in good condition though parts of the slab and infill brick
panels were rather weak' (113).

Pieces of the broken concrete showed

the steel to be in perfect condition, but a small area of the mill

subjected to continuous running water had shown distress (58).

The

findings of Parkinson are therefore in conflict with all the other

reports, which maintain that the mill was in good condition right up
to the end of its life.

Weaver's

Mill

supermarket.

was

demolished

early

in

1984

to

make

way

for

Pieces of this historic building, the forerunner of so

many constructions in Britain, can be seen displayed on the site, in

the Science Museum, London and at the Chalk Pits Industrial Museum,
Amberley, Sussex.

9.14

Woolston Quay (1899) (Fig. 9.11)

Woolston Quay, Southampton, was the first, reinforced concrete jetty
of

any

size

to

be

built

in

the

U.K.

It

was

constructed

in

ferro-concrete on the Hennebique System by L.G. Mouchel and Partners

in 1899.

The jetty was built on piles 10 in. by 10 in.

of a hammer-head

in the form

and had a river frontage 100 ft. long with a jetty

width of 46 ft.

The ferro-concrete handbook of 1921 (107), fig. 9.11, states that the
jetty was as good as new after 21 years of service, despite a collison
with a steamer, entailing some repairs.

91-

An article by Gueritte (114),

JHENNEBI QUTERB-CNCBE-T^j

Fig

WOOL8TON

THE

FIRST

JETTY.

FERRO-CONCRETE JETTY

BUILT IN THE UNITED

KINGDOM.

This work, calculated for the superload of 5 cwt. per square foot and a 30-ton crane at the
end, measures 136 feet long, and has a river frontage 100 feet long, the approach viaduct being
30 feet wide, and the jetty proper 46 feet wide.
A f t e r c o n t i n u o u s use u n d e r e x c e p t i o n a l l y h e a v y t r a f f i c f o r m o r e t h a n
21 y e a r s , t h i s j e t t y is a s g o o d a s w h e n f i r s t e r e c t e d .

It has cost n o t h i n g

f o r m a i n t e n a n c e , a n d t h e only money spent upon It w a s f o r t h e slight

r e p a i r s e n t a i l e d by a c o l l i s i o n In 1901, W h e n a l a r g e s t e a m e r c r a s h e d
i n t o it, b u t w i t h o u t c a u s i n g a n y t h i n g m o r e t h a n l o c a l i n j u r y .
Owners : MORDET, CASKET (SOUTHAMPTON), LTD.

92

9.11

the managing director of Mouchel and Partners in 1926, mentioned that

a recent inspection had shown the structure to be in a perfect state
This was despite the fact that only

of preservation after 25 years.

in. concrete cover was possible to the main reinforcing bars; Gueritte
went

on

to

say

that

'a comparatively

thin

layer

of

really

good

concrete affords, in fact, far better protection to the steel than a

thick layer of more indifferent material'.

The last time the quay was

inspected was 1963 (108), when it was noted that the structure was in
remarkably

good condition, with the piles and bracings showing very

little sign of spelling due to reinforcement corrosion, even in the

area

between

tide levels.

The deck beams had not

fared

so well,

however, and had spalled badly in places, exposing the reinforcement.

A study of some concrete samples in 1967 (108) showed the concrete to
be of excellent
10mm.

quality, very dense and carbonated to no more than

The steel reinforcement was in excellent condition.

Woolston

Quay

has

been

demolished

and

replaced

with

larger

structure.
9.15

Pressed Tile (1904)

A concrete roofing tile, made in a hand press c. 1904.

Similar tiles

can be seen at the Museum of Concrete, Chalk Pits Industrial Museum,

Amberley, Surrey.
9.16

Huddersfield Mill (1913)

A

sample

from

an

interior

beam,

said

to

have

been

in

moist

environment.
9.17

Ralli Building (1914) (Figs. 9.12 and 9.13)

The Ralli Building was a splendid warehouse built in Salford in 1914
for the locally well-known firm of Ralli Brothers.

The building was

constructed entirely in reinforced conrete and was one of the first

buildings to be so built in Manchester-Salford.
on the Hennebique
Mouchel

system

Ferro-Concrete

(38), although

Handbook

93

of

1921

It was probably built

it does not appear

(107).

The

site

in the
of

the

Figs. 9.12 and 9.13 The Balli Building, Salford,

diarinig demolition i n 1985.

building was excellent

Yorkshire

Railway

on

for communications, with

one

side

and

the

River

the Lancashire and

Irwell,

connecting

directly with the Manchester Ship canal, on the other, plus adjacent
local

roads.

basements.

The

building

was

nine

storeys

high,

including

two

The upper seven storeys were cantilevered about six feet

wide along the river frontage.

The completion of the building was

celebrated in the press at the time (122, 123) and the airiness and
well-lit qualities, made possible by the use of reinforced concrete,
noted.

The Ralli Building was demolished

development.

Some spalling

of

in 1985 to make way for further

the concrete, due to

reinforcement

corrosion, had occurred in places such as window ledges (Fig. 9.13);

this appeared

to be mostly superficial and an eye-witness, who was

present when the demolition started, stated that a lot of the spalling
had occurred when the first few blows with the ball and chain shook
the building.

Several pieces of concrete were retrieved

rubble heaps.

95-

from the

PROJECT: HISTORICAL CONCRETE 4I38H

STRUCTURE: CAMIROS 500BC, (SAMPLE 1).
SIZE OF SAMPLE EXAMINED: 50mm x 70mm x 50mm
THIS SAMPLE CANNOT HE DESCRIBED AS A 'CONCRETE' - IT IS MORE OP A MORTARLIKE MATERIAL
VISUAL CORE EXAMINATION
1. COMPACTION
Appears to be fairly compact with very few voids visible,
Excess voidage: N/A
2.

AGGREGATE
Type/Shape:
Grading:

N/A

3. DISTRIBUTION OF MATERIALS
4.

CRACKS
Many surface cracks - appear to be shrinkage cracks.

5.

REINFORCEMENT
None.

6.

ADDITIONAL COMMENTS
A very lightweight material - no visually detectable aggregate. The
sample appears to be 'filled' with very fine filaments.
Sample needs further study under microscope and by chemical analysis.

INSPECTOR
NAME:
DATE OF EXAMINATION:

CORE MARK/NO:
31.7.85

SIGNED :/%M; *Jm e^j^en^

96

so

100

150

aoo

APPROX SCALE IN mm

Carairos, Rhodes, c

97

500 BC,

aso

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: CAMIROS 500 BC (SAMPLE 2)
SIZE OP SAMPLE EXAMINED: 45 x 15 x 20mm MAIN INSPECTION SURFACE 45 x 15mm
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform.
Numerous small voids, negligible medium and large voids.
Excess voidage: 0.5%
2.

AGGREGATE
Type/Shape: Irregular granite.
Grading: Approximating to 10 - 5mm graded coarse aggregate.

3. DISTRIBUTION OF MATERIALS
Uniform.
4. CRACKS
One main crack through the sample. The crack runs parallel to the
exterior face, some smaller "branching cracks run from the main cracks.
The cracks do not run through the aggregate.
5. REINFORCEMENT
None.
6. ADDITIONAL COMMENTS
Sample size is too small to he a representative sample.
Cement is a light colour.

INSPECTOR
NAME:
DATE OF EXAMINATION:

CORE MARK/NO:
31.7.85

SIGNED: f%Jf vJ /i

-98

50

100

150

APPROX SCALE IN mm

Camiros, Rhodes, c. 500 B.C.

99

200

PROJECT:
STRUCTURE:

HISTORIC CONCRETE
MORTAR FROM LINING OF A ROMAN BATH.

VISUAL CORE EXAMINATION

1.

COMPACTION:

2.

AGGREGATE:

Type/Shape:

No v o i d s appear to be p r e s e n t in the m o r t a r .

1-2mm a n g u l a r s o f t b r i c k a p r t i c l e s in a pink m a t r i x .

Grading:

3.

DISTRIBUTION OF MATERIALS:

4.

CRACKS:

5.

REINFORCEMENT;

6.

ADDITIONAL COMMENTS:
features.

NIL

NIL

Small p i e c e of pink m o r t a r . L i t t l e obvious

INSPECTOR
NAME:

P-C. ROBERY

DATE OF EXAMINATION:

SIGN:

Uniform

24.3.86

PfaL,

- 100-

150

100

APPROX SCALE IN mm

Bath,

c . 1 s t Century A.D.

101

PROJECT:
STRUCTURE:

HISTORIC CONCRETE
MORTAR FROM HEROD'S PALACE, MASADA, S.E. ISRAEL c60BC-40AD.

VISUAL CORE EXAMINATION

1.

COMPACTION;

2.

AGGREGATE:
Type/Shape:
Elongated and f l a k y p a r t i c l e s of a g g r e g a t e .
Grading:

Mortar is heavily voided with 0.2-2.Omm sized air voids.

4mm m a x . a g g r e g a t e .

3.

DISTRIBUTION OF MATERIALS:

4.

CRACKS:

5.

REINFORCEMENT:

6.

ADDITIONAL COMMENTS:

Sample too small f o r comment.

NIL

NIL

Mortar i s l i g h t fawn i n c o l o u r .

INSPECTOR
NAME:

P-C. ROBERY

DATE OF EXAMINATION:
SIGN:

/Ctr

24.3.86

- 102-

Masada, Israel, c. 1st Century A.D.

103

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: HADRIANS WALL
SIZE OP SAMPLE EXAMINED: MAIN SAMPLE - 180n x 170m x 150mm
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform through sample.
Considerable small and medium voids. Few large voids.
Excess voidage: 2.0%
2.

AGGREGATE
Type/Shape: Mainly a mixture of irregular fine grained basalt,
crystalline granite and sandstone/gritstone.
Grading:

See below.

3. DISTRIBUTION OF MATERIALS
Generally uniform, but some 'pockets' of 'finer' coarse aggregation in
places. The general concrete is composed of basalt/granite coarse
aggregate of approx 14mm single-size grading, 'filled-out' with large
pieces of sandstone/gritstone/basalt of 30 "to 50mm size.
4.

CRACKS
Many cracks visible on surface of sample, some visible as penetrating
up to 20mm into sample. Lengths of cracks up to 40mm, widths 0.5 1.0mm.. Cracks do not run through aggregate.

5. REINFORCEMENT
None.
6.

ADDITIONAL COMMENTS
The cement paste 'mortar' is pale yellow in colour and contaminated
by pieces of lime or chalk up to 4 in size, soft clay-like blocks of
material up to 6mm in size, and in places appears to be bonded together
with fine hairs or threads. One corner of the sample is composed mainly
of large pieces of aggregate coated in a white deposit that appears to
be lime or chalk - thickness of deposit up to 0.5mm.
INSPECTOR

NAME:

CORE MARK/NO:

DATE OF EXAMINATION: 2.8.85

SIGNED: ffL

f^aJ-^ry^,

-104-

H a d r i a n ' s Wall, c . 200 A.D.

105

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: HADRIANS WALL, SAMPLE 2
SIZE OP SAMPLE EXAMINED: 80mm x 8Cmm x 80mm
VISUAL CORE EXAMINATION
Note: This sample of mortar was picked up from the ground under the wall
and appears never to have been part of the structure, therefore comments
on compaction, excess voidage, etc, are not valid if compared to concrete/
mortar that has been placed.
The sample contains one piece of gritstone aggregate of approx 30mm size,
one piece of gritstone aggregate approx 16mm size and several pieces of
gritstone/basalt aggregate of 10 - 5mm size. One corner of the sample is
heavily contaminated with plant leaves, many appear to be mixed in with
the mortar, rather than just being bonded to the exterior. Two pieces of
brick are partly embedded in the mortar, one approx 8mm in size and the
other 3mm. One piece of seashell is visible, partly embedded.
The entire sample is honeycombed - it appears that either there was a lack
of 'filler' material in the mix or that the mortar was mixed in a fairly
dry condition.
The 'cement paste' is a light yellow in colour, and the sand used is possibly of a fairly coarse grading. None of the fine hair of threads found
in the main structural sample are visible, but this may account for the
high concentration of leaves in one corner of the sample, eg, the leaves
had not been mixed in fully or that the sample was not in a fully mixed
stage when deposited ( it being presumed that the threads in the main sample
are plant fibres from, eg, leaves).

INSPECTOR
NAME:

CORE MARK/NO:

DATE OP EXAMINATION:

SIGNED: PMW

2.8.85

O. (*

106-

50

100

150

H a d r i a n ' s Wall, c . 200 A.D.

107

200

PROJECT:

HISTORIC CONCRETE

STRUCTURE:

MORTAR BULLA REGIA, TUNISIA,

c. 1ST AND 2ND CENTURIES A.D.

VISUAL CORE EXAMINATION

I

COMPACTION:

2.

AGGREGATE;
Type/Shape:
Grading:

Mortar appears to be well compacted with few v o i d s .

Angular Sand.
2mm max. a g g r e g a t e s i z e .

3.

DISTRIBUTION OF MATERIALS:

4.

CRACKS:

5.

REINFORCEMENT:

ADDITIONAL COMMENTS:
Mortar i s a t t a c h e d t o a d i f f e r e n t coloured
mortar a t one end. Bulk of sample i s w h i t e , while the a d j a c e n t mortar
i s fawn i n c o l o u r . One s i d e of the sample i s coated w i t h moss.

Heterogeneous mixture of sands and cement.

NIL

NIL

INSPECTOR
NAME:

P.C. ROBERY

DATE OF EXAMINATION:

24.3.86

SIGN:

- 108-

"s r\

Bulla Regia, c. 1st and 2nd Centuries A,D.

- 109

r\

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: READING ABBEY, 1121 (SAMPLE A)
SIZE OP SAMPLE EXAMINED: 3 PIECES, EACH APPROX 30mm x 40mm x 10mm
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform as fax as can "be determined.
Few small voids, considerable medium voids, negligible large voids.
Excess voidage: 0.5%
2.

AGGREGATE
Type/Shape: Combination of irregular flint, rounded flint, gravel and
chalk.
Grading: Not possible to determine owing to small size of sample coarse aggregate varies in size from 10mm to 5mm with 'grit' down to
1mm. Chalk 'blocks' up to 8mm in size.

3. DISTRIBUTION OF MATERIALS
Uniform as far as can be determined from sample size.
4. CRACKS
None.
5. REINFORCEMENT
None.
6. ADDITIONAL COMMENTS
Samples appear to have good cement paste/aggregate bond, cement paste
is light grey in colour.

INSPECTOR
NAME:

CORE MARK/NO:

DATE OF EXAMINATION:

SIGNED:

fjj,

^.PjLAfO^.

110

Reading Abbey, c. 1121

- Ill

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: READING ABBEY, 1121 (SAMPLE B)
SIZE OF SAMPLE EXAMINED: 80mm x 70mm x 30mm
VISUAL CORE EXAMINATION (MAIN BLOCK OF SAMPLE)
1. COMPACTION
Uniform, but one side of sample slightly better compacted than other.
Numerous voids below 0.5mm diameter, numerous small voids.
Negligible medium and large voids.
Excess voidage: Approx 0.5%
2.

AGGREGATE
Type/Shape: No coarse aggregate. Fine aggregate consisting of a
fine grained sand with large quantities of seashell and silicate 'grit',
Grading (without shell) approximating to BS882 overall limit for fine
aggregates grading.

3. DISTRIBUTION OF MATERIALS
Unable to determine specifically - one side of sample appears to have
a lower shell/grit content than other.
4.

CRACKS
None.

5. REINFORCEMENT
None.
6.

ADDITIONAL COMMENTS
i

Sample is a 'mortar' as opposed to a concrete. Main block has a

white deposit or mortar on surface, with embedded gravel of approx
5mm grading, the deposit being soft and crumbly. Main mortar is pale
yellow in colour.

INSPECTOR
NAME:

CORE MARK/NO:

DATE OF EXAMINATION:

/Vf -J.fr 'JP^j^r^.

SIGNED: fL'L.

112

Reading Abbey, c. 1121

113

PROJECT:

HISTORIC CONCRETE

STRUCTURE:

COADE STONE 1770-1840AD - DECORATIVE FEATURE FROM A CHURCH.

SIZE OF SAMPLE:

APPROX. 50 x 50 x 50mm DETAIL.

VISUAL CORE EXAMINATION

1.

COMPACTION:

Uniform throughout the sample.

Numerous small v o i d s , few medium and l a r g e v o i d s .

Excess Voidage:
2.

0.5 *

AGGREGATE:
Type/Shape:
Grading:

S i l i c a and other type or types unknown.

Very f i n e aggregate of l e s s than Imra in s i z e .

3.

DISTRIBUTION OF MATERIALS:

k.

CRACKS:

5.

REINFORCEMENT:

ADDITIONAL C O M M E N T S :
Sample has been fired. Sample material is coade
stone. Sample shows little deterioration. Outer surface is light grey in
some places and of slightly sandy colour in others. One surface is dark
grey with a 1-3mm thick band of mid-grey towards outer surface, which denotes
a weathered crack at that point.

Uniform.

NONE

N0NE

INSPECTOR
NAME:

P.J. PEARSON

DATE OF EXAMINATION:

SIGN:^

11.3.86

fltf/^AL-,

-114-

100

150

APPROX SCALE IN mm

Coade Stone,

115

1770-1840

200

PROJECT:

HISTORIC CONCRETE

STRUCTURE:

RENDER FROM A BUILDING IN WAKEFIELD

. 1843-5

VISUAL CORE E X A M I N A T I O N

1. COMPACTION:

Render is heavily voided and almost honeycombed in places.

Excess Voidage:

10

2.

AGGREGATE:
Type/Shape: V e r y little aggregate is visible. That which is present, appears
elongated and flaky of 1-2mm size. Aggregate is black, coal-like
Grading:
^n appearance.

3.

DISTRIBUTION OF MATERIALS:

4.

CRACKS:

5.

REINFORCEMENT:

6.

A D D I T I O N A L COMMENTS:
Render has been t r e a t e d w i t h a w h i t e , p r o b a b l y
c e m e n t i t i o u s c o a t i n g w h i c h i s f l a k i n g away. Thickness o f r e n d e r i s a p p r o x .
6mm.

NIL

NIL

INSPECTOR
NAME:

P.C. ROBERY

DATE OF E X A M I N A T I O N :

24.3.86

SIGN: fAy

-116-

100

150

APPROX SCALE IN mm

Joseph Aspdin Render, Wakefield, c1843-5

117

200

PROJECT:

HISTORIC CONCRETE

STRUCTURE:

HARDENED CEMENT FROM A BARREL

LOCATION:

c1848 AD.

TAKEN FROM THE PUB 'SHIP ON SHORE'.

VISUAL CORE EXAMINATION

1.

COMPACTION;

Uniform, v o i d - f r e e m a t r i x .

Excess Voidage:
2.

AGGREGATE;
Type/Shape: Very f i n e , a n g u l a r p a r t i c l e s .
Grading:

mm max. s i z e d m a t e r i a l forms 'the m a t r i x .

3.

DISTRIBUTION OF MATERIALS;

H.

CRACKS;

5.

REINFORCEMENT;

ADDITIONAL COMMENTS; F i n e white streaks run through the cut face of

the sample. The matrix is dense and heavy. One face is stained orange/brown
probably due to silt or other contaminant seeping down a fissure in the
barrel sample.

Uniform through the sample.

NIL

NIL

INSPECTOR
NAME:

P.C. ROBERY

D A T E O F EXAMINATION:

24.3.86

SIGN: ,

118

Cement Barrel, c. 1848

119

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: PORTLAND HALL, 1850 - SPECIMEN 1 (DECORATIVE BLOCK)
SIZE OP SAMPLE EXAMINED: TOTAL SAMPLE, SIZE APPROX I70 x 110 x 100mm
AREA OP SAMPLE EXPOSED FOR EXAMINATION - 120mm x 50mm 190mm x 90mm AND
100.mm x 60 mm
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform and reasonably good in examination areas.
Few small voids, considerable large voids, negligible medium voids.
Excess voidage: 0.5%
2.

AGGREGATE
Type/Shape: Irregular sandy limestone.
Grading: Approximating to 20mm single-size graded coarse aggregate.

5. DISTRIBUTION OF MATERIALS
Uniform in examination areas.
4. CRACKS
None.
5. REINFORCEMENT
None.
6.

ADDITIONAL COMMENTS
Sample appears to have good cement/paste aggregate bond. One piece of
'brick' found in one inspection area - purpose unknown. Cement paste
colour a darkish grey - darker than an ordinary OPC cement paste.

INSPECTOR
NAME:
DATE OF EXAMINATION:

CODE MARK/NO:
26.7.85

SIGN: fhhp J. P^oo*v^

-120-

-I50

4150

4-

100

A D D o n y cr* A i c IM m m

Portland Hall, c. 1850

121

200

PROJECT: HISTORICAL CONCRETE 4I38H

STRUCTURE: PORTLAND HALL, I85O - SPECIMEN 2 (CORE IN 2 BITS, ONE MARKED 4B)
SIZE OP SAMPLE EXAMINAED: 50mm DIAMETER, 45 - 55mm LONG
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform.
Pew small and medium voids, negligible large voids.
Excess voidage: 0.5%
2.

AGGREGATE
Type/Shape: Rounded flint gravel.
Grading:

20mm single-size graded coarse aggregate.

3. DISTRIBUTION OF MATERIALS
Uniform through core.
4. CRACKS
Some cracks at aggregate/cement paste interface, approx 0.05 to 0.1mm,
one main crack separating core into 2 pieces with other cracks radiating
down and through core from the main crack, none passing through
aggregate.
5. REINFORCEMENT
None.
6.

ADDITIONAL COMMENTS
Cement paste lighter in colour than specimen 1 (decorative block),
similar to that of an ordinary ope.
Generally good cement paste/aggregate bond.
Specimen size too small to gather any other than a general idea of the
above data.

INSPECTOR
NAME:

CORE MARK/NO:

DATE OF EXAMINATION:

SIGNED: Pfuf J f*
<CrtAv

-122-

P o r t l a n d H a l l , c . 1850

123

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: CONCRETE HOUSE I865
SIZE OP SAMPLE EXAMINED:

150-mmx 130mm x 200mm

VISUAL CORE EXAMINATION

1. COMPACTION
Uniform but very poor.
Considerable small, medium and large voids.
Excess v o i d a g e :
2.

50?

AGGREGATE
Type/Shape: Irregular fine-grained basalt. Some flaky aggregate.
Grading: Approximating to 40mm - 5mm graded aggregate.

3. DISTRIBUTION OF MATERIALS
Uniform throughout core.
4.

CRACKS
Multiple cracks, none running through aggregate. Many gaps between
aggregate and 'cement paste'.

5. REINFORCEMENT
None.
6.

ADDITIONAL COMMENTS
Most coarse aggregate coated in a reddish-brown clay-like silt up to
1mm thickness. Poor bond between coarse aggregate 'cement paste'.
Cement Paste
Colour a mid-dark grey with a pinkish tinge. The paste has more the
appearance of a mortar and is contaminated with large pieces of seashell and is soft and crumbly.

NAME:
DATE OF EXAMINATION:

CORE MARK/NO:
1.8.85

SIGN: fl/Jtf> I P-*

-124-

Concrete House, 1865

125

PROJECT: HISTORICAL CONCRETE 4I38H

STRUCTURE: RAILWAY TERRACES, HULL, 1877
SIZE OP SAMPLE EXAMINED: 140mm x 150mm x 75mm
VISUAL CORE EXAMINATION
1. COMPACTION
Type 1 : Uniform and fairly good. Type 2: Uniform and extremely poor.
Type 1 : Consideratile small voids, negligible medium and large voids.
Type 2: Numerous small, medium and large voids (large voids in form of
honeycombing.
Excess voidage: Type 1 - 0.5%
Type 2 - 12.0%
2.

AGGREGATE
Type/Shape: Type 1 - Irregular basalt gravel.
Type 2 - Irregular basalt gravel, yellow and red 'brick'
rubble.
Grading: Basalt - 5mm down. Brick - approx 5 - 10mm pieces.

3. DISTRIBUTION OP MATERIALS
Uniform in both types.
Type 2: Consisting of mainly brick rubble with some basalt gravel.
Type 1 : Is mainly mortar with a little basalt gravel.
4.

CRACKS
None.

5.

REINFORCEMENT
None.

6. .ADDITIONAL COMMENTS
Type 2 cement paste a mid-dark grey colour.
Type 1 a little darker. Type 1 appears to be a finishing mortar or
render and may have been applied over type 2 after casting or later.
A thin surface coating has been applied on the exterior surface of
Type 1 ; this coating has peeled off in areas to reveal a yellow
surface to Type 1.
INSPECTOR
NAME:
LATE OP EXAMINATION:

CORE MARK/NO:
1.8.85

SIGNED: Philip J. /*

126

Railway Terraces, Hull, 1877

- 127

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: RAILWAY TERRACES, HULL
SIZE OF SAMPLE EXAMINED: 135mm x 85mm x 70mm
VISUAL CORE EXAMINATION
1.

COMPACTION
Uniform and fairly poor.
Pew small and medium void, considerable large voids.
Excess voidage:

2.

1.5 - 2.0%

AGGREGATE
Type/Shape: No coarse aggregate.
Grading: Not visually determinable.

3. DISTRIBUTION OF MATERIALS
Appears uniform.
4. CRACKS
None.
5. REINFORCEMENT
6.

None.
ADDITIONAL COMMENTS
This sample is a mortar-type material, not a concrete. It would
appear to be a decorative element rather than structural.

INSPECTOR
NAME:

CORE MARK/NO: A

DATE OF EXAMINATION:

>.:/5

SIGNED: fiJuu U.nCK**~-i -

128

Railway Terraces, Hull, 1877

129

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: WEAVERS MILL 1898
SIZE OP SAMPLE EXAMINED: 200mm x 195mm x 110mm
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform but poor.
Numerous small and medium voids, considerable large voids.
Excess voidage: 6.0 - 8.0%
2.

AGGREGATE
Type/Shape: Combined irregular and rounded igneous basalt and granite
gravel.
Grading: Generally approximating to 20 - 5mm graded coarse aggregate
but a high percentage of coarse aggregate would pass through a 5mm
sieve.

3. DISTRIBUTION OF MATERIALS
Generally uniform but with signs of segregation in some areas, with the
coarser end of the coarse aggregate grading predominantly in the
(lower ?) 250mm surface layer.
4. CRACKS
No major cracks visible, some short (approx 5mm) cracks of around
0.05mm width on surface, they do. not pass through the aggregate.
Some cracks surrounding corroding ends of reinforcement straps at surface
of concrete.
5. REINFORCEMENT
Two pairs of rectangular smooth-sided reinforcing straps, section dimensions of 5 - 6mm x 50mm. Cut ends corrosion state 2* (both pairs).
Exposed ends 3* for one pair and 3 - 4 * for the other.
6. ADDITIONAL COMMENTS
Surface extremely
and deposit up to
easily. The bond
to be good at the

rough, with both dark and light grey/brown laitance

3mm thick. The deposits were soft and crumbled
between the concrete and reinforcing straps appears
cut surfaces of the straps.

INSPECTOR
NAME:
DATE OF EXAMINATION:

CORE MARK/NO:
26.7.85

SIGNED: / % X p J*fi&

-130-

50

4-

-+

100

150

APPROX SCALE IN mm

Weaver's M i l l , Swansea, 1897-8

131

200

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: WOOLSTON QUAY 1899
SIZE OF SAMPLE EXAMINED: 180 x I60 x 55nim
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform throughout the sample, one poor area at the surface. Considerable
small, medium and large voids. Honeycombing present in one area.
Excess voidage: 0.5 - 1.0%
2.

AGGREGATE
Type/Shape: Combined, rounded and irregular flint gravel (one or two
pieces elongated).
Grading: Approximately to 20mm single size graded coarse aggregate.

3. DISTRIBUTION OF MATERIALS
Uniform throughout the sample.
4. CRACKS
Two cracks on broken surface, 0 - 1mm wide, 10 - 20mm long. The cracks
do not run through the aggregate.
5. REINFORCEMENT
One horizontally running non-ribbed 20mm diameter bar. Cover 67mm to
top surface, 58mm to side. Two cut ends, both of which are corrosion
state 1 - 2 * .
6.

ADDITIONAL COMMENTS
Good bond between cement paste/aggregate and cement paste/reinforcement
bar.

INSPECTOR
NAME:

CORE MARK/NO:

LATE OF EXAMINATION:

SIGNED: P^f

26.7.85

^' / W * ^

-132-

Woolston Quay, 1899

133

PROJECT:

HISTORIC CONCRETE

STRUCTURE:

HAND-PRESSED CONCRETE ROOFING TILE C1904, FROM THE MUSEUM

OF CONCRETE, SURREY.

VISUAL CORE EXAMINATION

COMPACTION;

Mortar i s poorly compacted with numerous small-sized voids.

Excess Voidage:
2.

5.0 %

AGGREGATE:
Type/Shape:
Angular, crushed g r a v e l .
Grading:

3mm max. s i z e d aggregate.

3.

DISTRIBUTION OF MATERIALS:

4.

CRACKS:

NIL

REINFORCEMENT:

Uniform.

NIL

ADDITIONAL C O M M E N T S :
Pigmented (red) mortar has been bonded onto
unpigmented mortar which forms a lip on the underside of the tile. The
tile itself appears to have been bedded in place using a cement mix.
The tile surface is irregularly eroded, exposing the coarse aggregate.

INSPECTOR
NAME:

P-C. Robery

DATE OF EXAMINATION:

24.3.86

SIGN:

-134-

Concrete T i l e ,

135

1904

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: HUDDERSFIELD OLD MILL 1913
SIZE OF SAMPLE EXAMINED: ONE HALF OF A 10Cmm DIAMETER CORE SPLIT DOWN
LENGTH, 92mm
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform but poor.
Few small voids, considerable medium and large voids.
Excess voidage:
2.

1.5 - 2.0%

AGGREGATE
Type/Shape:

Irregular, coarse sandstone or gritstone.

Grading: Approximating to 20mm single-size coarse aggregate but with

a low percentage of aggregate at fine end of grading. Several pieces
of gravel mixed in with main aggregate of indeterminate type.
3. DISTRIBUTION OF MATERIALS
Generally uniform but with one of two areas lacking coarse aggregate.
4. CRACKS
Crack across of
coring face passing through length of core, runs
through aggregate. Crack width approx 0.15mm.
5. REINFORCEMENT
None.
6.

ADDITIONAL COMMENTS
Light coloured cement paste. Bond between cement paste and coarse
aggregate appears to be good.

INSPECTOR
NAME:
DATE OF EXAMINATION:

CORE MARK/NO
29.7.85

SIGNED: /%4 ^ / W * < ^ .

136-

Huddersfield M i l l , 1913

- 137

PROJECT: HISTORICAL CONCRETE 4138H

STRUCTURE: BALLT BUILDING, I914
SIZE OP SAMPLE EXAMINED: I3O x A5am x 10Cmm (CONCRETE ONLY}
130mm x 90mm x 100mm (WITH RENDER)
VISUAL CORE EXAMINATION
1. COMPACTION
Uniform but very poor throughout sample.
Considerable small and medium voids, numerous large voids.
Excess voidage: Approx 8.0%
2.

AGGREGATE
Type/Shape: Angular crystalline limestone.
Grading: Approximating to 20mm single-size graded coarse aggregate
but a little oversize at the coarse end of grading and lacking in
coarse aggregate at the finer end of grading.

3. DISTRIBUTION OF MATERIALS
Uniform throughout sample.
4.

CRACKS AND VOIDS

Many crack-like voids between cement paste and coarse aggregate.
Some short cracks running through aggregate.

5. REINFORCEMENT
None.
6. ADDITIONAL COMMENTS
Light grey cement paste. Cement paste is very 'aerated1. Crumbles
and poorly bonded to coarse aggregate in many areas. Sample has
exterior finish of 15mm - 20mm thick render well bonded to concrete
but aerated.

INSPECTOR
NAME:

CORE MARK/NO:

DATE OF EXAMINATION:
SIGNED: ft/ih

29.7.85

J- / ^ * * * * n .

138

Ralli Building, 1914

-139

R a l l i B u i l d i n g , 1914

- 140

10.

RESULTS
10.1

Optical Microscopy
10.1.1

Greek (Camiros) Concrete

10.1.1.1

Location
The examined

sample was prepared

perpendicular

to

both outer surfaces.

10.1.1.2

Aggregate
A

mixture

of

weathered

aggregates was present.

siliceous

and

calcareous

Some volcanic aggregate was

noted but none typical of Santorin Earth was found.

10.1.1.3

Cement
The cementitious phase was calcium carbonate formed
as

result

of

atmospheric

carbonation

of

lime.

Extensive cracking in the cement probably arose as a

consequence

of

drying

and

carbonation

shrinkage,

although some cracking may be due to weathering of

the surface.

Many voids were visible which may have

arisen either from bad compaction or from loss due

to disintegration of aggregate and cement.

Optical ptrographie work by the Building Research

Establishment
water

tank

carbonated.

(92)

on

confirmed

a
that

sample

from

the

this concrete

Camiros
is fully

No definite evidence of the original

presence of pozzolanic material was found although

unidentifiable, shadowy

relict grains were present

which may have been pozzolana.

It was surmised that

any CSH present as a result of pozzolanic reaction

would have been decomposed by carbonation.
many

small

Although

and irregular pores were noticed, this

141-

concrete was considered well compacted compared to

other

ancient

cracking

concretes.

observed

At

least

some

of

in the matrix was considered

the
to

be due to damage consequent upon sample extraction.

The concrete was thought to be slightly deficient in
fine

aggregate.

No

significant

evidence

of

alkali-aggregate reaction was found.

10.1.2

Woolston Quay
10.1.2.1

Location
The

examined

section

was

prepared

to

the

outer

surface of sample 3.
10.1.2.2

Aggregate
The coarse aggregate was flint gravel intermingled
with

quartzite

silica

particles.

sand,

glauconite.

The fine aggregate was

intermingled
Although

the

with
latter

particles
is

of

typical

marine sandstone, the aggregate does not appear to

have been sea-dredged, owing to the absence of shell
fragments.
this can

The minimum aggregate size was 120

be compared

to

the modern-day

urn,

aggregate

minimum size of 90 pm.

10.1.2.3

Cement
The cement
size;

this

particles
can

be

were

approximately

compared

with

80 pm

in

modern-day

Portland cement in which particle sizes range fromapprox. 2 to 100 /jm, with an average size of about
19 fjm.

A dearth of calcium hydroxide crystals was

observed, which may indicate that a dry concrete mix

was used.

-142

The measured depth of carbonation was approximately

7mm-

Traces of carbonation

crack

paths

perpendicular

were found

to the surface

following
down to

approximately 20mm.
Cracks

in

the

cement

paste

were

probably formed during curing.

of

the

cement

cracks.

paste

has

empty

and

were

No further hydration

taken

place

within

the

A few cracks parallel to the surface were

observed; these were probably due to weathering of

the outer surface.
Many

entrapped

air

voids

were

present.

Calcium

hydroxide crystals were found in voids adjacent to

aggregate particles.

10.1.3

Weaver's Mill
10.1.3.1

Location
The examined section was prepared perpendicular to
the outer surface of sample B.

10.1.3.2

Aggregate
All the aggregate was less than 10mm in size.

The

coarse aggregate was a mixture of cherts, quartzites

and silica-cemented

siltstones, with some mica and

fragments of shell and anthracite..

The aggregates

had been crushed, resulting in their angular shape.

The

fine

aggregate

was

fairly

coarse,

with

minimum size of approximately 240 jjm; this can be

compared with a modern-day aggregate minimum of 90
urn.

143

10.1.3.3

Cement
The cement particle size was approximately 120 pn;
this can be compared to a modern-day Portland cement
particle

size

distribution

between

with an average size of 19 (jm.

grains were present.

2 and

100 (jm,

Unhydrated cement

A high proportion of calcium

hydroxide crystals was visible.

The

concrete

was

carbonated

to

depth

of

approximately 10mm maximum.

Many entrapped air voids were visible.
10.1.3.4

Cracking
Cracking

through

at least one aggregate grain was

noted, as was cracking

in the cement paste.

All

cracks were empty.

10.1.4

Reading Abbey
This sample was studied at the Building Research Establishment
(92).
10.1.4.1

Aggregate
The

medium

composed

and

coarse

principally

fractions

of

flint

Limestone (Jurassic) pebbles.

within

the

quartzites
agregate

medium
and
was

quartz/quartzite
and

limestones

present.

with

were

were
and

ironstones,
The

fine

principally

of

ironstone,

The

Jurassic or Cretaceous origins.

-144-

(Cretaceous)

sandstones.

composed
sand,

5mm)

In addition to these,

fractions

calcareous

( >

glauconite

glauconite

suggests

10.1.4.2

Cement

The matrix was a completely carbonated lime paste,

coarsely crystalline and rather porous.
of

pozzolanic

divided

material

material

carbonate

and

in

could
the

siliceous

be

No evidence

found;

paste

finely

consisting

fragments

was

derived by attrition from the aggregate.

of

probably
Relatively

little cracking was found, possibly as a result of

the mix

design, which

grading, minimising

closely

resembles a modern

shrinkage.

A small amount of

entrapped air was present as irregular pores about

2mm in diameter.

10.1.4.3

Lime-Aggregate Reaction
A reaction rim was visible around each chert grain,
formed as a result of reaction with the lime.
types of reaction were identified.
evident

as

carbonate

rim, about

which

may

1mm

have

The first was

thick, of

originally

subsequently decomposed by carbonation.

type

is

present

0.1mm thick.

as a porous, amorphous

very

densified
been

CSH

The second
rim, ca.

The third type affects smaller flints,

causing internal cracking and leaving the

material

Three

porous.

None

of

these

residual
reactions

appeared to have caused cracking due to expansion.

10.2

Sieve Analysis of Aggregate

10.2.1

Weaver's Mill
The sieve analysis is compared with the limits for all-in 10
mm

aggregate

shaded area).

according

to

BS882

(93)

in

fig. 10.2.1

(the

The grading curve departs from these limits in

both the coarse and fine fractions.

- 145

FIO.10.2.1

Taylor Wood row

Research Laboratories
SIEVE ANALYSIS

GRAPHICAL REPRESENTATION OF SIEVE ANALYSIS

WEAVER'S.MIUU

METRIC SIEVE SIZE

A

20

100

37.5

e?
ii

en

<

200

100

52

25

14

Vie

B.S. SIEVE NOMHER OR SIZE

/*36a*
Taylor Woodrow Construction Ltd
345 Ruitlip Road Southall Middlesex UB1 2QX Telephone 01-578 2366

- 146

MG.10.2.2

Taylor Woodrow
Research Laboratories
SIEVE ANALYSIS
WOQL.T.QH.QPAY

GRAPHICAL REPRESENTATION OF SIEVE ANALYSIS

METRIC SIEVE SIZE
mm
1.18

.um

2.J6

C3
ii

co
<

o,

200

100

52

25

14

yi6

B.S. SIEVE NDKBER OR SIZE

feea*
Taylor Woodrow Construction Ltd
345 Ruislip Roed Southed Middlesex UBI 2QX Telephone 01-578 2366

- 147

14

10.2.2

Woolston Quay
The sieve analysis is compared with the limits for all-in 20
mm aggregate according to BS882 (93) in fig. 10.2.2 (the
shaded area).

The grading curve corresponds well with the

lower limits.
10.3

Depth of Carbonation Analysis

10.3.1

Weaver's Mill
10.3.1.1

10.3.1.2

Phenolphthalein Indicator
minimum depth

3 mm

maximum depth

9 mm

10 mm

Optical Microscopy
maximum depth

10.3.2

Woolston Quay
10.3.2.1

10.3.2.2

Phenolphthalein Indicator
minimum depth

0.5 mm

maximum depth

1 mm

7 mm

Optical Microscopy
average depth

Traces of carbonation were found following crack

paths perpendicular to the surface down to approx.
20mm.
10.3.3

Discussion
A simple inverse square law may be used to describe the
dependence of the depth of carbonation with time (94):

-148-

Kt2
where

depth of the carbonated zone in

mm

time in years

a constant which varies with conditions of

exposure and concrete composition.

Figg

(46), in

his

analysis

of

Portland

Hall

concrete,

considered values of k between 1 and 6 appropriate for outdoor

exposure in a sheltered position.

Adopting these limits, the

carbonation depth might be expected to be between 9 and 56 mm

for Weaver's Mill concrete.
samples examined within

Although the locations of the

the structure of Weaver's Mill

are

unknown, the fact that the observed carbonation depth is at

the lower limit of the anticipated penetration depth indicates
the quality of this concrete.

For Woolston
are also
within

Quay, the anticipated carbonation

9 and

56mm.

The location

the quay structure

depth limits

of the samples

tested

is unknown, but photographs show

that the structure was open and exposed.

Carbonation depths

of 1mm or less for an 86 year old structure are extremely low;

this might be expected

for an underwater

concrete, however

research on a 35 year old marine structure has shown that this

is not necessarily the case (98).

Both
ages.
Hall

concretes
Figg

have very

low carbonation

depths

for

their

(46) reported depths of carbonation of Portland

concrete

between

2 and

5mm, although

the

anticipated

depths are between 10 and 70mm for a 130 year old structure.
Cabrera and Woolley (106) examined by X-ray diffraction a 25
year old concrete, made with pulverised

fuel ash as a 20%

cement replacement, and found that the extent of carbonation

was virtually nil, even very close to the surface.

Weaver's Mill and Woolston Quay concretes have very different

permeabilities

(section

10.7) and the ingress of aggressive

agents such as carbon dioxide might be expected

149-

to be much

greater

for

Weaver's

carbonation
concrete.

depths

Mill

are

concrete,

only

however

slightly

the

greater

observed
for

this

The reasons for the resistance of both concretes to

carbonation would appear to be:

a)

high cement contents (Section 10.4.3), providing a large

reserve of alkaline material.

The amounts of unhydrated

cement present in both concretes after 86 years points to

the

possibility

for

occurred

through

further

calcium

the

the

hydration

concretes'

hydroxide

and

process

lifetime,

to

have

producing

alkalis,

thereby

The dense microstructure of the cement paste.

Although

maintaining the high pH environment.

b)

Weaver's Mill concrete contains considerable voidage, the

density of the cement paste (as observed by SEM, section
10.5)

is

such

that

considerable

diffusion

resistance

of the paste might be expected.

10.4

Bulk Chemical Analysis

10.4.1

Samples Examined
Two samples each of Woolston Quay and Weaver's Mill concretes
were examined.

10.4.2

Lime Saturation Factor

Table 10.4.1 shows the results of the analyses of the concrete
samples.

If the figures for CaO, Si02>

AI2O3 and Fe23 are

assumed to be due only to the cement then the compositional

analysis

for

calculated.

the cement,

as shown

in

table

10.4.2

can

be

These figures can be compared with those of a

typical 0PC (78).

The major difference lies in the silica

content, which is higher for the two old concretes.

be expressed

in

terms of

the lime saturation

This can

factor

(LSF)

(1,101), which assesses the maximum proportion of lime which

can be made to combine with the acidic oxides during cement
burning (101):

150

% by weight of sample

Acid
Sample

Loss

insoluble
residue

Woolston

on

CaO

Si02

AI2O3

Fe 2 0 3

ci-

ignition

61.6

7.33

18.35

8.38

1.67

0.70

0.16

62.9

6.22

18.53

7.87

1.63

0.74

0.16

62.25

6.78

18.44

8.13

1.65

0.72

0.16

70.0

8.59

13.58

5.26

1.09

0.67

0.05

70.4

8.58

13.58

5.27

1.08

0.64

0.05

70.2

8.59

13.58

5.27

1.09

0.66

0.05

CaO

AI9O-5

Cement

Si02

Fe 2 0 3

Content

2.3

2.3

29

2.6

1.7

21

Quay

average
Weaver's
Mill

average

Table 10.4.1

Bulk Chemical Analysis of Woolston Quay and Weaver's Mill Concretes

% by weight of cement

Cement

CaO

Sample

SiO-2

A1 2 0 3

Fe23

ci-

aggregate
cement

Woolston

content

LSF

kg m -'

63.72

28.09

5.70

2.49

0.55

2.2

666

0.73

65.92

25.58

5.29

3.20

0.25

3.4

483

0.82

64.5

20.7

5.5

2.5

Quay

Weaver's
Mill

OPC
(78)

Table 10.4.2

0.97

Bulk Chemical Analyses of Woolston Quay and Weaver's Mill Concretes.

LSF =

(CaO) - 0.7 (SO3)

(10.1)

2.8 (Si02) + 1.2 (AI2O3) + 0.65 (Fe203)

Neglecting the sulphur contents (not analysed), which would
account for a minor correction, the LSF values are 0.73 and
0.82 for Woolston Quay and Weaver's Mill respectively.

These

values lie within the permitted range of 0.66 and 1.02 for an
0PC in BS 12 (101), but nevertheless show that the cement is
somewhat deficient in lime.
10.4.3

Cement Content
The calculated cement contents (table 10.4.2) of 666 kgm"-' for
Woolston

Quay

concrete

and

483

kgm"^

for

Weaver's

Mill

concrete can be compared to a range of 300-350 kgm -' for a

typical, modern, grade 30 concrete.
Such high cement contents are likely to have a profound effect
upon the durabilities of the concretes.
Although the concretes cannot be directly compared with modern
ones, because of the differences in cement mineralogy and
particle size, the high cement contents would be expected to
form high strength concretes, with dense cementitious matrices
of low porosity.
excellent

Such concretes would be expected to afford

protection

to reinforcing

steel, given adequate

cover.
10.4.4

Cement Compound Compositions

If

the

potential

compound

compositions

are

calculated

according to Bogue (102,1), the figures shown in table 10.4.3

are obtained and are compared with those calculated for a
modern 0PC in BS 12 (101).

They show that, while the amounts

of C3A and C4AF are very similar, the two old cements would
contain significantly greater amounts of C2S and much less
C3S.

-153-

Sample

C3S

c2s

C3A

Oi
4t

C4AF
%

Woolston Quay

4.06

77.48

10.89

7.57

Weaver's Mill

33.88

47.79

8.59

9.73

OPC

59.57

14.42

9.30

7.6

(78)

Table 10.4.3

Bogue Calculated Compound Compositions

Between the two old cements there is a wide discrepancy, with

Weaver's Mill cement apparently containing much more C3S than
Woolston

Quay

cement.

This

difference

may

reflect

inaccuracies in the calculation due to the assumptions made.

The

results

Halstead

can

compared

with

analyses

tabulated

by

(51) for cements from England, Germany, France and

the U.S.A.
13

be

between the years 1849 and 1963.

analyses

of

English

cements

in

1890

An average of

give

computed

compound composition of 9% C3S and 59% C2S and an average of

12 analyses of French cements for the same year gave 18% C3S
and 53 C2S.

The results for Weaver's Mill and Woolston Quay

cements are therefore broadly in agreement with other analyses

of the same period.

The difference between the two cements

may be significant and indicate a different provenance.

It

has been said that Hennebique imported all the materials for
Weaver's

Mill

from

France

(47), but

this

has

never

been

claimed for Woolston Quay and would seem to be unlikely, given

the

size

of

analyses

of

the

English

Weaver's Mill

Portland
and

cement

Woolston

industry.

Quay

may

The

therefore

represent those of French cement of 1897-8 and English cement

of 1899 respectively.

10.4.5

Setting Times and Strength

The two cements with their high C2S contents, would be poor
Portland

cements by today's standards.

setting, with low early strengths.

They would be slow

Weaver's Mill cement, with

a higher C3S content, would exhibit a higher, early strength

than Woolston Quay.

This may account for the difference in

calculated cement contents for the two concretes; the higher

proportion of cement for Woolston Quay being employed by L.G.
Mouchel

with

material.

knowledge

of

the

strength

properties

of

the

Setting times and strength are, of course, also

dependent upon other variables, such as fineness and water to

cement ratio.

- 155

104.6

Heats of Hydration
With modern, fine ground, high C3S, Portland cements the high
cement contents as used in Weaver's Mill and Woolston Quay
concretes might be expected to cause problems due to thermal
cracking as a result of the heat of hydration of the cement.
The heat of hydration of C2S (44.6 kJ/mol, 62 cal/g), however,
is half that of C3S (114 kJ/mol, 120 cal/g) and the hydration
and

development

of microstructure

are about

twenty

times

slower for C2S than C3S (1, 132), so that high belite cements
will evolve considerably less heat . than high alite cements
upon hydration.

Added to this effect will be the lower

reactivity to be expected from the old cements less finely

ground than modern cements and with a wide particle size
distribution.

That thermal cracking was not a problem is

evident from the nature of the concrete itself.

10.4.7

Chloride Content
Chloride contents were measured by weight of concrete sample
(table 10.4.1) and were calculated by weight of cement (table
10.4.2).

Weaver's Mill stood on a quayside and may have been

exposed to salt spray.

is from unwashed

Another possible source of chlorides

aggregate.

The presence

of sea shells

indicates that the aggregate may have been sea-dredged.

The level of chloride by weight of cement in Woolston Quay is
higher than the 0.4% activation level commonly accepted for
the corrosion of reinforcing steel (105).

Since the aggregate

does not appears to have been sea-dredged, the source of this

chloride is obviously the sea.

This result correlates with

the observation of some spalling of concrete and rusting of

steel when the structure was examined in 1963 and with the
observation

of

reinforcement

laboratory samples.

156-

corrosion

in

some

of

the

10.5

Scanning Electron Microscopy

10.5.1

Experimental
Samples were

impregnated

with

polished to fjm finish.

epoxy

resin, sectioned and

The polished sections were coated

with carbon and examined in an ISI DS 130 scanning electron

microscope at Blue Circle Research, Greenhithe and in a JEOL
35CF scanning electron microscope at Imperial College.

Both

microscopes were equipped with back-scattered electron (BSE)

detectors.

The ISI DS 130 was equipped with a Princeton Gamma

Tech (PGT) System 4 energy dispersive X-ray microanalytical

system.

X-ray

accelerating

microanalyses

voltage, with

were

recorded

the specimen

at

tilted

15 kV

to a 42

X-ray take-off angle.

10.5.2

Results and Discussion

1.

Weaver's Mill
Fig. 10.5.1 shows a low magnification BSE image, giving
an overall view of the microstructure.

In the BSE image

aggregate grains are dark, generally large and angular.

Bright areas are unhydrated cement grains.

The grey

interstitial phase is the hydrated cement.

The dense

microstructure of the cement paste is evident.

magnification

image,

fig.

microstructure in greater detail.

10.5.2,

A higher

shows

the

It is possible that

some of the cracks observed may have been introduced

during sample preparation.
can be distinguished.

Several, different regions

The grey, fibrous, porous matrix

is 'outer' calcium silicate hydrate (CSH), whilst those

homogeneous areas of similar greyness, with a smoother
appearance, correspond to 'inner' CSH and are relicts of
the

original

alite

or

belite

grains.

As

regions

containing unhydrated grains show, the original cement

grains were

often

polymineralic, so that

a definite

identification of the original grain composition remains

157

Fig. 10.5.1

Low magnification BSE image of Weaver's Mill concrete. The

area outlined is that shown at higher magnification in fig. 10.5.2

15KU
Fig. 10.5.2

350X

SOU

4331

BSE image of Weaver's Hill concrete, showing the area outlined in

fig. 10.5.1

- 158-

tentative.

The grain marked A in Fig. 2 has completely

hydrated, leaving featureless CSH (areas 12 and 13, table

A.3.3).

The large grain B at centre is about 120 jjm

across;

here

hydrated

and

all

the

original

remaining

silicate

unhydrated

areas

interstitial aluminate and ferrite phases.

two

minerals

(ferrite

are

identified

exhibiting

the

both

by

brightest

phases

have

are

the

These latter

their

contrast

contrast

of

the

Portland cement minerals) and by microanalysis (table

A.3.3).

It is interesting

that these minerals have

remained unhydrated whilst the surrounding silicates have

completely
non-silicates

reacted.
has

The

CSH

apparently

surrounding

acted

as

the

diffusion

barrier preventing hydration over a period of more than

eighty years.

Analyses of CSH (table A.3.4) indicate an

average Ca/Si ratio of 1.5.

Other samples (examined at Imperial College) indicated
that

the

larger

cement

grains had

hydration rims of 10-20 jjm.

relatively

narrow

As with other samples, no

obvious areas of calcium hydroxide were found.

could

be

indicative

of a low

alite

content

This
in the

original cement (alite hydrates to produce three times as

much calcium hydroxide as does belite) and/or a low water
to cement ratio.
found.

Evidence, of twinned belites has been

Polysynthetic twinning in belites arises as a

result of cooling

from high temperature polymorphs (

oC-+oC-*/3 C2S) and the observation of microstructures can

be used as an indication of kiln temperatures (89, 90).
Lack of a twinning

structure indicates a low firing

temperatures, less than those for modern cements.

2.

Woolston Quay
A low magnification BSE image is shown in fig. 10.5.3 and
shows aggregate (dark, irregularly shaped), CSH matrix
(grey),

unhydrated

porosity (black).

cement

grains

(light

grey)

and

Voidage is particularly noticeable at

159

Fig. 10.5.3

Fig. 10.5.4

Low maEnification BSF ir^F <~>f W^^lst^n O'.ny ~?r.~r^i-".

area cjt.iir.yc; is triat snown in i'ig. luo.*

BSE image of Woolston Quay concrete, showing the area outlined in

fig. 10.5.A at higher magnification.

160-

Fig. 10.5.5

BSE image of Woolston Quay concrete, showing a polymineralic,

unhydrated grain; A = alite, B = belite, AM = aluninate,
F = ferrite.

'"^'.'.'

Fig. 10.5.6

BSE image of Woolston Quay concrete showing a twinned, fractured

crystal of belite.

161

the edges of aggregate grains.

the

midst

of

unhydrated

These

probably

liquid

phase

hydration

rim

arose
in

cement

from

the

Smaller pores occur in

gas bubbles

kiln.

around

the

grains,

There

fig.

10.5.4.

present

appears

large, central

in

to

pore

the

be

in

fig.

10.5.4, but its extent is very limited, about 5-15 pi,

implying restricted access of water to this region.

The

unhydrated grain in fig. 10.5.4 is made up predominantly

of alite

grains.

polymineralic,

A large

unhydrated

(180 jjm x 80 jjm approx.),

grain

containing

all

four

Portland cement minerals is shown in fig. 10.5.5.

grain

is

mostly

made

up

of

alite

The

sub-grains,

with

aluminate as the second most abundant phase, followed by

belite and ferrite.
seen surrounding
pm.

A rim of hydrated material can be

the grain, with a depth of about 3-25

Analyses of CSH (table A.3.4) indicate an average

Ca/Si ratio of 2.1.

Fig. 10.5.6 shows an interesting phenomenon.

of belite containing
twin planes.

A crystal

twin lamellae has fractured

along

The fracture has propagated along one twin

plane and 'stepped across' several times to proceed along

different twin planes.

Other

samples

examined

(at

Imperial

College) showed a

wide cement particle size distribution.

unhydrated

cement

grains

contained

Some of these
intergrowths

of

ferrite and aluminate on a fine scale, giving a 'stripey'

appearance.
melt

and

may

exsolution.

Such textures have perhaps arisen

represent
The

a cooling

amount

of

phenomenon,

unhydrated

in the
such

material

as
was

estimated as between 10 and 20%.

3.

Camiros (Ancient Greek)

Fig. 10.5.7 shows a low magnification image of a typical
area.

The cement matrix is fine-grained

and dense in

places, but is extensively cracked, with fine material in

- 162

Fig. 10.5.7

Fig. 10.5.8

Low magnification, BSE image of Camiros concrete. The area

outlined around the grain marked 'A' is that shown in fig. 10.5.

BSE image of Camiros concrete, showing the grain marked 'A' in

fig. 10.5.7 at higher magnification.

163

the cracks.

Within the matrix calcium counts predominate

in a typical analysis; this material is mostly a fully

carbonated

lime

mortar.

interesting features.
away

from

the

There

are,

however,

certain

The cement appears to have shrunk

aggregate

in

probably

connected

with

matrix;

the

fine

material

precipitated

after

the

many

places

the extensive
in

cracking

the

and

this

cracking
cracks

or may

is

in the

may

simply

have

be

the

remaining debris.

Fig. 10.5.8 shows the grain marked A in fig. 10.5.7 at

higher magnification.

The analysis of the centre of this

grain (area 1, table A.3.1) indicates that it is nearly

pure

SO2;

it

originally
however,

probably

with a smooth
has

an

reaction with
grain

was

a wind-blown

surface.

eaten-away

(analyses

grain,

The perimeter

appearance

the surrounding

sand

now,

indicative

matrix.

of

The rim of the

2, 3, 5 and 6, table A.3.1) contains

significantly more Na, Mg, Al, K, Ca, Ti and Fe than the

interior and the surrounding carbonate matrix (analyses 4
and 7, table A.3.1).
possessed

It may be that the grain initially

reactive

silicate

rim

and

that

reaction

stopped when the more pure, silica region was reached.

No

definite

evidence

was

found

for

the

use

of

pozzolanic material, as claimed by Efstathiadis (7). The

particle marked B in fig. 6 (analysis 13, table A.3.1)
may be a particle of volcanic earth.

The analysis is

compared that of Santorin Earth (7) in table 1.

Given that the electron beam may have been encompassing a

multi-phase

area

and

composition

of natural

given

the

variation

in

pozzolanas, it might

chemical
be argued

that there is some similarity in the analyses and that a

very

small

present;

amount

this

of

volcanic

conclusion

microscopy (Section 10.1).

- 164-

is

earth

was

supported

originally
by

optical

Santorin Earth

Area 13

Na
Mg

0.33

0.78

Al

6.19

7.9

Si
S
K

34.86

30.8

Ca

1.55

Ti
Fe

0.18
1.12

47.69

0.76

0.04
3.44

Table 10.5.1

2.9
3.8

Analysis of Area 13 (Table A.3.1)

compared with Santorin Earth (7).

Figures expressed in weight %.
10.5.3

Samples Examined at Imperial College

1.

Cement Barrel (1848)

The microstructure of a piece of a cement barrel from the
'Ship on Shore' public house, Sheerness has been examined
(91).

A wide cement particle size distribution was

found; there was a considerable amount of material less

than 5 jjm and sizes ranged up to 600 jjm plus.
smaller

than

100 /jm had

completely

Particles

hydrated, but

particles larger than this (some of these approaching

0.5mm in size) contained anhydrous cores.
completely
remained

hydrated
intact

and

grains,
showed

the

ferrite

In otherwise
phase

had

no evidence of reaction.

Hydrated belite relicts showed no striations indicative

of an originally twinned structure; this was taken to be
evidence of a low cement burning temperature.

Massive

areas of calcium hydroxide were not found and this was

interpreted as probably being due to the small amount of
alite originally present, i.e. this was predominantly a
belite cement. Particles of silica, thought to have been
introduced inadvertently during grinding, had undergone
no noticeable reaction in the cement.

- 165-

2.

Portland Hall

Preliminary investigations of the concrete from William

Aspdin's

Portland

Hall

showed

the presence

of

twinned

belite grains.
3.

Hadrian's Wall

Preliminary

investigations

indicated

very

fine

microstructure.
4.

Ralli Building
Preliminary

investigations

showed

the

presence

of

the

clusters of-belite grains.

10.6

Taywood Engineering Water Sorption Test

10.6.1

Samples Tested
One sample of Woolston Quay and one sample of Weaver's Mill
concrete were tested.

10.6.2

Results
Sorptivity (mm/min2)

Sample

10.6.3

Woolston Quay

0.08

Weaver's Mill

0.04

Discussion
Values

of

water

sorption

have

been

permeability for concrete (96, 97).

correlated

with

On this basis a scale of

acceptability is as follows:
Sorptivity

<

0.10

0.10-0.20

Good

average

>

0.20

(mm/minz)

-166

water

Poor

Woolston Quay and Weaver's Mill both have a good performance

on this scale.
concrete, which

This seems surprising

has

a high

water

for Weaver's Mill

permeability

and would

therefore be expected to have a sorptivity greater than 0.20

mm/min*.

10.7

Water Permeability

10.7.1

S amples Tested
Two samples of Woolston Quay and two samples of Weaver's Mill
were examined.

10.7.2

Results

Valena's
Sample

Coefficient

m/s
Woolston Quay
Woolston Quay
Weaver's Mill
Weaver's Mill

14
(1) 1.03 x IO"
(2) 2.02 x IO - 1 4
9
(1) 2.09 x IO"
(2) 3.05 x IO"8

Table 10.7.1
10.7.3

Darcy's
Coefficient Void Content

m/s

10.14

13.6

2.36 x IO"9

6.55

6.48

1.06 x IO"

Water Permeability Results

Discussion
The

current, proposed

classification

(97) for

permeability of concrete is:

permeability coefficient m/s
< 10-12

10-12.10-10

Low

average

-167

> io-io
high

the

water

Woolston Quay, therefore, has a very low permeability in this

classification, but Weaver's Mill has a high permeability,
some five orders of magnitude greater than Woolston Quay.
10.8

Oxygen Diffusion
10.8.1

Samples Tested
Two samples of Woolston

Quay

concrete and

one sample of

Weaver's Mill were examined.

10.8.2

Results
Woolston Quay

(1)

D02 = 9.76 x 10"9 m 2 s"1

(2)

D02 = 8.28 x IO"9 m 2 s"1

average
Weaver's M i l l
10.8.3

D02 = 9 . 0

x 10~ m2 s~l

D02 = 2 . 5

x 10" 7 m2 s " 1

Discussion
The

current,

proposed

classification

(97)

for

oxygen

d i f f u s i v i t i e s i n concrete i s

Do2 (m2 s" 1 )

< 5 x 10" 8
Low

5 x 10" 8 -5 x 10" 7
Average

> 5 x 10~7
High

Woolston Quay, according to these criteria, has a low oxygen

diffusivity, whilst Weaver's Mill has a considerably higher
diffusivity and is of 'average' rating.
10.9

Mercury Intrusion Porometry (MIP)

10.9.1

Results
A summary of pore parameters for the samples examined is given
in table A5.1.

Figs. A5.1 to A5.16 include cumulative pore

size distributions and differential pore size distributions

for these samples.

168

10.9.2

Interpretation of Pore Parameters

Pore parameters such as the total intruded pore volume (TPV)
and the pore volume for pores with diameters greater than
0.132 um (or 660 A radius, as is frequently referred to) have
been correlated with water permeability, oxygen diffusion,
water sorption and compressive strength of concretes (81, 82,
83, 84, 95, 96).
The upper limit of 15 im pore diameter in the measurement
range of the porosimeter means that those samples possessing
considerable
Since,

voidage

however,

are

these

not

large

necessarily
pores

are

distinguished.
not

necessarily

continuous, they may have little or no effect on the transport

properties, although they will affect the strength of the
material.

The correlation between the transport properties of

concretes and pores with diameters greater than 0.132 urn is

less certain

for concretes

than cement

pastes.

This is

thought to be due to microcracking at the interface between

the aggregate and the cement paste and other effects which can
arise through sample preparation.
10.9.3

Quality Criteria
Quality criteria can be roughly stated thus (96):
Pore Volumes ( ^ 0.132 urn diameter)
>

10%

5-10%

< 5%

Quality
assessment

poor

average

good

Table 10.9.1 ranks each of the concretes studied within these

categories.
1)

The following points are of interest:

Nearly all the concretes fall into the average and poor
categories.

Only two lie in the good category, although

- 169-

CLASSIFICATION OF CONCRETE QUALITY IN TERMS OF

PORE VOLUME FOR PORES WITH DIAMETERS GREATER THAN 0.132 u.m

POOR

AVERAGE

Portland Hall F2

Portland Hall k

GOOD

Portland Hall F
Railway Terraces, Hull
Reading Abbey B

Reading Abbey A

Greek (Camiros)
Woolston Quay - Surface

Woolston Quay - Bulk

Ralli Building M1 Mortar

Ralli Building N

Ralli Building K

Ralli Building M1

Ralli Building 01
Weaver's Mill - Bulk 1
Weaver's Mill - Bulk 2

Table 10.9.1

- 170-

some (Woolston Quay surface and Weaver's Mill bulk) are

borderline average to good.
2)

The analysis distinguishes between dissimilar concretes

from the same source.
Portland

Hall

Examples of this are the two

concretes,

samples

being

from

the

decorative Fleurs de Lys and sample 4 being a core from

the wall, and Reading Abbey samples A and B.
3)

The analysis gives a false impression of the quality of

Weaver's Mill concrete.

Water permeability and oxygen

diffusion tests have shown that this concrete is highly

permeable. Weaver's Mill concrete would therefore appear
to possess inter-connected channels and voids in the size
range too large to be measured by the porosimeter.
10.9.4

Pore Size Distributions

Pore dimensions in this section are discussed in Angstrom
units (A) in order to correspond with the distributions, Figs.
A.5.1 to A.5.16 (1 A = 10-10m = 10~ 4 fin).

660 A pore radius

is that dimension above which the porosity is thought to

dominate the water permeability.
1.

Portland Hall (Figs A5.1, A5.2, A5.3)

Both samples from the decorative Fleurs de Lys (samples F
and

F2) show

similar

distributions, which are quite

different from that given by the core from the wall

(sample 4 ) .

In samples F roughly two thirds of the

porosity lies above 660 radius, with a peak at ca. 7 x

10-* A; this concrete would be expected to have poor
permeability characteristics.

Sample 4 has less total

porosity than sample F and the distributions show that

the majority of this lies sub - 660 A, with a peak at
about

70 A radius; this concrete would be expected to be

of average permeability.

171

2.

Railway Terraces Hull (Fig. A5.4)

This concrete has a high total pore volume of nearly 22!8,
approximately 3/5 of this lies above 660 A, with a peak
at ca 6 x 1CK A; this concrete would be expected to be of
high permeability.

3.

Reading Abbey (Samples A and B, Figs. A5.5 and A5.6)

The two samples are quite different.

Sample A has a high

total pore volume, but two thirds of this porosity lies

below

660 A.

Permeability characteristics would be

expected to be average to poor.

the total porosity
above

of A, but

Sample B has about half

nearly all of this lies

660 A, peaking at ca 2 x 10^ A.

This sample would

be expected to have high permeability.

4.

Greek (Camiros) (Fig. A5.7)

The total pore volume is moderately high at 18% and most
of this, 15%, lies above 660 A.

This concrete would be

expected to have poor permeability characteristics.

5.

Woolston Quay (Figs. A5.8 and A5.9)

Two

samples

were

examined,

one

from

the

another from the bulk of the concrete.

total porosities of about IOS.
volume lies below 660 A.

surface

and

Both have low,

Roughly half of the pore

The surface concrete contains

more large pores than the bulk, the former being of good
to

average

Moderate

quality

and

the

latter

of

good

quality.

to low permeabilities would be predicted

from

these results.

6.

Ralli Building (Figs. A5.10 to A5.14)

Five samples were examined; the results demonstrate the
variability of this concrete.

- 172-

Although sample K has a

high total pore volume only a small proportion lies above

6 6 0 A and this sample would be expected to have good
permeability characteristics.

Samples N and 01 are of

average quality and Ml is poor with significant porosity

above 660 A and a peak at ca. 5 x 10^ A.

The mortar

sample from piece Ml has a moderately high

total pore volume, the majority of which is above 660 A,

peaking at ca 3 x 10^ A.

This material would be expected

to be very permeable; it may have been designed as a high

water/cement, low strength render.

7.

Weaver's Mill (Figs. A5.15 and A5.16)

Both

samples, of bulk

concrete, gave similar results.

The total pore volumes are quite low, ca. 10S and roughly
50% of the porosity is above 660 A, giving this concrete
a good to average rating.

Since, however, we know that

this concrete is highly permeable a measurement of larger

pore

diameters

than

have

been

measured

(max.

15 jm

diameter) would be useful.

Discussion

Fig. 10.9.1 shows an experimental relationship, derived from a

study

of

'normal'

concretes,

between

the

Valena

water

permeability coefficient and the pore volume greater than 660

A (96).
marked

The position of each sample, as per pore volume, is

on

the curve.

The positions

of Woolston

Quay

and

Weaver's Mill concrete, as determined by pore volume and water

permeability measurements, are also marked and it can be seen
that these fall off the curve.

It may be, therefore, that the

criteria applicable to modern day, 0PC concretes do not apply

to old and ancient concretes; this discrepancy emphasises the
need for a range of experiments to determine the properties of
a concrete and hence assess its quality.

- 173-

Fig. 10.9.1
/ATER PERMEABILITY
(Valena m/s)

1 Weaver's MMI (measured)

2
5*

10S

13 T

POOR

10^"

1011

AVERAGE

OO.

K)"
GOOD

XP"

10r15

Woolston Quay(measured)

S
10
*
VOLUME OF PORES 6 6 0 7 5 0 0 0 A (%)

20

Fig 10.9.1 Relationship between pore volume and water permeability. The smooth
curve is an experimentally determined relationship (96). On this curve the
positions of the samples examined are marked,from their determined pore volumes,
as predictions of their water permeabilities. The water permeabilities
experimentally determined for Weaver's Mill and Woolston Quay concretes are also
marked.

174

10.10 Thermal Analysis

10.10.1 Experimental
The samples were finely ground in an agate pestle and mortar.
About 100 mg of sample were placed in a platinum crucible,
alumina powder in a matched crucible was used as a reference
for DTA.
a heating
recorded

The samples were heated from ambient to 1000C at

rate of 20/min.
simultaneously

DTA, TG and TG curves were

with

Stanton

Redcroft

STA

781

thermal analyser.
10.10.2 Results (see Appendix 2)
Figs. A.2.1 to A.2.16 show the graphical output from the
thermal analyser for each sample.
analysis of these results.

Table 10.10.1 contains an

Some of the assignments of peaks

in the thermograms are made tentatively; thermal analysis is a

technique

which

often

requires

the

back-up

of

another

analytical technique to confirm an identification.

10.10.3 Important Peaks in the Thermograms of Concretes
1.

Calcium Silicate Hydrate (CSH)

CSH exhibits a broad, endothermic hump in the DTA curve
between 100 and 150C, due to water loss.
broad

because

CSH

is

indeterminate structure.

semi-amorphous

The peak is
material

of

The peak can be identified with

confidence in Portland cement concretes such as Weaver's

Mill and Woolston Quay, but in other, non-Portland cement
concretes, where, if CSH occurs, it may have a different
structure and composition and be present in much smaller
amounts, it is less easy to identify.
case with the Ancient Greek

An example is the

(Camiros) concrete, Fig.

A.2.4, where the broad hump which peaks ca. 100C is

probably

mostly

due

to

unbound

water,

but

perhaps

contains contributions from Ca, Si or Al hydrates.

175

In

this sample, however, the presence of such hydrates was

not detected by optical microscopy or scanning electron
microscopy.
2.

Calcium Hydroxide (Portlandite)

Calcium

hydroxide

is identified

by

an endothermic

DTA

peak at ca. 490C, due to loss of structural hydroxyl.

It is therefore

of use analytically

Portland

concretes

cement

in

for both lime and

determining

the state of

carbonation.
3.

Calcium Carbonate
Calcium

carbonate,

valerite

and

and

due

Calcium

carbonate

is

calcium

hydroxide

and

of

crystalline
can

be

forms

identified

calcite,
from

shaped, endothermic DTA peak between

900C,

constituent

its

aragonite,

characteristically
750C

in

lime

to

loss

formed
is

of

upon

the

therefore

concretes,

carbon

but

dioxide.

carbonation

the most
also

of

important

occurs

when

portlandite is carbonated in Portland cement concretes.

The presence of calcium carbonate cannot always be taken
as evidence of carbonation, however, since it can also
occur in aggregates, e.g. limestones.

10.10.3 Discussion
1.

Ralli Building
The piece sampled

contains no calcium hydroxide and is

therefore fully carbonated.

Other peaks are typical of a

Portland cement concrete.

2.

Weaver's Mill
Peaks characteristic of a Portland cement concrete, with
some evidence of carbonation.

176

3.

Woolston Quay
A

Portland

cement

carbonation.

The

concrete,
peak

with

observed

insignificant

at

ca. 320C

is

probably due to calcium chloroaluminate hydrate formed as

a result of the ingress of chloride ions.
4.

Ancient Greek (Camiros)

In accord with the optical microscopic and SEM evidence
that this concrete is a fully carbonated lime mortar, a
very large calcite decomposition peak is observed with
no calcium hydroxide evident.

It is possible that the

broad hump in DTA and DTG centred on 100C contains

contributions
result

of

from

cementitious hydrates

pozzolanic

reaction,

but

formed

these

were

as a
not

detected by microscopic methods.

5.

Reading Abbey
This sample is fully carbonated, with no evidence of
calcium hydroxide.

Little else but calcium carbonate is

detected, but peaks in the region 100-300C may be due

to the presence of complex hydrates.
6.

Concrete House, 1865

This sample is fuly carbonated, no calcium hydroxide peak
is present.

The presence of CSH and other hydrates is

indicated from the broad humps in the 100-300C

region.
7.

Concrete Fort, 1899

Peaks consistent with this sample being a Portland cement
concrete are evident; only a small calcium hydroxide peak
is present, indicating a high degree of carbonation.

-177

8.

Huddersfield Old Mill, 1913

No calcium hydroxide peak is evident, so this sample is

fully carbonated.

The peaks in the region 90-200C are

rather uncharacteristic of Portland cement concrete.

9.

Joseph Aspdin Render, c. 1825

The thermogram contains no calcium hydroxide peak, but a
large

calcium

sample

is

carbonate

fully

peak

is

carbonated.

present,

hence

The large peak at

this
169C

(DTA, DTG) indicates that a complex hydrate is present,

this

cannot

Blezard

be

(42)

Wakefield

taken

noted

was

limestone

further

that

Joseph

'essentially

and

clay

without

with

more

Aspdin's
calcined

little

evidence

study.

cement

at

mixture

of

of

Ca0-Si02

interaction as the temperature of the burning was too low

for

compound

synthesis'

proto-Portland cement.
analysis

could

terming

the

material

The hydrate observed by thermal

therefore

have

arisen

either

from

rehydration of burnt clay or through hydration of calcium

compounds

formed

as

result

of

interaction

between

limestone and clay.

10.

Cement Barrel, 1848

A

strong

calcium

carbonation
present.

hydroxide

has occurred
CSH and

consistent

with

peak

is evident, but

as calcium

carbonate

some

is also

other hydrates are present. This is

the

observations

of

Blezard

(42) who,

terming this material a meso-Portland cement, noted that

it

was

heterogeneous

essential Portland

but

nevertheless

cement minerals.

contained

the

The absence of a

peak due to quartz in the DTA thermogram is indicative

that this material is a cement paste; this technique is
not

sensitive

introduced

enough

during

to detect

grinding,

optically (42).

178

the grains of quartz,

that

have

been

observed

11.

Bulla Regia, Tunisia

This sample is fully carbonated.

The broad humps in the

100-350C region may indicate the presence of complex

hydrates.
12.

Pressed Tile, 1904

The sample analysed was fully carbonated.

The thermogram

is characteristic of Portland cement.

13.

Herod's Palace, Masada

This sample is probably a gypsum concrete.

The large,

endothermic DTA peak at ca. 150C has been assigned to

gypsum; the characteristic double peak of gypsum in this
region is not present and this may be due to the sample
condition.

A simple, chemical test for sulphate proved

positive.

The high temperature peaks at ca. 720 and

820C

can

be

assigned

to

dolomite

or

dolomitic

limestone as aggregate, but may also include calcium

carbonate arising from carbonated lime in the cement.
14.

Lining of Roman Bath, Bath

This sample appears to be a fully carbonated lime mortar.
The

100-300C

region

may

show

contributions

from

complex hydrates.
15.

Railway Terraces, Hull

Fully carbonated, probably a Portland cement.

16.

Portland Hall
The sample was taken from a fully carbonated region. The
thermogram does not show the typical characteristics of a
Portland cement; a single, broad cement hydrates peak is
present.

179

TABLE 10.10.1
THERMAL ANALYSIS RESULTS

KEY;
DTA

Differential Thermal Analysis

TG

Thermogravimetry

DTG

Derivative Thermogravimetry

Broad

Exothermic

CSH

Calcium Silicate Hydrate

AFt

Ettringite

APm

Monosulphate

All DTA peaks are endothermic unless otherwise stated.

All TG steps and DTG peaks are weight losses unless otherwise stated.

-180

DTA
SAMPLE

1 : Ralli Building
(Fig. A.2.1)

110

Weavers Mill
(Fig. A.2.2

3: Woolston Quay
(Fig. A.2.3)

TG
o

110

110

ASSIGNMENT

Free Water

151b

CSH, AFt

265

AFm

580

Quartz

755

2:

DTG

755

124

Ca CO

124

136

CSH
CSH

178

178

178

AFt

490

486

486

Ca (0H) 2

578

Quartz

739

Ca CO,

754

754

Ca CO,

136

127

136

CSH

178

175

AFt

322

Calcium Chloraluminate
Hydrate

490

490

490

577
697

Ca (0H) 2
Quartz

701

885e

Table 10.10.1

181

701

(Aggregate)

SAMPLE

4: Ancient Greek
fCamiros)
(Fig. A.2.4)

ETA

DTG

TG

98b
115b

Free Water

11?
36O

630

632

5: Reading Abbey
(Fig. A.2.5)

862

63O
Ca CO

860

97b

Ca CO,

Free Water

110

110b

Free Water (Si + Al

Hydrates?)
-

846

858

ASSIGNMENT

Free Water

286
578

843

6:

Concrete House
1865
(Fig. A.2.6)

Quartz

849

849

110b
144b

144

Free Water (Cement

Hydrates)
Free Water (Cement
Hydrates)
Quartz

577
850

Ca CO

854

Table 10.10.1

-182

850

Ca CO,
3

ETA

DTG

TG

SAMPLE

ASSIGNMENT

7:

133

127

130

CSH

181

184

486

490

Concrete Fort
1899
(Fig. A.2.7)

AFt

486

Quartz

578

8: Huddersfield
Mill, 1913
(Fig. A.2.8)

820

818

820

Ca CO,
3

86

84

86

Free Water

217

266

266

(AFm)
Quartz

577

9:

Joseph Aspdin
Render Wakefield 1825
(Fig. A.2.9)

Ca (0H) 2

810

810

814

110

110

169

160

I69

250

25O

Ca CO,
3

Free Water
CSH? Cement Hydrates?

302
359
(Ca (OH) 2 )

494

822

822

Table 1 0 . 1 0 . 1

- 183-

822

Ca CO,

DTA

DTG

TG

SAMPLE

ASSIGNMENT

10: W. Aspdin
Cement
Barrel 1848
(Fig. A.2.10)

145

145

CSH
AFt

190
491

491

772

491

Ca (0H) 2

772

Ca CO,
3
Ca CO,

118

Free Water (Si or

Al hydrates?)

783

111 Bulla
Reggia
(Pig. A.2.11)

118b

110b

339

Quartz

579
636

12: Pressed Tile

1904
(Pig. A.2.12)

13: Herod's Palace

Masada
(Fig. A.2.13)

8I4

818

814

Ca CO,

136

130

136

CSH (other hydrates?)

Quartz

578

822

822

822

Ca CO,
3

111

105

105

Free Water

154

151

154

(Gypsum)
Ca SO4 (Gypsum)

389e
678

713

7I8

713

Dolomite, Mg CO,

822

822

822

Ca CO, Dolomite

Table 10.10.1
184

DTA

DTG

TG

SAMPLE

ASSIGNMENT

14s Lining of
Roman Bath,
Bath
(Fig. A.2.14)

119

121

119

Free Water

271
392

392

582
814

Quartz

816

8I4

Free Water, CSH

11 Jb

15 Railway Terraces
Hull
(Fig. A.2.15)

136

136

415
'

(AFm)

390

Quartz

818

822
Ca CO,

830

16: Portland Hall

(Fig. A.2.16)

159

CSH

292

581

822

Ca CO,
5

155

159

CSH (other Hydrates)

641

Mg CO,, Dolomite
5

392

64O

641

798

814

Table 10.10.1

185-

Ca CO,

10.11 Compressive Strength

10.11.1 Samples Tested

Cores were taken from large pieces of concrete salvaged from
Weaver's

Mill, Woolston

Quay

and

the Ralli Building.

The

coring direction was assumed to be horizontal in all cases.

10.11.2 Results and Their Treatment

The results of the testing are presented
The

estimated

strengths,

in-situ

design

cube

strengths

in Table 10.11.1.

strengths,

and

potential

characteristic
strengths

were

calculated according to published procedures (129,130).

The

compressive strength at 28 days was estimated by dividing the

in-situ cube strength by a factor of 1.6 taken from a curve
published by Tanner in 1911 (128), showing the strength gain
of concrete up to 3 years, using
workers.

This

curve

shows

data obtained

the strength

by various

of concrete

still

increasing at 3 years (about 1.5 times the 28 day strength),

but

the

strength

gain

is

levelling

off

and

appears

to be

asymptotic at approx. 1.6 times.

10.11.3 Discussion
The

estimated

in-situ

cube

strengths

are

very

high

for

Woolston Quay concrete, high for Weaver's Mill, but low for
the

Ralli

Building,

aggregate concrete.

apart

from

the

sample

(3)

of

small

The excess voidages of both Weaver's Mill

(6-83>) and the Ralli Building (858), however, are very high and
consequently the strength correction factors to be applied in
the calculation of potential strength are large (the largest
multiplication factor published (129), 1.5 times for an excess
voidage of 55S, has been used).

This has the result that the

estimated potential strength of Weaver's Mill concrete is very

high at approx. 84 MPa, greater than that of Woolston Quay,
which has a lower excess voidage.

It should be remembered

that such corrections are, of course, rather approximate.

-186-

The high strength of Weaver's Mill concrete is probably the

result

of

design

such

that

the

building

could

withstand

internal dust explosions, in common with other flour mills and

grain silos (127).
The very high strength of Woolston Quay concrete may well have
been

the

result

of

collisions from ships.

design

to

withstand

heavy

loads

and

One such collision is reported to have

happened in 1901, when nothing more than local injury occurred

(107).
The measured

low strength

of Ralli Building concrete is in

accordance with the comment of the foreman of the demolition

gang, who described the concrete as 'rather weak'.

187-

Sample

Estimated

Characteristic

Design

Estimated 28

Estimated

kgm"-'

In-situ Cube

Strength,

Strength

day strength

Potential

Strength

feu

MP a

MPa

(1)

2278

41.7

(2)

2309

45.0

(3)

2295

42.7

average

2294

43.1

(1)

2301

54.2

(2)
(3)

2297

54.5

2299

54.9

average

2299

54.5

Ralli Building (1)

2298

21.4

(2)

2293

20.3

*(3)

2313

37.9

Weaver's Mill

Woolston Quay
00
00

Density

(4)
average (1,2,4)

2296

Strength

MPa

MPa

MPa

53.9

35.9

27.0

84.5

68.2

45.4

34.1

73.6

47.4

31.6

23.7

74.3

25.6

17.1

12.8

40.2

19.7
20.5

Table 10.11.1

Density and Compressive Strength Data

*

Small aggregate Concrete

11.

REFERENCES

1)

Lea, F. M. (1970)., "The Chemistry of Cement and Concrete", 3rd Ed., Edward
Arnold.

2)

Vicat, L. J. (1837)., "A Practical and Scientific Treatise on Calcareous

Mortars and Cements, Artificial and Natural", Translated by Captain J.T.
Smith; John Weale, London.

3)

Vitruvius (27 BC - 14 AD)., "De Architecture" translated as "The Ten Books

on Architecture" by M.H. Morgan, Dover Publications Inc., New York, 1960.

4)

Wallace, W. (1865)., "On Ancient Mortars", Chemical News, April 21st 1865,
pp 185 and 186.

5)

Davey, N. (1947)., "Examination of the Materials of Construction from the

Park Street Villa"., appendix from O'Neill, H.E. "The Roman Villa at Park
Street, Near St. Albans, Hertfordshire,' Archeological Journal, Cll.

6)

Davey,

N.

(1950).,

"Building

Materials

in

Antiquity",

Chemistry

and

Industry, Jan 21st 1950, pp 43-47.

7)

Efstathiadis

(1978).,

"Greek

Concrete

of Three Millenniums," Hellenic

Ministry of Public Works, Athens.

8)

British Standards Institution (1985), BS 8110 "Structural Use of Concrete,"

1985.

9)

Malinowski, R.

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199

ACKNOWLEDGEMENTS
This project was funded by the Commission of the European Communities, the
Department of the Environment and Taylor Woodrow.
Special thanks are due to Mr. C.C. Stanley, of the Cement and Concrete
Association, for guidance and the provision of many samples.
The help and
provision of electron microscope facilities of Blue Circle Technical, Research
Division, is gratefully acknowledged.
The assistance of the following is gratefully acknowledged:
N. Winter
A. Harrisson
P.L. Pratt
K. Scrivener
3.A. Steadman
A.3. Majumdar
3.G. Cabrera
3.G. Crow

- Blue Circle Research Division.

- Blue Circle Research Division.
- Imperial College of Science Technology.
- Imperial College of Science & Technology.
- Building Research Establishment.
- Building Research Establishment.
- University of Leeds.
- National Trust.

Much gratitude is due to the following, who contributed samples for study:
M. Bound
J.G. Cabrera
3. Figg
3.A. Forrester
M.L. Franks
E. Marsh
D. Phillipson
C.C. Stanley

200

12.

APPENDICES
Appendix Al

Glossary of Terms

203

Appendix A2

Results of Thermal Analysis

207

Appendix A3

X-Ray Microanalytical Results

227

Appendix A4

Investigation of Three Ancient Concrete By The

Building Research Establishment.

245

Appendix A5

Results of Mercury Intrusion Porosimetry.

249

Appendix A6

Definition And Classification of Cements.

269

Appendix A7

Compressive Strength and Density Results.

277

Appendix A8

T.E. Sorption Test Results.

289

Appendix A9

Water Permeability Test Results.

293

Appendix AIO

Sieve Analysis Results.

301

Appendix All

Oxygen Diffusion Test Results.

305

201

APPENDIX Al
GLOSSARY OF TERMS

-203-

GLOSSARY OF TERMS

1.

2.

Cement Chemist's Notat:ion

C

CaO

A1 2 0 3

Si02

= SO3

F =
M =
H =
C =

T =

FeO

Fe 2 0 3

Na20

MgO

K20

H20
C02

Li20

P205

Ti02

Cement Compounds
C-S-H

Calcium

silicate

hydrate,

an

amorphous

(or

semi-amorphous) m a t e r i a l o f v a r i a b l e c o m p o s i t i o n .

Alite

Impure C3S (tricalcium silicate) substituted with other

oxides, as found in Portland cement.

Belite

Impure C2S (dicalcium silicate) substituted with other

oxides, as found in Portland cement.

Aluminate

C3A

(tricalcium

aluminate),

as

found

in

Portland

cement.
Ferrite

The iron-containing phase, present in Portland cement,

whose composition varies between CgA2F and CgAF2 with a
mean close to C4AF.

Ettringite

Calcium tri-sulphoaluminate hydrate, C3A.3C S* H31

Monosulphoaluminate

Calcium monosulphoaluminate hydrate, C3A.C S H^2

AFt

phase, formed

cement, which

during

the

is considered

hydration

of

Portland

to be derived

from

ettringite with partial substitution of A by F and

SO42- by other anions.

205

AFm

phase,

cement,

formed
which

during
is

the

considered

hydration
to

be

of

Portland

derived

from

monosulphoaluminate with partial substitution of A by F

and SO42- by other anions.

-206-

APPENDIX A2
RESULTS OF THERMAL ANALYSIS

207

APPENDIX A.2
BESUI/TS OF THERMAL ANALYSIS

FORMAT OP FIGURES A.2.1 TO A.2.16

Each figure contains three curves output simultaneously from the thermal
analyser : TG, DTG and DTA. A key in the top right hand corner of each
figure shows which curve belongs to which form of analysis. The abscissa
is the temperature axis; the ordinate has no units and serves as follows
for each technique:-

(a)

DTA

: Exothermic upwards; endothermic downwards.

(b)

TG

: Weight loss upwards.

(c)

DTG

: Weight loss upwards.

209

FIG. A2-0
FORMAT OF THERMOGRAMS

DTA
TG
DTG

exothermic

weight
loss

DTA

endothermic

weight
loss
;1

TG

DTG

weight
gain

Temperature (c )

210

weight
gain

Key.
1:

THE RALLI BUILDING

DTA

TG
DTG

1000
Temp. C

Key.
DTA
WEAVER'S MILL

T G
DTG

i*

1000
Temp. C

to
IO

s
OJ

Temp. C

Key.
DTA
4:

ANCIEN
T

GREEK (CAMROS)

TG
DTG

H-

100

200

300

400

>

500
Temp. C

600

700

800

900

IO

1000

e*

Key.
DTA

READING ABBEY

TG
DTG

200

i
300

400

500
Temp. C

600

i
700

>

1000

to

Key.
6: CONCRETE HOUSE. 186*;

OTA

TG
DTG

to
>

1000

fO

Key.
DTA

7: CONCRETE FORT. 1899

TG
DTG

S)
I>

H-

f*
800
Temp. C

900

1000

ro

Key.
8:

HTODERSFIELD MILL. 1913

DTA
TG
DTG

S)
I'

00

K"-

>
1000

ro
CD

Key.
9:

ASPDIN RENDER. WAKEFIELD

DTA
TG
DTG

1000
Temp. C

IV)

10:

CIMENT BABBEL. 1848

Ni
O

Temp. C

Key.
DTA
11:

BULLA REGGIA

TG
DTG

1000
Temp. C

Sero

Key.
OTA
12:

PH ESSED TILE. 1904

TG
DTG

ro

1000

Key.
DTA
13:

HEROD'S PALACE. MASABA

TG
DTG

0>)

1000
Temp. C

14:

LINING OF ROMAN BATH. BATH

to

*1
Ol

1000
Temp. C

Key.
15:

RAILWAY TERRACES. HULL

DTA

TG
DTG

0>1

1000

Key.
DTA
16: PORTLAND HALL

TG
DTG

0\

1000
Temp. C

APPENDIX A3
X-RAY MICROANALYTICAL RESULTS

227-

Tables A.3.1 to A.3.3

Results of X-Ray Microanalysis

Notes

a)

The results are expressed in percentage

than weight per cent of elements.

atomic proportions rather

This enables the composition

of a single phase to be directly translated to a chemical formula.

b)

The technique detects all elements from fluorine upwards in atomic

number.

Carbon and oxygen are therefore not detected.

Consequently

the figures for oxygen presented in each table have been calculated.

c)

The accuracy of each analysis is approximately 2%.

229-

TABLE A.3.1

X-RAY MICROANALYSES OF GREEK (CAMIROS) CONCRETE

(ELEMENTAL PROPORTIONS IN ATOMIC %)

Na

0.24

0.75

0.56

0.27

0.37

0.56

Mg

0.07

4.51

4.06

0.15

0.67

1 .38

0.44

Al

0.41

3.67

4.51

0.13

2.43

7.40

0.41

Si

32.77

23.83

22.16

0.43

28.63

22.25

2.10

0.08

0.02

0.06

0.05

0.52

0.77

0.13

0.27

5.68

0.28

Ca

0.03

1 .85

1 .82

48.75

2.44

0.75

45.15

Ti

0.07

0.45

0.05

Fe

1 .69

2.82

0.5

0.56

66.42

63.05

62.82

50.14

65.01

61 . 6 0

51 . 0 0

100.00

100.00

100.00

100.00

100.00

100.00

100.00

AREA

0
(Calc.)
TOTAL

AREA

10

11

12

13

14

Na

1 .11

0.62

0.93

0.81

0.91

0.71

0.53

Mg

0.73

0.39

0.46

22.85

20.26

0.29

4.67

Al

0.50

0.08

0.23

0.89

4.93

0.61

Si

2.14

0.67

0.69

0.14

17.21

26.69

4.57

0.06

0.03

0.02

0.06

0.03

0.24

0.19

0.17

0.10

1 .89

0.17

Ca

44.26

47.82

47.34

26.14

0.13

0.83

36.89

Ti

0.03

0.00

0.08

Fe

0.00

0.00

1 .61

0.43

0.24

50.93

50.19

50.15

49.90

59.00

64.10

52.32

100.00

100.00

100.00

100.00

100.00

100.00

100.00

0
(Calc.)
TOTAL

-230-

CAMIROS CONCRETE
COMMENTS
AREA
1

Centre of round sand grain.

Rim of sand grain, higher Na, Mg, Al, K, Ca, Ti,

Fe than Area 1.

Rim of sand grain, comments as for 2.

Matrix around sand grain - Ca CO.,.

Rim of sand grain, minor elements lower than 2

and 3.
Rim of sand grain, higher K and Al than other rim
analyses.
Matrix around sand grain, mostly Ca CO , some Si
present.

Some grains as Area 7.

Material in crack - mostly Ca CO .

10

Dense matrix - mostly Ca CO .

11

Aggregate - probably dolomite.

12

Aggregate - mostly a magnesium silicate.

13

From a dark, matrix area, possibly a particle of

volcanic earth.

14

231-

TABLE A.3.2.

X-RAY MICROANALYSES OF WOOLSTON QUAY CONCRETE

(ELEMENTAL PROPORTIONS IN ATOMIC %)

Na

0.55

0.44

0.90

0.71

0.43

0.06

0.32

Mg

0.12

0.09

2.60

0.29

0.51

0.14

0.18

Al

13.65

0.26

10.27

0.18

0.42

2.13

0.94

Si

14.19

13.88

11 . 4 4

0.82

2.63

12.72

13.17

0.03

0.15

Cl

0.01

0.02

0.13

13.52

0.27

0.25

0.21

0.14

0.09

0.19

Ca

0.55

28.19

15.78

47.46

44.47

27.38

28.46

Ti

0.04

0.04

Fe

0.34

0.03

0.61

0.01

0.10

0.13

57.07

56.83

58.15

50.27

51 . 3 0

57.03

56.71

(Calc.)
TOTAL

99.99

100.00

100.00

100.00

100.00

100.00

100.00

AREA

10

11

12

13

14

Na

0.51

0.35

0.39

0.55

0.53

0.39

0.41

Mg

0.52

0.61

0.62

2.32

0.67

0.09

0.41

Al

16.26

16.20

0.55

9.03

16.28

0.92

9.16

Si

1 .20

1.25

10.63

1.64

1 .08

13.32

6.78

AREA

0.01

0.02

CI

0.09

0.11

0.14

0.11

0.13

0.16

0.14

Ca

26.33

26.28

32.25

22.14

26.16

28.44

27.26

Ti

1.53

0.01

Fe

0.46

0.51

0.07

7.17

0.55

0.03

0.24

54.63

54.69

55.34

55.50

54.59

56.75

55.61

100.00

100.00

100.00

100.00

99.99

100.01

0
(Calc.)
TOTAL

232-

100.01

TABLE A . 3 . 2

AREA

(Cont.

15

16

17

18

19

20

21

Na

0.49

0.64

0.39

0.38

0.36

0.32

0.64

Mg

0.58

2.44

0.51

0.62

0.69

1 .03

0.28

Al

13.77

9.82

0.36

0.58

1 .49

1.55

1 .05

Si

3.12

1 .46

10.67

10.46

12.69

12.51

12.94

0.19

0.20

0.07

Cl

0.12

0.10

0.13

0.10

0.13

0.12

0.09

0.11

0.15

Ca

26.A3

22.44

32.51

32.50

27.19

26.87

27.62

Ti

1 .17

0.10

0.07

0.13

Fe

0.51

6.68

0.11

0.07

0.23

0.38

0.34

54.97

55.26

55.33

55.27

56.86

56.86

56.77

100.00

100.01

100.01

100.00

100.01

100.00

99.99

0
(Calc.)
TOTAL

AREA

22 '

23

24

25

26

27

28

Na

0.13

0.32

0.42

0.38

0.56

0.46

0.40

Mg

0.17

1 .07

0.92

0.42

2.08

0.25

0.33

Al

1 .67

1 .61

1 .41

0.76

11 . 4 6

0.65

0.70

Si

13.21

11 . 0 8

12.70

10.34

0.94

10.29

10.26

0.22

0.25

0.21

0.03

0.04

CI

0.10

0.18

0.11

0.02

0.14

0.14

0.13

0.16

0.09

0.14

0.14

Ca

27.00

28.89

26.75

32.18

22.15

32.84

32.86

Ti

0.04

0.08

0.06

0.06

0.82

0.01

Fe

0.11

0.23

0.40

0.29

6.66

0.10

0.11

57.20

56.14

56.88

55.35

55.24

55.22

55.19

(Calc.)
TOTAL

99.99

99.99

99.99

99.99

100.00

100.00

99.99

-233

TABLE A . 3 . 2 .

(Cont.)

29

30

31

32

33

34

35

Na

0.49

0.45

0.28

0.55

0.34

0.18

0.16

Mg

0.16

0.14

0.16

2.18

0.51

0.30

0.54

Al

0.67

0.53

0.47

11 .35

15.45

1.15

1 .28

Si

13.31

13.45

13.66

0.94

0.10

0.04

0.02

Cl

0.21

0.18

Ca

28.42

Ti
Fe

AREA

0
(Calc.)
TOTAL

13.77

14.54

0.09

0.07

0.06

0.16

0.11

0.16

0.12

0.10

28.34

28.35

22.15

26.44

26.79

25.39

0.02

0.03

0.65

0.07

0.07

0.04

0.07

0.04

6.88

0.21

0.17

56.76

56.77

56.86

55.19

54.68

57.26

56.67

100.00

100.00

100.00

100.00

100.01

100.00

99.99

1 .37

1 .06

36

37

38

39

40

41

42

Na

0.40

0.06

0.04

0.37

0.42

0.02

0.23

Mg

0.55

0.65

0.22

0.63

0.36

0.47

0.30

Al

8.84

11 .05

2.34

2.13

9.64

11.11

4.32

Si

3.48

2.49

12.50

13.00

1 .20

5.77

9.83

1 .68

3.02

0.75

0.60

0.20

1.11

0.89

CI

1 .30

0.70

0.14

0.10

0.11

0.11

0.32

0.16

0.07

0.25

0.18

0.09

0.10

0.14

Ca

24.97

24.51

25.97

24.74

33.38

22.30

26.92

Ti

0.04

0.03

Fe

2.71

0.52

0.25

0.63

1.17

55.86

56.95

57.54

57.63

53.38

57.08

56.77

(Calc.)
TOTAL

99.99

100.00

100.02

100.01

99.98

99.99

100.01

AREA

-234-

1 .74

0.29

TABLE A . 3 . 2

(Cont.)

A3

44

45

46

47

Na

0.31

0.23

0.29

0.37

Mg

0.40

0.39

0.24

0.54

0.35

Al

4.94

3.05

4.00

4.75

1 .36

Si

4.43

11 .31

8.32

10.40

7.94

1 .16

0.58

0.93

0.80

0.37

Cl

0.36

0.20

0.21

0.22

0.14

0.11

0.14

0.16

0.18

0.18

Ca

33.38

26.97

29.70

25.39

34.51

Ti

0.04

Fe

0.34

0.22

0.35

0.33

0.23

54.52

56.91

56.09

57.10

54.56

(Calc.)
TOTAL

99.99

100.00

100.00

100.00

100.01

AREA

-235

WOOLSTON QUAY CONCRETE

COMMENTS
AREA
1

Aggregate.

Unhydrated grain - belite.

Unhydrated grain - aluminate.

Ca (OH) .

Fine grained Ca (OH) + overlapping CSH.

CSH
Ca/Si

2.15

Unhydrated grain - belite.

Unhydrated grain - aluminate.

Unhydrated grain - aluminate.

10

Unhydrated grain - alite.

11

Unhydrated grain - interstitial ferrite phase.

12

Unhydrated grain - aluminate.

13

Unhydrated grain - belite.

14

Unhydrated grains - largely aluminate, but

including small traces of alite or belite.

15

Similar to Area 14. Aluminate in between 'dots'

of belite.

16

Unhydrated grain - interstitial ferrite phase.

17

Unhydrated grain - alite.

18

Unhydrated grain - alite.

19

CSH
Ca/Si

20

2.14

2.15

CSH
Ca/Si

21

Small, unhydrated grain - belite.

-236-

AREA
22

CSH
Ca/Si

23

2.04

2.61

2.11

CSH
Ca/Si

24

CSH
Ca/Si

25

Unhydrated grain - alite

26

Unhydrated grain - interstitial ferrite phase.

27

Unhydrated grain - alite.

28

Unhydrated grain - alite.

29

Unhydrated grain - belite.

30

Unhydrated grain - belite.

31

Unhydrated grain - belite.

32

Unhydrated grain -

33

Unhydrated grain - aluminate.

34

CSH
Ca/Si

35

interstitial ferrite phase.

1.95

1.75

2.08

1.90

CSH
Ca/Si

36
37
38

CSH
Ca/Si

39

CSH
Ca/Si

237-

AREA
40
41
42
43
44

( CSH
2.38

Ca/Si
45
46
47

-238-

TABLE A.3.3.

X-RAY MICROANALYSES OF WEAVER'S MILL CONCRETE

(ELEMENTAL PROPORTIONS IN ATOMIC %)

10

11

12

13

14

15

16

Na

0.32

5.87

0.26

0.5A

O.AA

0.44

1 .00

Mg

0.17

0.26

0.96

2.07

0.A8

0.11

5.94

Al

0.52

9.A4

1 .80

2.37

3.10

7.87

11 .81

Si

32.58

21 . 2 5

15.70

13.98

12.70

22.82

11 . 3 6

0.01

0.32

1 .20

1.15

0.07

Cl

0.25

0.25

0.19

0 .

0.06

0.13

0.09

0.14

0.12

7.32

0.03

Ca

0.02

1.53

21 . 8 6

2 0 . A8

21 . 6 6

0.02

Ti

0.08

0.20

Cr

0.08

0.11

0.11

Fe

0.18

0.16

1 .64

11 . 3 2

66.32

61 . 5 0

58.A9

58.61

58.22

61 . 4 4

58.44

100.00

100.00

100.00

100.00

100.00

100.00

100.00

AREA

0
(Calc.)
TOTAL

17

19

20

21

22

23

24

Na

0.21

0.30

0.30

0.38

1 .22

0.60

0.07

Mg

0.10

2.55

1.17

0.85

0.71

2.24

0.78

Al

O.AA

2.A8

1.97

2.09

15.47

10.65

1.59

Si

32.72

14.05

15.33

15.33

1.19

1 .20

15.72

0.01

0.42

0.35

0.32

0.04

0.24

Cl

0.39

0.28

0.30

0.05

0.05

0.12

0.12

0.08

0.10

0.09

0.08

Ca

0.01

21 . 0 7

21 . 6 1

21.76

25.88

23.13

22.44

Ti

0.02

0.12

O.OA

0.06

0.68

0.08

Cr

0.01

0.14

0.12

0.13

0.07

Fe

0.02

0.38

0.3A

0.30

1 .31

7.90

0.36

66.42

57.96

58.38

58.38

54.13

53.47

58.51

100.00

100.00

100.00

100.00

100.00

100.00

100.00

AREA

0
(Calc.)
TOTAL

-239-

TABLE A . 3 . 3

AREA

(Cont.)

25

26

Na

0.62

0.66

Mg

2.15

0.22

Al

10.72

5.65

Si

1.24

9.04

0.01

0.12

Cl

0.12

0.10

Ca

23.11

27.47

Ti

0.76

0.13

Cr

0.12

Fe

7.77

0.53

53.50

55.95

100.00

100.00

(Calc.)
TOTAL

240

WEAVER'S MILL CONCRETE

COMMENTS
AREA
10

Aggregate - quartz.

11

Aggregate - a plagioclase feldspar.

ions on the basis of 32 (0) :
Na
Mg
Al
Si
S
K

12

1.39

1.46

1.71

CSH matrix
Ca/Si

15

Rim of grain of Area 12 - CSH

Ca/Si

14

3.05
0.1 A
4.91
11.06
0.01
0.80

ie, an oligoclase with mol % Or , Ab _ , An ,

1 .7
75.4
23
CSH grain
Ca/Si

13

Number of

Aggregate - an alkali feldspar.

on the basis of 32 (0) :
Na
Mg
Al
Si
K

0.23
0.06
4.10
11.89
3.81

ie, an orthoclase with mol % Or

16

Aggregate - silicate.

17

Aggregate - quartz.

19

CSH - grain
Ca/Si

Number of ions

-241 -

1.50

Ab ,. , An

AREA
20

CSH - angular grain (formerly alite?)

Ca/Si

21

1.41

CSH - round grain (formerly belite?)

Ca/Si

1.42

22

Unhydrated grain - alumnate

23

Unhydrated grain - interstitial ferrite phase

2k

CSH, grain near 19 and 21.

Ca/Si

1.43

25

Unhydrated grain - interstitial ferrite phase

26

Unhydrated grain - alite.

242

TABLE A.3.A,

X-RAY MICROANALYSES OF WEAVER'S MILL AND WOOLSTON QUAY CONCRETES

SUMMARY OF ATOMIC RATIOS FOR UNHYDRATED AND HYDRATED CEMENT PHASES

ALITE
Ca/Si

ALUMNATE
Ca/Al

BELITE
Ca/Si

WQ

WM

WQ

3.11

3.04

WM

FERRITE
a: Ca/Al b: Ca/Fe

WQ

WM

WQ

WM

2.13

1.71

1 .67

3.19

2.12

1.54

3.20

2.11

1.62

3.03

2.08

1 .62

a.

1.95

a.

3.05

2.03

1 .61

b.

3.2

b.

3.11

2.16

1 .92

2.14

CSH
Ca/Si

WQ

WM

1.93

a.

2.17

2.15

1 .46

47.46

b.

5.16

b.

2.92

2.04

1.71

44.47

2.61

1 .50

2.16

2.11

1 .41

2.97

1.95

1 .42

1.75

1.43

a.

2.45

2.08

b.

3.09

1.90

a.

2.29

b.

3.36

2.14
av.2.09

WM - Weaver's Mill
WQ - Woolston Quay

WQ

a.

2.15

KEY:

Ca (OH)
% Ca

av.1.49

WM

APPENDIX A4
INVESTIGATION OF THREE ANCIENT
CONCRETES BY THE BUILDING RESEARCH
ESTABLISHMENT

-245

INVESTIGATION OF THREE ANCIENT CONCRETES BY THE BUILDING RESEARCH

ESTABLISHMENT
1.

SAMPLE SOURCES

Samples of concrete from a water storage tank at Camiros, Rhodes, and from
Reading Abbey, England (see main report for details) were supplied to BRE
by Taylor Woodrow. The third material examined was from a core drilled by
BRE from a section of Hadrian's Wall in Northern England, which is believed
to have been built about 200 A.D; the material originated from near the
centre of the wall cross-section, at a point about 750 mm from the
present-day top and side surfaces.
2.

INVESTIGATION METHODS

The samples were studied primarily by ptrographie examination of thin

sections. Particular regions of interest were also examined by chemical
and thermal analysis and by X-ray diffraction.
3.

RESULTS

The Camiros sample was found to be fully carbonated. No definite evidence

of the original presence of pozzolanic material was found, and any CSH that
may have been formed must have since decomposed. The material is a true
concrete (slightly deficient in fine aggregate) and the aggregate comprises
a variety of rock types. Numerous pores and cracks were seen, but compared
to other ancient concretes the matrix is relatively well compacted. The
sample was supplied already impregnated with resin, which precluded thermal
analysis.
4. The Reading Abbey sample was also found to be fully carbonated, and no
evidence of pozzolanic material was found. The coarse aggregate was
composed mainly of flint and limestone. A narrow reaction rim was seen to
surround each flint particle, which may have resulted from reaction with
lime to form a type of CSH that subsequently decomposed by carbonation to
give a denser structure than that of the normally carbonated lime paste.
Differential calorimetry showed no endothermic peaks typical of CSH or
portlandite, confirming that carbonation was complete.
5. Two transverse slices of the Hadrian's Wall core were prepared as
ptrographie thin sections. The infill of the wall (between coursed
masonry faces) consists of large irregular stones up to 300 mm across, with
the voids between them filled by a coarse mortar. One of the sections
consisted of a 50 mm thickness of mortar and parts of two adjoining stones,
one the local sandstone (quartz arenite) and the other from the igneous
intrusion known as the Whin Sill (quartz dolerite) on which the Wall is
built. The second section consisted wholly of mortar, which was similar in
all respects to that in the first section.
6. The Hadrian's wall mortar is almost wholly uncarbonated; the small
carbonated regions distributed through it may represent the onset of
carbonation or may be derived from the aggregate. The matrix is compact
and of low porosity, though extensively microcracked. Several fragments of
a fired clay product were identified; such material, finely ground, was
used by the Romans in Britain as a substitute for pozzolana, but the amount
found in the Hadrian's wall mortar is not sufficient to have produced a
significant pozzolanic effect. The large quartz dolerite block showed
cracking and discoloration to a depth of 3 mm from the mortar interface,
which may have resulted from alkali attack.
BRS67/86
-247-

7. The coarse aggregate in the mortar consists mainly of chert, much of

which has been altered from its initial cryptocrystalline state to an
isotropic, friable and very porous material. Many fragments have been
entirely converted, though some retain a harder core. Chemical analysis of
the altered material gave the following results:%

Si0 2

CaO

co 2

Combi ned H20

32,.8
32,.5
10,.9
18,.0
94.,2

These, together with X-ray diffraction and DSC, indicate that the material
is largely CSH, with a little carbonate and quartz also present.
8.

CONCLUSIONS
(i)
No evidence of surviving CSH was provided by the Camiros or
Reading Abbey samples, because they were fully carbonated.
(ii) The Hadrian's Wall mortar contained abundant CSH but no
significant carbonation; formation of CSH must therefore have been the
main setting mechanism.
(iii) The CSH was probably formed by reaction between lime and chert in
the coarse aggregate (but another possibility is that a hydraulic lime,
made from argillaceous limestone, was used).
(iv) It is not possible to say whether alteration of the chert
occurred after the mortar was placed, during the lime-burning and
slaking process, or naturally by thermal alteration in the contact zone when
the Whin Sill was intruded against the adjacent limestone. Further geological,
ptrographie and analytical work may enable this question to be
resolved.

ACKNOWLEDGEMENT
The work reported above was carried out by K Pettifer (petrography), Dr N
Crammond (XRD) and M J Bowley (Chemical analysis) of the Building Research
Establishment, as part of the research programme of the UK Department of
the Environment, and is published by permission of the Director. The generosity
of the National Trust in giving permission for samples to be taken from Hadrian's
Wallis greatly acknowledged.
Building Research Establishment
Garston
Watford WD2 7JR
(Tel 0923 6740H0)
February 1986

248

APPENDIX A5
RESULTS OF MERCURY INTRUSION POROSIMETRY

249-

TABLE A 5.1
MERCURY INTRUSION POROSIMETRY - SUMMARY OF RESULTS

No.

SAMPLE

SURFACE

TOTAL PORE

PORE VOLUME

HYDRAULIC

HYDRAULIC

TOTAL

MAXIMUM

VOLUME
3. 3
cm- /cm

>660 8
cm3//cm3

RADIUS

RADIUS

SURFACE

CONTINUOUS

AREA

PORE

>660 8

>660 8
8

AREA
2
m //cm3

RADIUS 8

2
m //cm3

PORTLAND
0.15315

0.05069

66.8

2087.4

22.9200

31250

0.2429

0.2446

0.1523

212.5

1387

11.5097

16875

1.0985

0.2038

0.1260

256.3

1447

7.9527

13750

0.8708

0.2173

0.1518

337.5

1434

6.4371

31250

1.0586

0.1476

0.1422

1635.7

1998

0.9 022

31250

0.7115

0.2674

0.0889

116.8

918.7

22.9052

4706

0.9673

(CAMIROS 0.1821

0.1503

459.5

1042.6

3.9642

31250

1 .4417

0.1049

0.0509

221 .2

1181 .8

4.7438

31250

0.4308

0.0967

0.0440

143.0

722.5

6.7623

10937

0.60890

0.1967

0.0328

79.9

586.1

24.6229

3823

0.5590

0.2007

0.0840

127.8

820.2

15.6998

5803

1 .0244

0.0853

167.5

793.2

9.3236

5804

1.0756

HALL 4
PORTLAND

2
3
A

HALL F2
PORTLAND
HALL F
RAILWAY
TERRACES
HULL

5
6
7
8
9

READING
ABBEY B
READING
ABBEY A
GREEK
WOOLSTON
QUAY SF
WOOLSTON
QUAY
BULK
RALLI

10

BUILDING
K
RALLI

11

BUILDING
N

12

RALLI
BUILDING
01

0.1562

-251

No.

13

SAMPLE

TOTAL PORE

PORE VOLUME

HYDRAULIC

HYDRAULIC

TOTAL

MAXIMUM

SURFACE

VOLUME
3. 3
cm /cm

>660 8

RADIUS

RADIUS

SURFACE

cm3 //cm3

CONTINUOUS

AREA

AREA
2
/ 3
m /cm

PORE

>66o8

RADIUS 8

2. 3
m /cm

>660 8

RALLI
BUILDING
M1 MORTAR

14

0.155

0.1375

1118.6

1957.6

1.3003

31250

0.7026

0.1651

0.111

240.7

1352.3

6.8606

13750

0.8239

0.0927

0.050

190.0

1337.3

.8779

31250

0.3770

10.1007

0.0553

13.3

1296.2

7.0266

31250

0.270

RALLI
BUILDING
Ml
WEAVER'S

15

MILL
BULK 1

16

WEAVER'S
MILL
I BULK 2

252

PIG. A5.1

PORTLAND H ALL (4)

CUMULATIVE PORE S I Z E D I S T R I B U T I O N
STRUCTURE: HISTORICAL CONCRETE
POUT. HULL *
160 KUSTBO!

in S

.._

, . .

io3

10'

PORE RROIUS

CltflPHIHC ST51EH PROOllCCO BT

COMPUI IG SERVICES D IVISION

1 1

I I I I

105

(9NG STR0MS)

AAAA

DIFFERENTIAL PORE S I Z E D I S T R I B U T I O N
STRUCTURE: HISTORICAL CONCRETE
s,

...A..

PORT. HAU 1SM0THED

AHCSTROMS

6 W

....

...
:

.. .. i

! : i

. i. J :.. i

_ _ i......Li i iii..;

frS-

: 1: : i i

i _i_ L.LijLi__

0 "
0
9
1 B
^m.

>*

__

0
_i

1
i

-A

1
:

p| 1 : i

IX

j ; j i

! ! ; ; ! ! ! ;

'

j _ .....

_...

] j LJ ...Li .LL

! I ; ; iii1

! 1 ! :

_,..

1 i i !

1...

t i l : : : ;

. I

'\h\
; \

'

,:

........ 1 . - |

M ! 1

.i,:

1; i

; ; : ! j ;

i l !

! : ; ! !

^ * ^

! i

: '!

MM
1

' : : : :

10'

i :

; '
1

; i ; ! ;:ii

1 1:

i
1

: l!

il 1 1 i
Lf

St
ia
0

10 s

10'

PORE RRDIUS

IRNG STROHSI

ib

Yo
AAAA

UWnlNC STS1EN flOOUCt ST

COKUlKC StIC[S O U l i l f l

-253

FIG. A5.2

PORTLAND HALL (F2)

-**--

660 MC3TMIIS

0.20

0.210

0.320

CUMULATIVE PORE S I Z E DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE

Il

Ii

O.IBO
0.120
0.010
0.0110
0.0

INTRUOEO PORE VOLUHE

ICM3/CH3I

0.200

.,. ::r~
:

0'

^P^
io2

H' '

PORE RAO I US

10 s
(ANGSTROMS)

SIC PKOOUCtO BT

10"

10 s
# J 0 # #

/7/7/5/J 1

mi as DIVISION

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
POUT.KULL F2SH00THCD
610 MCSTIUnS

cnapniM s i s u PIUDUCIO I t
COnfulIC SEHvlCES Division

PORE RAO I US

-254-

(ANGSTROMS)

AMtA

FIG. A5-3

PORTLAND HALL (F)

CUMULATIVE PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
POUT. HALL F
StO CSI OBS

!.

8
=<3

10'

PORE RADIUS

(ANGSTROMS)

GMH|K STITCH MOOUCtO BI

coMruimc jtBYicn OIDHIOH

AA

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
ram. HRLL rsnoomo
MO MC31MMJ

.i

"

Si

CD
O

58

10'
PORE RADIUS
Mamme U H paooucto I T
COHPUTIIIG itmicEi oiYHioK

255

(ANGSTROMS)

V
AAA

FIG. A5.4

HAILVAY TERRACES, H LL

CUMULATIVE PORE S I Z E D I S T R I B U T I O N
STRUCTURE: HISTORICAL CONCRETE
o

u McsiM

'

B
:

r*

.-

' -

- - ; ;

;"--'

"

"

. i .

:
O o
tn

x:

es
o

1 .

mi"*

" 1.

3C
= o
> o
UJ

^W^

: ! .

oc

I ^

s.
a o
J

SES
2"
o

s.

^"^

10'
cnnrniK

TSIC

y *

: li

10 3
PORE RAD IUS
(ANGSTROMS)

10'

10"

IO 5

M O O U U O BT

&A \

COlUTING SEBVICE! D IVISION

DIFFERENTIAL PORE S I Z E D I S T R I B U T I O N
STRUCTURE: HISTORICAL CONCRETE
o

BS NCSTAOHS

'

a
:

si.

i i

'.

! ; ! : '. J

;.

'
.

'.

i i

! '. ', ' '

: l'

i '

: i

. : : : : . ! :

'

! '.
.

"

. '.

'

! .

. ,

o
9

'
^ 5.'

<n

ill;;:;!

i : M ij! ; ! :

' . . ' . ' ' ' . ' . ' .

'.

'.

:
t

)
:
'
:

i ; : ' i ; ;; :

; ; ! ''

.1.

! ! !

i :
' I

i
i

l I i
: .

';

i
i

.
o

> *

i
'

: t :

i

! . .
;
. :

! ! ' : : i:

i
:
'
:
i

1 i
i
1 .
, J
| .

' / V ' "'1:

1 r

:
j

.
i i

"!-.

: :

J\m'-'

8.

o \

10'

! . '. , .

t
'--?':->

io1

io'
PORE RAO I US

I -

10*

1 I -T-^-l-)

10'

(ANGSTROMS)

AAAA

GflflFHlMG S1STEH MOOUCCO BT

CQ*UTIMG VICES 0IVISIN

256-

FIG. A5.5

READING ABBEY (B)

CUMULATIVE PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
neno B I K T 1
660 RNI6TNMS

en

IO2

10'

PORE

RAD IUS

(ANGSTROMS)

GMPXIaG SISTE PBOOuCEO ST

COHfUIlMC SERVICES D IVISION

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
*...

BE BO BBBEI tSMOllCD
660 HNCSTnons

m
0
D - 1
O

_.

.. _

:....

sS.

' -

* -! -:

'-

5i.
CO

^ s .
I

. ~r :ir. . '-

_ 0
ec S .

^
8
> . ix-

~r~iT*j"V'i

8.

_.

_.

e
l

0'

10'
PORE

RAD IUS

dinmmc J T J U moouctD I T
COnfuTllC M I C MHIOH

-257

(ANGSTROMS)

FIG. A5.6

READING ABBEY (A)

CUMULATIVE PORE SIZE D ISTRIBUTION
STRUCTURE: HISTORICAL CONCRETE
e

MO ffcGSTRORS

a,
a

( J
"v
<n
ac

.
UJ
ac

Si.
UJ
oc

s.
O
J

OC a

s.
o

e
e

::jfe:

i 0'

10'

10S

PORE RAOIUS

IO5

IO"

(PNGSTROMSI

CPIAPnlNC ST IE PROD UCED Ol

<#,##,#
couru!ING s nviccs D ivision f
f
f
/ /Jy / ^

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
neu

meer OSMOTICO

1(0 (SIMMS

I
si

; i ; :;:i

1.. ...:.......,..j.^.fJ

J .Jr...i.. !_j 4 .

'

i I

i i : ,

!
i

i
j

i !
. i i .

i
i

'

>

I i i ' '

; ' ,

i i ! i

i
i I

i i i

i
i

i
i

'

3 8
i

S=8

i i i

'.

',

I '

i ; ! iij

i ! i i '

I0'
CKMMtmC SISU MIOD UCEO 01
COWfUlIkC SIHVICCS D IVISIOM

PORE RADIUS

(ANG STROMS)
jjttt

258

FIG. A5.7

GREEK (CAJCffiOS)

CUMULATIVE PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
GEEK SIMPLE
6(0 mcsinons

e S

ib

10'

PORE RPOIUS
cnnPitiHC H U E

PROD UCED

COHPUIIMC iEnncsa

(fiNGSTROMSI

IT

omsitw

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
CHEEK smriEMOOTico
6(0

MCSTHOKS

"8

PORE RADIUS

(AN
G STROMS)

CRormac s u n rnoouCED I T
COHPIHIIC SIIWICIS 0 U H 1 0 H

259

FIG. A5.8

WOOLSTON Q.AY ( SURFACE )

CUMULATIVE PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
WMXSIO Jf
6 M MCSIMMS

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
HOUSTON w n o m o
>IO MttJMMJ

Hr-t-fH

^8

10'
anime sun riuxwciD i
confu i st stiincei oimiQN

PORE RAD IUS

(ANGSTROMS)

MM*

260-

FIG. A5.9

VOOLSTON QUAY (BULK)

CUMULATIVE PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
HOUSTON IUL
6t0 MCSTBOm

.... ,.

m S

e S

1 1 * 1 1

ib

10'

10'

PORE RADIUS

ib1

10s

(PNCSTROHS)

GMmlNG 5I51E PBOOUCEO IT

C W U I I H t VICES D ivision

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
oasTON ginsnoomcD
to NcsTnons

s S.

10'
PORE RAD IUS
CMVUINC lisien fooocio i t
e w m n c s; Y i CE s misin

261 -

IflNGSTROHS)

i i i i

10 s

PIG. A5.10

RALLI BUILDING (K)

CUMULATIVE PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
UHU
660 MCJIKOIIS

= S

10'
PORE RAMUS

(RNGSTROMSI

Malac STSIEH MOUCEO ST

con'uimc SERVICES Division

T T T T I

10b

AAA

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
MILI >
SltOOTHtD
660 MCSinOM

3s

io'
GMPalaC STSIEa MOOIXEO i l
CORMIlaG SERVICES OUISIOW

PORE ROOIUS

-262-

(ANGSTROMS)

AMA

PIG. A5.11

HALLI BUILDING (H)

CUMULATIVE PORE SIZE DISTRIBUTION
STRUCTURE: HISTORICAL CONCRETE
RULLI II
MO MC3TMM3

a 8

10'

POflE RROIUS

(fiNGSTROMS)

GMVHitG SISTER PROOUCEO IT

COWUTING SERVICES DIVISION

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
RULLI II
SHOOTKD
660 HN6]TR0>S

sS
i.
PO g .

10'
CRWalNC SISTE PROOUCEO BT
COnfalIC SERVICES 0IVIS1OM

PORE RROIUS

-263-

(ANGSTROMS!

FIG. A5.12

BAT.T.T BUILDING (Ol)

CUMULATIVE PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
( L l l 0!
660 MCSIKMS

S S

10'

PORE RADIUS

Gitnrnitc STSTCH rnooucco s i

COUNT lue stICtS 0IV1SI0H

IRNGSTROHS)

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE

1,

MULI Ol
5K0OID
660 MKSinOa]

o "

G
s
_i 8

10'
PORE RfiOlUS
GMtfriING STSIE fHOOUCED IT
COnfullug SUYICtS OUISIO

-264-

IfiNCSTROMS)

105

RALLI BUILDING M

FIG. A5.I3

-MORTAR

CUMULRTIVE PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
4...

nnn I n nani
o RNCsrnoKS

s
1
1

.... ..

1
-

--jfi

. 1

-s.

en

- e1.

!
. . .

bJ

az

s.
> d
J
ac

2 i.
O
bJ
O

OC

=>

m
m

s*"

;-;-;

01

10'

.-1Q2-

ib'
PORE RROIUS

10'

10

(BNCSTROHS)

AAA

r.ARPniHC s u i f * FM D UCEO B I
confutine S E R V I C E ; 01 V I S I O N

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
HALLI H nD KISnOO'HED
660 BKCSIIIO11S

S
0

ES

iV

Ir

PORE RROIUS

atrni KG STSTCH MOOUCCO e i

Confinine S l n I C I l D UISIO

265

(RNCSTROHS)

AA

PIG. A5.14

RALLI BUILDING (Ml)

C U M U L A T I V E PORE S I Z E D I S T R I B U T I O N
S T R U C T U R E : H I S T O R I C A L CONCRETE
g

so ANCS1MMS
:- -

ft.
e

. . - . . . . . - - .

A - y-r

- -

'

'

.
.

o
-

. .

'
.

b> 8

4_ 1 " .L " 1.1 "

J.

UJ

|1 ! i 1

en
z

'

- * -

. .

' ! i '

:"

; i ;;

'

' !

'

' :

'

i!"*"**!

" .

I ;

_u u .* i L J. _L
;

.
.

L i a

i
1

1 '

'
t

H
l.
>

i i i ~ . ; .
.

'

: : ; : : * : '

UJ

ce

* "

ac "!"
o

1
.

O
UJ

1 '

"

1
i

J
j r

o
3

'

. ; .
"
. . . .

CC O

. ,

- ^M~mP

.
, |. . .
;_.....,...-.4i**i

__

*..

. . . .

.
.
.
..i. i . A _ i ^ i . , . ^

'

"

; .

<

! . . ; :
: .

Jar
m

2o

; ,:;

e
o

10'

'

10 J
PORE RfOIUS
IRNGSTROHS)

10*

i'os

10"

CNRPnlMC STSTCH PAOOUCEO BT

CONfUTlHC SERVI CES DI VI SI ON

DIFFERENTIAL PORE SIZE DISTRIBU!ON

STRUCTURE: HISTORICAL CONCRETE
IWLll m
SHOOTK
D
S60 nuSTMMS

*...

0
o

f . : ,

. *
.
:

s
a

!: :

T
O

. I

.i'
' I '

:!

:
; i;

:
t .
:

'

i i

__4_i._

:;;,,

! ; ;* ;

. ;:
:

; : j ; >>

'

'

I:

i :

'

'

'

! !

4--4-4-

: '

!
i

i ! i

a:
^ a

: . i

1 .

Ss
n

:
1 .

.It

H i f t

- - -

'
1

44

'

i i '

1 .

! : ' ; 1 :;;

: i :
,

- - - '->'

! :i
' - -

'

-f r~~r-rr-; _ j l~:~ 1 ' -rr

"8
O

'

' \

'

::

.9. i 4

8,

:I !

'

' J

r
li

10'

10 '

"T

._ 4. -41 ,

' " T ",

1
1

1 :

'

j . . . ,f i ..}.,(

; | ;

_ _:_

^!^***

'1

J L_4_.
'

-/

.._ 4.
M

r * :

1 * 1 1 1

PORE RAD IUS

10 J
IRNGSTROHS)

empirne lisie* pnooucco >i

cawuiKG stBic[j oimioii

:^TL_

'

* v ^

1
1

1 i.:

T f"H' '! T'. '!

;
'

.1 __.._.

, , .

:
ib'

' ' 'ib

AAA

266-

FIG. A5.15

WEAVER'S MILL (BULK)

CUMULATIVE PORE S I Z E D ISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
*

660 ANCSTMMS

d
o
e

"^ 2.
LJ
v.
en
a:

e i.
d
UJ
O
>

5
d

UJ
cc
O o
Q_ u
o
O e
LU

=)

CC o
M

o
e

i 0'

10*

CWnlNC SI sit PROOUCEO ar

CDKPUIKG 5i BUCES ! VI SION

PORE RAD IUS

io3
(ANGSTROMS)

10'

10 5
4444,

f
J JIA/T'

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
MEBVEB

BUIK

SHOOTHEO

6(0 NC5H0HS

s=S

IO5

10'
PORE RAD IUS

IRNGSTR0MS)

AA

GMPHINC STSU PKOOUCEO I I

COMfUlKG StXICES OIVHIOK

267

FIG. A5.16

WEAVER'S MILL (BULK)

CUMULATIVE PORE SIZE D ISTRIBUTION
STRUCTURE: HISTORICAL CONCRETE
g

ants i newts

M 0

i ' '. '.

!. . i

m .

en

e 8.
UJ
X
:

>

'

'

: ;:

' ' J*

liJ

Lx*"

ce
'

1.
O o

'

'

o
(C o

~it!"~

'

f
:

'
'

: !::

'. \

'ib*

10'

ib'
PORE RAD IUS

ertami ac ITSTE PUOUCED

10"

i'os

IflNGSTROHS)

BT

'AMA

coNfuiiNC sconces D IVISION

DIFFERENTIAL PORE SIZE DISTRIBUTION

STRUCTURE: HISTORICAL CONCRETE
HCfltCn auiK2Srl00lrC0
eto RNUINM]

= S

_l 5

10'

10'

10
PORE RR0IUS

Gnon] G sisu rnoouCCO I T

coumTiHC v i c i i OIVISIOH

i i i

7o*

[ANGSTROMS)

AAA

268

APPENDIX A6
DEFINITION AND CLASSIFICATION OF CEMENTS

269

Definitions and Classification of Cements

1.

Gypsum - Plaster and Mortar

Gypsum plasters and mortars consist mostly of calcium sulphate.

They are

prepared by calcining rocks from deposits of natural gypsum, CaS0 4 . 2H 2 0,

to jTormeither calcium sulphate hemihydrate, CaS0 4 .2H 2 0 or anhydrite, CaS0 4 .
CaS0 4

>

CaS0 4 .H 2 0 + le H 2 0

130
gypsum

hemihydrate

CaS0 4 .H 2 0

>

CaS0 4 +

H20

165
hemihydrate

anhydrite

The dehydration

temperatures are quite low, being approximately

165C for gypsum

then

crushed

and hemihydrate

and

mixed

with

rehydration to make gypsum.

respectively.

water

to

form

The calcined
a

cement

130 and

rocks are

which

forms

by

The hemihydrate is usually known as plaster of

Paris (Class A, BS 1191 : 1955), a name derived from the hill of Montmartre
in Paris, where natural deposits of gypsum are found.

Ordinary plaster of

Paris may set too quickly, owing to the presence of remnant gypsum which
accelerates the setting process; a protein, such as keratin, may be added
as a retarder, this material is then known as retarded gypsum plaster(Class
B, BS 1191

: 1955).

200 C produces

Calcining gypsum at temperatures in the region of

a soluble

plaster

(Class C, BS 1191

rapidly

in

the

presence

form of anhydrite known as anhydrous gypsum

:
of

1955).
water

This reactive material

vapour

to

form

the

hydrates

hemihydrate.

Calcination at higher temperatures still (up to 600C) produces insoluble

anhydrite, a relatively
make it hydrate.

Insoluble anhydrite forms the basis of Keene's plaster

(Glass D, BS 1191 :
Further

heating

inert material which requires an accelerator to

up

1955), with a sulphate or lime acting as a catalyst.

to

1100-1200C

causes

sulphate:

CaS0 4

>

CaO + SO3

-271

some dissociation

of calcium

The free lime so formed acts as an accelerator for the set of the remaining
anhydrite; this is the slow-setting flooring plaster known as Estrich Gips
in Germany.
Lea (1) points out that the transformation chemistry of gypsum is still
imperfectly understood; for instance, it is not known if the hemihydrate is
a specific chemical compound or merely a component in a composition range.

Gypsum

plaster

moulds.

expands

on

setting,

useful

property

when

casting

in

This expansion is a phenomenon of crystal growth, as the total

solid volume actually decreases during crystallisation.

There is a considerable variation both in the colour and composition of
gypsum, as would be expected of a natural material.

The colour of plaster

varies from white to shades of grey and brown, and sometimes pink.

The

grey colour can be due to the presence of unburnt fuel, whilst the pink
colouration can be a surface phenomenon due to ageing.

2)

Limes
Limes

may

hardening

be

classified

process,

ie.

into
those

two

categories

that

set

in

solely

accordance
by

reaction

with

their

with

air

(non-hydraulic) and those that set, at least partly, by reaction with water
(hydraulic).
Non-Hydraulic Limes
This form of lime is manufactured

by calcining pure forms of naturally

occurring calcium carbonate, ie. limestone, chalk or marble.

On heating

above approximately 800C calcium carbonate decomposes to produce lime.

CaCO.3
High purity

>

CaO + CO2
limestones

produce

limes containing 95% or greater

oxide which are known as fat limes.

calcium

The reaction with water is known as

slaking, forming crystalline calcium hydroxide together with the evolution

of heat.

272-

CaO + H 2 0

Ca (0H)2
(portlandite)

The hydrated

lime, or lime putty, hardens by reaction

with

atmospheric

carbon dioxide, forming calcium carbonate.

Ca (0H) 2 + C 0 2

>

CaC0 3 + H 2 0
calcite
aragonite

There is an increase in solid volume as a result of the reaction, 11% if

calcite is formed and 3% if aragonite is formed.

The mass of the lime as a

whole, rather than just the surface, may be permeable to atmospheric C0 2 so

that the carbonation product forms on the surface of each grain, even in
the

bulk.

together

The

and

volume

the

mass

usually accompanied
carbonating

layer

evaporation.

increase
gradually

causes

the

hardens.

The

by shrinkage, resulting
either

through

grains

to

become

carbonation

cemented

process

from loss of water

absorption

into

underlying

is

from the
layers

or

This shrinkage can cause cracking of the mortar and can be

reduced by moistening the surface.

Pure

lime cements

inferior

have poor

properties

structures.

to

workability

hydraulic

limes,

and

this,

limited

together

their

with

use

in

their

ancient

The ocurrence of pure calcium carbonate rock deposits is also

somewhat rare.
Hydraulic Limes
Limestones containing impurities in the form of amorphous or crystalline
silica

(siliceous) and/or clay

limestones.

On burning

(argillaceous) are more common than pure

at temperatures above 850C silica

reacts with

lime to form dicalcium silicate, 2CaO Si0 2 (C 2 S), and alumino-silicates in

clays

react

with

aluminoferrites
limestones

can

lime

and

to

calcium

produce

form

calcium

aluminates.

portlandite, calcium

aluminoferrites

and

aluminosilicates,
Hydration
silicate

calcium

of

these

hydrate

aluminates.

calcium
burnt

(C5H) and

hydrated

calcium

The

term

hydraulic

is used because the hydrated phases may be formed under water

and, being relatively insoluble, will crystallise in the presence of excess

water.

273

All the phases formed upon hydration of hydraulic limes may carbonate to some
extent

upon

exposure

to air, forming calcite and carbonated

products of the

calcium aluminate, ferrite and silicate phases.

Because

the setting of hydraulic limes is prolonged owing to the presence of

dicalcium silicate, these materials have improved workabilities over pure limes
and thus have a wider range of uses.
Pozzolanic Cements

A pozzolan or pozzolana is a material which produces cementitious compounds by

reaction with lime and water at ordinary temperatures.

The name comes from a

locality in Italy, Pozzuoli, where there is a natural source of this material and
which has been for making concrete since Roman times.

Pozzolanas can be either natural or artificial.

Natural pozzolanas are usually

of volcanic origin and consist of various silicates, both glassy and crystalline.
Santorin

earth and

pozzolanas.

trass are examples.

Diatomaceous earths are also natural

They are composed of the minute skeletons of diatoms laid down from

either sea or fresh water and are often mixed with sand or clay.

Amorphous

silica, in the form of opal, is the majority constituent of these materials.

They are often burnt to make them more effective pozzolanas.
Artificial pozzolanas are prepared by burning clays, shales and siliceous rocks;
they also include industrial by-products such as pulverised fuel ash and silica
fume.

They were known as long ago as Roman times; when volcanic ash pozzolana

was not available (as in Britain) the Romans would substitute crushed brick and
tiles.

Pozzolanas
additive

are
to

durability

employed

concrete.
since

Roman

with

slaked

Pozzolanic
times, when

lime, with cement

lime
they

mortars
were

have

of

in a blend

and as an

been

for

special

noted
value

for

their
marine

constructions.
The mechanism of the pozzolanic reaction is still imperfectly understood.
Natural Cements
Natural cements are prepared by calcining naturally occurring cement rocks, which
contain

a mixture

of calcareous

and argillaeous
-274-

components.

In the burning

process the temperature is kept below that necessary to form a clinker.

the composition
cements

vary

Cement'

was

of a single, natural substance cannot be controlled, natural

considerably
the

Because

most

in

composition.

important

natural

In

cement

Britain
and

the

so-called

its place

in

'Roman

history

is

significant since it was attempts to duplicate this material from a mixture of

clay and limestone that led to the formulation of Portland cement.
Portland Cement
Portland

cement

predetermined

is a product

composition,

obtained

by burning

of calcareous

and

an homogeneous mixture, of

argillaceous, or other

material

containing silica, alumina and iron oxide, components at a temperature sufficient

to cause clinkerisation, followed by grinding of the clinker.
Portland cements must be composed largely of calcium silicates and not a mixture
of lime and silicates.
employed.

This means that a limersilica ratio of about 3:1 must be

To ensure that complete reaction takes place between the lime and the

silica a minimum burning temperature of 1300C is required.

-275-

APPENDIX A7
COMPRESSIVE STRENGTH AND DENSITY RESULTS

277-

WEAVER'S MILL

COMPRESSIVE STRENGTH A N D DENSITY RESULTS:

1.

PREPARATION:

Capped Length:

73.5mm

2.

STORAGE:

3.

AGE OF SPECIMEN:

4.

DENSITY (water displacement):

5.

MAXIMUM FAILURE LOAD:

6.

CORRECTION FOR STEEL:

7.

STRENGTH:

Diameter:

Method: SULPHUR

73rnm

AIR

YEARS

87

Compressive Strength:

2278

kN

41.57

Estimated In-Situ Cube Strength:

kg/m

MPa

1.68

Failure Mode:

NORMAL

Coring Direction:

HORIZONTAL

M P a

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

D.L. TEMPLE

CORE MARK/NO: 1

DATE OF TEST:

20.3.85

SIGN:

b-G/y-rJL^

^ t

APPROVED
PROJECT ENGINEER:
DATE:
SIGN:

L.G. MALLINSON

22.3.85

L.t*.

tU^^

279-

WEAVER'S MILL

COMPRESSIVE STRENGTH AND DENSITY RESULTS;

1.

PREPARATION:
Capped Length:

75.5mm

Diameter:

Method: SULPHUR

73mm

AIR

2.

STORAGE:

3.

AGE OF SPECIMEN:

4\

DENSITY (water displacement):

5.

MAXIMUM FAILURE LOAD:

6.

CORRECTION FOR STEEL:

7.

STRENGTH:

8?

YEARS

2309
186

Compressive Strength:

44.44

Estimated In-Situ Cube Strength:

45.04

Failure Mode:

kg/m 3
kN

MPa
M

^a

NORMAL

Coring Direction:

HORIZONTAL

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

D.L. TEMPLE

DATE OF TEST:

SIGN:

CORE MARK/NO:

20.3.85

bo/vwyJ L^
APPROVED

PROJECT ENGINEER:
DATE:
SIGN:

L.G. MALLINSON

22.3.85

l~.(* f*4^>_-

-280-

WEAVER'S MILL

C O M P R E S S I V E S T R E N G T H A N D DENSITY RESULTS:
1.

PREPARATION:
Capped Length:

68mm

2.

STORAGE:

3.

AGE O F S P E C I M E N :

<f.

DENSITY (water displacement):

5.

MAXIMUM F A I L U R E L O A D :

6.

C O R R E C T I O N F O R STEEL:

7.

STRENGTH:

Diameter:

73mm

Method: SULPHUR

AIR
87 YEARS

Compressive Strength:

184

43.96

Estimated In-Situ Cube Strength:

Failure Mode:

2295

42.70

kg/m 3
kN

MPa
MPa

NORMAL

Coring Direction:

HORIZONTAL

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

D.L. TEMPLE

DATE OF TEST:
SIGN:

CORE MARK/NO:

20.3.85

cX/h^
APPROVED

PROJECT ENGINEER:
DATE:

22.3.85

SIGN:

L.6t.

L.G. MALLINSON
JJ^f.

281

WOOLSTON QUAY

COMPRESSIVE STRENGTH AND DENSITY RESULTS:

1.

PREPARATION:
Capped Length:

1 00mm

2.

STORAGE:

3.

AGE OF SPECIMEN:

4.

DENSITY (water displacement):

5.

MAXIMUM FAILURE LOAD:

6.

CORRECTION FOR STEEL:

7.

STRENGTH:

Diameter: 99mm

Method:

SULPHUR

AIR
86 YEARS

Compressive Strength:

2301
416

54.0

kN

MPa

Estimated In-Situ Cube Strength: 54.22

Failure Mode:

kg/m 3

MPa

NORMAL

Coring Direction:

HORIZONTAL

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

D.L. TEMPLE

DATE OF TEST:

CORE MARK/NO:

20.3.85

APPROVED
PROJECT ENGINEER:
DATE:

22.3.85

SIGN:

t.

r .

L.G. MALLINSON
t\*kh>

1X1-

WOOLSTON QUAY

COMPRESSIVE STRENGTH A N D DENSITY RESULTS:

1.

PREPARATION:
Capped Length:

97.5mm

Diameter:

99mm

Method:

SULPHUR

AIR

2.

STORAGE:

3.

AGE OF SPECIMEN:

<f.

DENSITY (water displacement):

5.

MAXIMUM FAILURE LOAD:

6.

CORRECTION FOR STEEL:

7.

STRENGTH:

86 YEARS

Compressive Strength:

2297
422

54.82

Estimated In-Situ Cube Strength:

Failure Mode:

54.48

kg/m3

k N

MPa

MPa

NORMAL

Coring Direction:

HORIZONTAL

The above results were obtained using the method, of BS lS81:Part 120:1983 and
include all mandatory i n f o r m a t i o n .
TESTER
NAME:

D.L. TEMPLE

DATE OF TEST:

SIGN:

CORE MARK/NO:

20.3.85

^ J ^-Q^Ji^
APPROVED

PROJECT ENGINEER:
DATE:
SIGN:

L.G. MALLINSON

22.3.85
L.Cr.

283-

WOOLSTON QUAY

COMPRESSIVE STRENGTH AND DENSITY RESULTS;

1.

PREPARATION:
Capped Length:

95mm

2.

STORAGE:

3.

AGE QF SPECIMEN:

b.

DENSITY (water displacement):

5.

MAXIMUM FAILURE LOAD:

6.

CORRECTION FOR STEEL:

7.

STRENGTH:

Diameter:

9qmm

Method: SULPHUR

AIR

86

YSARS

Compressive Strength:

, 30

55.86

Estimated In-Situ Cube Strength:

Failure Mode:

2299

5493

kg/m
kN

MPa
MPa

NORMAL

Coring Direction:

HORIZONTAL

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

D.L. TEMPLE

DATE OF TEST:

SIGN:

CORE MARK/NO:

20.3.85

> t -G^ju^
APPROVED

PROJECT ENGINEER:
DATE:

SIGN:

L.C.

MALLINSON

22.3.85

_.Gr .

tULh^

284

RALLI BUILDING

COMPRESSIVE STRENGTH AND DENSITY RESULTS:

1.

PREPARATION:
Capped Length:

78mm

2.

STORAGE:

3.

AGE OF SPECIMEN:

4.

DENSITY (water displacement):

5.

MAXIMUM FAILURE LOAD:

6.

CORRECTION FOR STEEL:

7.

STRENGTH:

Diameter:

72.5mm

Method:

SULPHUR

AIR
71 YEARS
2298
86

kg/m 3
|<N

Compressive Strength:

20.8

MPa

Estimated In-Situ Cube Strength:

21.40

MPa

Failure Mode:

NORMAL

Coring Direction:

HORIZONTAL

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

D.L. TEMPLE

DATE OF TEST:

SIGN

CORE MARK/NO:

1.5.85

t i-Wj^
APPROVED

PROJECT ENGINEER:
DATE:
SIGN:

L.G. MALLINSON

2.5.85
...

f t l / >

285-

RALLI BUILDING

COMPRESSIVE STRENGTH AND DENSITY RESULTS;

1.

PREPARATION;
Capped Length:

82mm

Diameter:

72.5mm

Method:

2.

STORAGE:

3.

AGE OF SPECIMEN:

t*.

DENSITY (water displacement):

2293

kg/m 3

5.

MAXIMUM FAILURE LOAD:

80

|<N

. 6.

SULPHUR

AIR

71 YEARS

CORRECTION FOR STEEL:

7.

STRENGTH:
Compressive Strength:

19.4

Estimated In-Situ Cube Strength:

Failure Mode:

20.34

MPa
MPa

NORMAL

Coring Direction:

HORIZONTAL

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

D.L. TEMPLE

DATE OF TEST:

SIGN:

CORE MARK/NO:

1.5.85

> t WrJU.
APPROVED

PROJECT ENGINEER:
DATE:

2.5.85

SIGN:

L<*-

L.G. MALLINSON

f**^^_

-286

RALLI BUILDING

COMPRESSIVE STRENGTH AND DENSITY RESULTS:

1.

PREPARATION:
Capped Length:

109mm

Diameter:

! 00n

Method:

SULPHUR

AIR

2.

STORAGE:

3.

AGE QF SPECIMEN:

't.

DENSITY (water displacement):

5.

MAXIMUM FAILURE LOAD:

6.

CORRECTION FOR STEEL:

7.

STRENGTH:

71 YEARS

Compressive Strength:

2313
288

36.7

Estimated In-Situ Cube Strength:

Failure Mode:

37.95

kg/m'
kN

MPa
MPa

NORMAL

Coring Direction:

HORIZONTAL

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

DATE OF TEST:

SIGN:

CORE MARK/NO:

D.L. TEMPLE
1.5.85

SMALL AGGREGATE (DENSITIES OF

OTHER SMALL AGGREGATE CONCRETES:
2313, 2383, 2384 kg/m3)

^ d ^7-U_
APPROVED

PROJECT ENGINEER:

L.G. MALLINSON

DATE:

2.5.85

SIGN:

_-Cr. K * U A _ ^ _ ~

287

RALLI BUILDING

COMPRESSIVE STRENGTH AND DENSITY RESULTS;

1.

PREPARATION;
]0Qmm

Capped Length:

Diameter:

00mra

Method: SULPHUR

AIR

2.

STORAGE:

3.

AGE-OF SPECIMEN:

i*.

DENSITY (water displacement):

5.

MAXIMUM FAILURE LOAD:

6.

CORRECTION FOR STEEL:

7.

STRENGTH:

? 1 YEARS
-

kg/m

288

kN

Compressive Strength:

19.1

MPa

Estimated In-Situ Cube Strength:

19.68

MPa

Failure Mode:

NORMAL

Coring Direction:

NOT KNOWN

The above results were obtained using the method, of BS 1881:Part 120:1983 and
include all mandatory information.
TESTER
NAME:

D.L. TEMPLE

DATE OF TEST:
SIGN:

CORE MARK/NO:

1.5.85

S of S^yJiS^
APPROVED

PROJECT ENGINEER:

L.G. MALLINSON

DATE:

2.5-85

SIGN:

C-.Gt. t~<h^=z-

-288

APPENDIX A8
T.E. SORPTION TEST RESULTS

289-

T.E. SORPTION TEST

.
.
HISTORIC CONCRETE
structure: .

Test Date: .. 6.-,9.-.85. .

M.A. WARD
Tested By:

Sample: .. .W.E.A.V.E.R.'.S. .I 1 .^
Age at Test: .. ,8.7. J.E.A.R.S.
Dimensions: .. & . . J . . ? , t ..i..?. W . . ) mm
mm 2

Cross Sectional Area (A) : . ...TQ

9

Oven Dry Sample Weight (Wd) : . . . \ \ . : . 1 . . . g

MEASUREMENTS
TIME V (mins )
0
WEIGHT Wt. (g )

Wd

10

30

60

120

240

119.90 119.94 120.04] 120.07120.16120.26

Wt - Wd 1 g.)

3.23

0.27

0.37

0.40

O.49

0.59

3.30

0.36

0.49

0.53

0.64

0.78

5-48

7-75

10-95

15-49

j (mm /mm

/ t (mins '4 )
HEIGHT RISE (mm)
a t given distance
from edge

NOTE

i = Wt - Wd * 10 mm / m m

2-24

3 16

0 mm.

2.5

5 mm.

15mm.

30 mm.

for water sorption

RESULTS

SORPTIVITY. S=0.04wi/in!'
(Determined from graph.)

291

T.E. SORPTION TEST

HISTORIC CONCRETE
Structure :
Sample: .-WLSTON^QUAY

Test Date:
Tested By:

6.0.85
M.A. WARD

Age at Test: ..??."*??

Dimensions: . K 3?..)..?. ii ?..)..?. L8.5.. ) mm
702
Cross Sectional Area (A) :
mm*
Oven Dry Sample Weight (Wd): ,1.\8.-..A

MEASUREMENTS

TIME 't' (mins )

0
WEIGHT Wt. (g )

Wd

Wt - Wd ( g )

I 5

30 | 60
120
240
10
1 4 8 . 3 2 148.28 I 4 8 . 5 9 I 4 8 . 6 7 I4.82 i A a . y j

0.28

0.34

0.55

0.63

0.78

0.89

i (mm / mm )

0.40

0.48

0.78

0.90

1.11

1 .27

/t

(mms '4 )

2-24

3 16

540

7 75

10-95

15-49

0 mm

2.5

5 mm

2.5

15mm.

30 mm

HEIGHT RISE (mm)

at given distance
from edge

SORPTIVITY. S : 0 . 0 W r t n i '
(Determined fron graph.)

-292-

APPENDIX A9
WATER PERMEABILITY TEST RESULTS

293

FIG. A9-1

APPARATUS FOR MEASURING WATER

PERMEABILITY

Steel base
and cap-

Outlet to
measuring
pipette

Water
10 bar

50mm long core

section with cast
epoxy resin sides

295

PERMEABILITY
DATE

OPERATOR

PROJECT MO.

MATERIAL TYPE

PRESSURE

LOCATION WEAVERS MILL

HISTORICAL CONCRETE
SPECIMEN

WT OF SPECIMEN

728.5
SPECIMEN DEPTH

C 291 (1 )

VT OF SPECIMEN + RESIN
WT OF SPECIMEN
851 e AFTER TEST

873 6

P,

m PRESSURISED AT . . . .9... .. ON .?2;8..85>#

9 - 3

0.0438
SURFACE AREA

0.00774
PENETRATION

'PP..... O N

SATURATED AT . P.
AT

..??: 8 ;?5.

. ON

Delete as required
REMARKS
Darcys Coefficient

After 5 minutes water

appeared on the sample
surface.

-9
2.36 x 10 m/sec
Valenta's Coefficient

1 ml of water collected
in 24 sees.

_q
2.09 x 10 m/sec

Void content = 6.55%

DARCY'S COEFFICIENT

K.

4-.-

m/sec

= Coefficient of Permeability (m/eec)

= Pressure head (m)

_
Q

n
. / T/ x TT x rad of tubera i rlae (a)
= Flow
rate (m'/sec) = u
i
*~t

= Cross sectional area of specimen (m )

VALENTA'S MODIFIED
COEFFICIENT

* - TF * T

Specimen depth (n)

/s c

" '

.r j

^ /o/\

wet weLttht dry weight

= Voids content {%) =

Tine (sees)

-296-

g, w i

.,

x 100

PERMEABILITY
DATE

; OPERATOR

L. Ma.

PROJECT NO.

MATERIAL TYPE

! PHESSTTRE

10 BARS

LOCATION WEAVERS MILL

CONCRETE

SPECIMEN

VT OF SPECIMEN
485.1

SPECIMEN DEPTH
0.0307

SURFACE AREA
0.00724

'WT OF SPECIMEN + RESIN

576.7
9

WT OF SPECIMEN
TEST

e AFTER

10

PRESSURISED AT ,.-...... .. ON

SATURATED AT .. ?.'??.... ON ...21:?-85

PENETRATION

No. 2

591 1

..?9; ;? .
*
*

AT

lilil

* Delete as r e q u i r e d
REMARKS
Darcy's Coefficient

Water immediately
rushed out through
the sample surface.

= 1.06 x 1 0 ~ 8 m/sec

(- 10 sec.)

Valenta's Coefficient
= 3.05 x 1 0 " 8 m/sec.

1 ml of water collected
in 4 sees.
Void content = 6.48%

1.

DARCY'S COEFFICIENT

;
/

A t ?

= Coefficient of Permeability (m/aec)

= Pressure head (m)

"/s'c

TT i rad of tube 2 * x rise (m)

= Cross sectional area of specimen (m )

= Specimen depth (m)

t>

, *,

VALENTA'S MODIFIED
COEFFICIENT

K '

. ,
..
,,s
= voids content {%) =
v/
'
= Tixe (sees)

297

wet weight - dry weight . ^,

x 10
r 01
r-rr

dry weight

PERMEABILITY
DATE

; OPERATOR

3.7.85

MATERIAL TYPE

PrSSSuE

L>

PROJECT SO.

Ma

LOCATION wooLSTON QUAY

10 BARS

CONCRETE

SPECIMEN

VT OF SPECIMEN
612.4

0.032

0.00778

2
m

SPECIMEN DEPTH
SURFACE AREA
PENETRATION

VT OF SPECIMEN + RESIN
702.9

Cor

e No.

sim

WT OF SPECIMEN
AFTER TEST

710.0

. . ON ..8.-7.-85..
*

ON
AT . .9.-0.0.... . ON . . 2 3 . 9 . 8 5 .

mm

* Delete aa required
REMARKS
Valenta's Coefficient

After 46 days in the rig

no water appeared on
the sample surface.

1 .03 x 1 0 " U m/sec.

Void content - 10.14%

1.

DARCY'S COEFFICIENT

-.d.

m/sec

VALENTA'S MODIFIED
COEFFICIENT
d

= Coefficient

- P r e s s u r e h e a d (m)

, xi
rr
N
= Flow r a t e ( m V a e c ) =

= C r o s s s e c t i o n a l a r e a o f s p e c i m e n (m )

<

= S p e c i m e n d e p t h (m)

.,
trj\
wet w e i g h t - d r y w e i g h t
l n n
= V o i d s c o n t e n t (%) =
* w i g
* " " x 100
? i i e (sees)

-298

of P e r m e a b i l i t y

(m/eec)

i r a d o f tube 2 !!! i r i s e (m)

1

PERMEABILITY
DATE

OPERATOR

MATERIAL TYPE

PESSSEE

L. Ma
10

PROJECT NO.
IX3CATI0N

BARS

CONCRETE

SPECIMEN

VT OF SPE CIME N

VT OF SPE CIME N + RE SIN

652.9

567.1
SPECIMEN DEPTH
0.0342
SURFACE ARE A

0.007354m 2

WOOLSTON
QUAY
No#

VT OF SPE CIME N
e Arrmt TE ST

658.9

PRESSURISED AT . . . 9 .-. 1 . 0 .... ON . . 3 C ; : 5 .

SATURATED AT

PENETRATION

ON

AT JP,3P.

ON ..13,9.85.

* Delete as required
REMASES
Valenta's Coefficient (Penetration)
= 2.02 x 1 0 " U m/sec.

After 14 days in the

rig no water appeared
on the sample surface.

Void content = 13.6%

1.

DARCY'S COE FFICIE NT

A t ?

CUKiriCLtafi'

K -

v
*

it?

.
>"/sec

= Coefficient of Permeability (m/sec)

= Pressure head (m)

, j, f

** VALENTA'S MODIFIE D

dz

TT i rad of tube2 m x r i s e (m)

= Cross s e c t i o n a l area of specimen (m )

= Specimen depth (m)

., . ,
//\
wet weight - dry weight
^,
= / o l d s c o n t e n t (%)
=
=
r-jr
="=- x 100
v/
'

= Ti2ie ( s e c s )

-299

dry w e i g h t

APPENDIX A1O
SIEVE ANALYSIS RESULTS

-301 -

Taylor Wood row

Research Laboratories
SIEVE ANALYSIS
SIEVE ANALYSIS REPORT No
Project... ^A3.1;0.1.1-.0. PPPPFP?

Job Number... 4133

Material.. .A&?&?.a

Nature of Stone. .Ite^ej:'.s Jill

Sample received

From

Supplier

Date of Analysis..

SIEVE SIZE

75mm

(3)

63mm

(2")

WEIGHT
RETAINED (grm)

% WEIGHT

% WEIGHT

RETAINED

PASSING

i}......

3S.882 GRADING
LIMITS

37.5mm (l")
20mm

(iM)

14mm

(J")

10mm

(f")

15.8

6.0

94

(3/16")

42.4

16.3

77-7

2.36mm (7)

50.00

19.3

58.4

1.18mm (14)

60.6

23.3

35.1

600

(25)

47.8

18.4

16.7

300

(52)

33-8

13.0

3.7

150

(100)

7.0

2.7

1.0

75

(200)

2.0

0.8

0.2

0.6

0.2

5mm

Pan
Remarks

MM

2^7^
. . . . . . . . t . T. t / . . . . i~r-i y . . for and on behalf of
Taylor Woodrow Construction Ltd
345 Ruisiip Rotd Southall Middlesex UBI 2QX Telephone 01-578 2366

tffWW
303

Taylor Wood row

Research Laboratories
SIEVE ANALYSIS
S U S V U AJ[ALYSIS

r,

-+

...

H i s t o r i c Concrete

. .

REPC
Job

Afferefi"ates

Nat\are of Ston
Woolston O^uay

Sample r e c e i v e

V
Dat s of Analysis...'-J.' .U...

SIEVE SIZE
75

(3")

63mm

(2i")

% WEIGHT
RETAINED

WEIGHT
RETAINED (grm)

% WE IGHT 1 BS.882 GRADING

PASSING 1 LIMITS

37.5mm (1")
20mm

(i")

14mm

(")

10mm

(f")

68.0

35.1

64-9

52.4

27.1

37.8

2.36mm (7)

24.2

13.O

24.8

1.18mm (14)

12.1

5-3

19.5

600

(25)

11.7

6.1

13.4

3OO

(52)

18.0

9.3

4.1

150

(100)

5-8

3.1

75

(200)

1.3

0.7

0.3

0.5

0.3

5mm

(3/16")

Pan
Remarks

tt
.. ^ C w J ^ w . . . .

for and on behalf of

Taylor Woodrow Conttruction Ltd

345 Ruislip Road Southall Middlesex UBI 2QX Telephone 01578 2366

APPENDIX All
OXYGEN DIFFUSION TEST RESULTS

305

SAMPLE REF
OXYGEN DIFFUSION TEST
HISTORICAL CONCRETE
Structure :
Sample :... .WE.A.V.E.R.'.S. !L.L.

26.6.85
Test Date :
M A
WARD
T e s t e d By: ..-./. .....

Age at Test:..87..Y.E.A.R.S.
Specimen depth, d
*
cm Position of Specimen in Core...,
Exposed Concrete Surface Area, A..........cm

MEASUREMENTS
Oxygen Concentration, 0-.... ,2.5.-.6.9.
1
Oxygen Pressure
.V.2.
Helium Flow, He^
A'.8.

% Conditioned In 9 0 % R.H..,~.
cm Hg + 760mm Hg = 9 0 2 mm Hff
ml/mm =
.-.0.7.9.
ml/sec

-3
Oxygen Diffusion Constant, DOp. .2.-.5...x. .1... ..cm/sec
Air Flux, Jair

-9
-I..9.0 .x .1.0.

2
mole/sec/cm

307

S 102

SAMPLE REF

S108

OXGEN DIFFUSION TEST

Test Date : . . . 2 .V. 7 .\ 8 . 5 .

S t r u c t u r e : . . . W5IPBIC. CpfcJCREJE
Sample :

DLSTON QU

^ H . ?.U.A.Y

Age a t T e s t :

Tested By:. . M /.V. .WAR.D.

8 6 YEARS

Specimen depth,
d
dej

3."
"5
.

cm Position of Specimen in Core...,

en py

Exposed Concrete Surface Area, A..........cm

MEASUREMENTS
Oxygen Concentration, 0-.... .V.5.1
Oxygen Pressure,
J/.6.
Helium Flow, j.He2... .3.\7.5.

% Conditioned In 90% R.H...".

cm Eg + 760mm Hg = 8 3 6 m m H g
ml/mm =
..-.0.7.7.6.
ml/sec

O x y g e n D i f f u s i o n C o n s t a n t , D 0 2 . .8.-.2.8..x..1.0.. . . c m / s e c
Air Flux, Jair

-10
V.2.9. ,x# .1.0.

2
mole/sec/cm

-308-

SAMPLE REF
OXYGEN DIFFUSION TEST
c.

,
HISTORICAL CONCRETE
Structure:
Qn,i.
WOOLSTON QUAY
bample:
.m ,
Age at Test:

26.6.85
A ^ ^
Test
D ate:
_
, ,_
M.A. WARD
Tested
By:

86 YEARS
3.7
."

Specimen depth, d

cm Position of Specimen in Corei

50 27
2
Exposed Concrete Surface Area, A.....'.... .cm

MEASUREMENTS
Oxygen Concentration,

0^

"

Oxygen Pressure,
Helium Flow, F H e 2

% Conditioned In 9 0 % R.H...".
cm H g + 760mm H g =

. .\ .

ml/mm =

Oxygen Diffusion Constant, D0.. .q.-.7.6. .x..1.. ..cm /sec

Air Flux, J a i r

.V.5.2. . x . .1..

10

mole/sec/(cm

309

.'.1.0.6.

ml/sec

S101

European Communities Commission

EUR 10937 A historical e x a m i n a t i o n of c o n c r e t e
L. G. Mallinson.

I. LI. Davies

Luxembourg: Office for Official Publications of the European Communities

1987VI, 309 pp., 30 tab., 57 fig., 63 photos 21.0 x 29.7 cm
Nuclear science and technology series
EN
ISBN 9 2 - 8 2 5 - 6 9 6 3 - 2
Catalogue number: C D - N A - 1 0 9 3 7 - E N - C
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USD 25

The requirement that concrete in radioactive waste repositories be stable physically

and chemically for very long times has initiated studies of ancient and old concretes.
This report is a contribution to this effort.
After a description of the history of cement and concrete, the published literature
relating to the analysis of old and ancient concrete is reviewed. A series of samples
spanning the history of concrete has been obtained; a variety of physical and
chemical techniques have been employed to characterize these samples.
Reasons for survival of ancient concretes, and for durability of early, reinforced
concretes are identified. Recommendations for further studies are given.

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