Prfanstalt Mannersdorf

CENTRE TECHNIQUE EUROPE CENTRALE GMBH

Roter Weg 2
A-2452 Mannersdorf a. L
Tel.: +43/2168/68150
Fax.: +43/2168/68150-13

Report
BottleRollTest

Customer:
Examination for:
Order from:

CTEC-TL
CTEC-TL
Heinrich Karoh

Order No. PM:

Author:
Date:

00204 L
Sandler
05.06.2001

Distribution:

TQD, TQL, TQP

Pages: 12

Annex: -

Account : LAB PRFMETH

Sign: ES

Photos:-

Copies: 1-fach

SUMMARY:
The fluidity of cement is responsible for the time a cement takes to flow out of a silo.
Less fluidity of cement can cause customer complains. Therefore it is necessary to
determine the fluidity of cement. But yet there is no reliable method available.
This report points out that the BottleRollTest (BRT)
indicates low fluidity of a tested cement
as well as lump formation in the cement.
results depend on the circumstances of performing. tests should be done by
the same person using the same bottle.
The BRT is a easy and cheap method which can be used in plants and on the
building site as the only prerequisite is a horizontal basis.
Obviously the normal range of BottleRollWide (BRW) has to be determined for each
cement type.

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1.

Bottle Roll Test

The fluidity of cement is responsible for the time it takes a cement to flow out of a
silo. This property depends on the forces that act between the particles (surface
forces) and therefore the main influence factors are fineness of cement and
additives (grinding aid). Apart from that the time to flow out of a silo becomes longer
due to lump formation. Lump formation is caused by surface forces but mainly
because of pre-hydration of cement (in the silo).
Low fluidity can cause customer complains as it provokes delays when cement shall
flow out of the silo. Nowadays it is difficult to handle such complains as there is no
reliable method available to determine the fluidity of cement.

1.1

The Method

The Bottle Roll Test (BRT) was developed to characterise the fluidity of cement. The
test is performed by:
1. Cement (40,00 g) is filled into a bottle.
2. Homogenisation and fluidising of cement is done by turning the bottle around its
axis.
3. The bottle then rolls down a ramp and along a flat until it stands still.
4. The roll wide on the flat part is measured.
5. Repeat steps (2) (4) five times.
6. As the result the average (BRW= bottle roll wide) is calculated. It serves as the
indicator of the fluidity of cement.
Fig. 1: Ramp for the BRT

The results of the BRT can indicate low fluidity of cement as well as lump formation:
Low fluidity BRW below normal range
Lump formation BRW exceeding the normal range
This is in accordance with the below mentioned results (2.1) and with the theoretic
estimations (3).
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2. Tests done
Overview
1. Results of BRT:
Cement of low fluidity
Cement with lump formation
2. Usage quality of the method:
Monitoring dispatch samples (PZ 375(H), MDF)
Different bottles/different preparation
Different users

2.1

Results of BRT

2.1.1 Cement of Low Fluidity

Customer Complain
BRT was performed on a PZ 475 MAN that was complained because of low fluidity.
The BRW was compared to that determined on a former taken sample:
BRW of former taken samples:
BRW of complained cement:

21,4 and 27,8 cm.

12,0 and 11,2 cm.

The BRT gives a clear difference between the objected cement and the normal
cement: The BRW of the cement with bad fluidity (reported by customer) is about
half the wide of the good cement.
DSC results gave no distinctive differences in sulphate phases. Also the Blaine was
more or less the same for all samples. A slight difference was observed in heat of
hydration.
Influencing the Fluidity by Addition of Grinding Aid
Clinker is ground with addition of grinding aid and the BRW of the obtained cement
is determined:
Ordinary Portland clinker produced in MAN.
6% sulphate (2/3 di-hydrate, 1/3 hemi-hydrate).
Grinding aid: ADM I from Chryso, di-ethylene-glycole (DEG), HEA from Grace.
Addition of grinding aid: 50, 100, 150, 300, 450, 600 g/t.
Mill: BB10, CTEC Lab.
Fineness: 4000 Blaine.
Test Results:
Fig. 2 gives the BRW of a cement as a function of the amount of grinding aid added.
Generally speaking an increase in grinding aid causes a higher BRW. The reason why
grinding aid has an influence on BRW is probably because it changes the potential.
Besides, this is the reason why it prevents coagulation and by that reduce the energy
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60

Fig. 2: Effect of Grinding Aid

BRW /[cm]
20
40

HEA

DEG

ADM1

1000

2000

3000

4000

Grinding Aid /[g/t]

effort necessary for grinding. This change in surface forces improves the fluidity of
cement and leads to a higher BRW.
2.1.2 Cement with Lump Formation
Cement with Lumps Reported by Plant
BRT were performed on a cement that showed lumps according to the plant
statement. The BRT result is compared to the normal range of this cement.
Cement: PZ 375(H) (= CEM II/A-S according to EN) from MAN, silo 17; dispatch
sample; entrance nr. 20002946.
Normal range is determined by monitoring of dispatch samples (3.1).
normal range of PZ 375(H) MAN:
BRW cement with lumps:

17,5 3 cm
30 cm

The cement with lump formation is marked by larger BRW. It is about 1,5 times as
wide as cements with no lumps and usual fluidity.
Artificial Silo Storage
If the temperature in a cement silo is above 70C the gypsum added during grinding
will dehydrate and the released water will cause lump formation.
To simulate this effect cement is stored in a closed box at the given temperature
(Tab. 1) for 24 hours immediately after grinding:
Clinker from MAN.
Sulphate Phase: varying amounts of gypsum (DH) and anhydrite (AH), sum: 7
w% of cement.
Mill: BB10 CTEC Lab.
Fineness: 4000 Blaine.
Afterwards during cooling the box is opened.
Analyses:
DSC (DH, HH) and Eltra (total SO 2 AH) before and after storage.
BRW of cement after artificial storage.
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Tab. 1: Artificial Storage

gypsum : anhydrite

temperature
/[C]

30:70
50:50
70:30

each at
70, 90 and 110 C

Test Results
Fig. 2 shows the change in gypsum content (DH) and hemi-hydrate (HH) content
when curing cement at different temperatures (artificial storage). The labels in Fig. 2
give the original relation between DH and AH (tab. 1).
At about 70C gypsum starts to split off water and hemi-hydrate is formed. With
increasing temperature the reaction occurs faster and the amount of HH increases.
Fig. 2: Sulphate Phases and Artificial Storage

Sulphate Phases /[%]

1,5
1
HH

0,5

50:50

30:70

70:30

30:70

-0,5
DH

-1

50:50
70:30

-1,5

DH

-2
20

40

60
80
Storing Temperature /[C]

100

120

Remark: Changes in AH content (anhydrite and rest SO 3) are not printed in the
diagram as the content in AH stays the same (T <120C).
Fig. 3 gives the correlation between BRW and the ratio of HH to total sulphate. The
labels give the initial rate of DH/AH. Because of the above mentioned assumptions,
HH which develops during storage serves as an indicator for lump formation. The
Fig. 3: BRW as function of ratio HH/sulphate phases

BRW /[cm]

30

50:50

25

30:70
70:30

20

15
0,03

0,13

HH/SO4, tot

0,23

0,33

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BRW increases with increasing ratio of HH. Obviously there is a linear relation
between HH and BRW. This correlates very (R2=91%) well for high amounts of HH
independent form the initial rate of DH/AH.
2.1.3 Resume
The BRW for cement
decreases if the fluidity becomes worse
increases if there is lump formation.
These effects were observed for complained cements as well as for artificial
produced samples.

2.2

Usage Quality of BRT

2.2.1 Continuously BRT on dispatch samples (MDF)

Test procedure
Twice a week dispatch samples of a PZ 375(H) (= CEM II/A-S) from plant
Mannersdorf were analysed by BRT. The samples originate from two different silos
supplied by different mills (silo 12 supplied by mill 7, silo 17 by mill 8). Samples were
taken at the lorry dispatch.
Tests were done by the same person every time.
The results obtained by BRT were compared to the ratio hemi-hydrate to total
sulphate phases (analysed by DSC technique and ELTRA).
Note: If problems in fluidity of cement occur the content of hemi-hydrate (HH) is
usually analysed. The HH origins when gypsum dehydrates (temperature > 70C). If
this reaction occurs in the silo the released water hydrates cement particles and lead
to lump formation. Though HH is no reliable indicator for lump formation:
Dehydration of gypsum in the mill will not have negative effects on fluidity and
there are other factors which have a negative influence on fluidity but have
nothing to do with HH!
Test Results and Interpretation
The Fig. 4 and 5 show the results of monitoring. Fig. 4 shows the samples taken
from silo 12, Fig. 5 those from silo 17.
Fig. 5: Continuous Samples Silo 17

BRW /[cm]

25

20

15

10
15.7.00

14.8.00

14.9.00
Date

14.10.00

14.11.00

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Results are printed versus the date of sample taking. The roll wide (each
measurement) is printed as small points, the average (BRW) is signed by a big circle.
Results vary (diagram 4): measures are between 10 and 25 cm, the results (average,
blue circles) between 11,4 to 23,8. The overall average (17.7.00 14.11.00) of the
samples from silo 12 is 15 3cm.

Bottle Roll Wide /[cm]

Fig. 4: Continuous Samples Silo 12

25
20
15
10
15.7.00

14.8.00

14.9.00

14.10.00

14.11.00

Date

Fig. 5 gives the equal diagram for samples taken from silo 17. Again results vary:
Measures are between 10 and 25 cm, averages (BRW) are between 14 - 23 cm. The
over all average (16.07 13.11.00) is 18 cm with a standard deviation of 3cm.
The fluidity of the investigated cement samples was not monitored by other
techniques. Therefore we have to presume that outliers in BRT results are related to
bad fluidity of the cement.
There are no regularly problems with fluidity reported in one of the silos and in both
silos they store the same cement type (PZ 375(H)).
No difference in the fluidity of PZ 375 (H) related to the silo are reported by plant.
Anyway, differences could be expected because of differences in process of mill 7
and mill 8:
Mill shop 7 consists of:
vertical press, ball mill (50t/h), dynamic separator, filter.
Mill shop 8 consists of:
ball mill (100 t/h), static separator, dynamic separator, hurriclon, filter.
The temperatures in mill 8 is higher than in mill 7 (measured after mill) according to
the following facts:
1/3 of the process gas in mill shop 8 is driven through the hurriclone and
therefore cannot be exchanged by fresh air.
Lower energy consumption in mill 7 due to usage of vertical roller press.
Mill 7 is smaller; The smaller the mill the easier it can be controlled.
Therefore a higher temperature in the silo 17 can be expected which promotes lump
formation and probably explains the higher average of BRW of cement from silo 17
compared to that from silo 12.

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Fig. 6 gives the standard deviations as % of the average for cements from both silos:
Fig. 6: Standard Deviation of BRT
relative deviation /[%]

20
15
10

silo 12

silo 17

0
1

number of tests

It demonstrates that:
Deviation of the measurement is about 8%.
Standard deviation becomes better with training.
Fig. 7 gives the correlation between the sulphate phases (HH/sum of sulphates) and
the BRW. The diagram shows results from cements from both silos, those from silo
12 as grey dots, those from silo 17 as yellow dots. Points without frames are
regarded as outliers (no correlation between fluidity and sulphate phases?).
Fig. 7: BRW and Sulphate Phases
30

BRW /[cm]

25

20

Silo 17
Silo 12

15

10
0,0

0,2

0,4
0,6
HH/SO 4, tot /[1]

0,8

1,0

Considering that there are influence factors on fluidity - which have nothing to do
with the ratio of sulphate phases (note on page 7) - the linear correlation for the
other points fits quite well. As stated before one would expect that the lump
formation becomes worse if the ratio HH- content to total content in sulphate phases
(HH/SO 4, tot ) increases as water released from gypsum would trigger lump formation.
Diverts in Fig. 7 might be caused by
other yet unknown parameters influencing the fluidity,
HH level already established in the mill,
varying contents of sulphates in the clinker and different types of gypsum added
to the clinker.
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Resume
Variation in the BRW of 15 3 cm (silo 12) and 17,5 3 cm (silo 17) indicate that
there are apparently always some variation in the fluidity of the products. Results
depend clearly on the silo/mill shop. This is expectable.
Accuracy of the method (standard deviation during monitoring) is 8%. It can be
improved by training.
Obviously the BRW depends on the correlation between the sulphate phases.
2.2.2 BRT with Different Bottles/Different Preparation
Test Procedure
To characterise the influence of the bottles the same cement was tested by the same
person using different bottles. Fluidising was achieved in two different ways:
- rotating the bottle around its symmetric axis.
- turning it from its top to its bottom.
5 revolutions each time. Measurements were repeated 10 times per test.
Test Results
In Fig. 8 the BRW is printed versus the mass of the bottle for the two different ways
of preparation. The small points indicate the individual measures while the big black
points indicate the average. Five glass bottles were used. They are all of the same
type but of course show fabrication tolerances (mass and geometry).
Influence of bottle: The results show that the bottle has a great influence on the
BRW. The effect is probably related to the mass of the bottle. Of course the
geometry of bottle is very important too, but it is difficult to investigate this effect.
Generally speaking the higher the mass of the bottle the wider the bottle rolls.
Fig. 8: BRT with Different Bottles/Different Preparation
BRT with Different Bottles

35

BRW /[cm]

30
rotating around sym.axis
25
turning from top to bottom
20
15
121,4

121,6

121,8
122
122,2
mass of bottle /[g]

122,4

122,6

Influence of preparation: Results also depend on the preparation. When the bottle is
rotated along its symmetric axis, BRW will be about 5 cm longer compared to
fluidising by turning the bottle from the bottom to its top. Standard deviation will
decrease.
Resume
Results of BRT depends on the bottle.
BRW and standard deviation do depend on preparation.
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2.2.3 BRT Done by Different Users

Test Procedure
The aim is to characterise the influence of the user who performs the BRT. Therefore
tests were done on the same cement by three different persons (E, S, W) using the
same bottle. Preparation of the sample (cleaning the bottle, filling in cement, turning
the bottle before measuring), is done with high accuracy and in the same way by
each user. Measurement is repeated thirty times per test.
Test Results
Though preparation and testing was done with high accuracy and in the same way
by everyone there were differences in average, standard deviation, minimum and
maximum measured depending on the person who performed testing.
Fig. 9: BRT done by Different Users
60
55
50
B
R
45
W
/[c
m] 40

35
S

30
25
1

10 Measurement

20

30

Fig. 9 shows three graphs, one for each user (E, S, W). E and S are well trained
whereas W is not. There are outliers for W which are about 1,5 times wider than the
average. E and S do not show such significant outliers.
Measured BRW are between 33 and 40 cm for all users, average and standard
deviation are similar for all users.
As shown above (2.2.1) standard deviation can be reduced when the user is well
trained (E, S). By deleting the most obvious outliers (BRW >50) for the untrained
user comparable results are obtained (average: E= 36,8; S= 34,5; Wcorr=35,3).
Resume
Results of BRT do depend on the user.
Standard deviation are about the same for different user.

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3.

Suggestions on the Mechanism of BottleRollTest

When a bottle rolls down the ramp its velocity increases. The bottle has its
maximum speed when it reaches the flat part of the ramp. From than on its velocity
decreases and finally the bottle stands still. During rotation of the bottle the cement
inside moves, too, and by that consumes energy. There are two important effects:
Turning moment, it depends on the distance between centre of mass (m) and
geometric centre (g) of the bottle.
Inter-particular forces, they determine the
energy consumption of relative movement of
Fig. 10: Braking into Scales
particles.
The extend to which energy is consumed has an
influence on the velocity and on the distance the
bottle rolls (BRW) as shown in the following
examples:
1. At slow rotation the cement will slide along the
g
m
g
glass wall there is no relative motion in the
cement. The energy consumption is related to
the distance between the centre of mass and
the geometric centre. The BRW mainly
depends on density/particle size distribution
(PSD) of cement.
2. When the speed increases cement will be lift up on the inside wall of the bottle
and due to gravity it will break into scales on top. These scales of cement slide
down on the layers that are lift on the side of the bottle (relative movement).
BRW mainly depends on forces between particles (fluidity).
3. At a further increase in velocity centrifugal force is too strong. Cement scales
wont slide down on cement layer. Unwanted situation, ramp is too steep or
fluidising of cement not sufficient.
What we call fluidity of cement summarises the effects of various properties of
cement. The main parameters which influence the fluidity are forces that act
between particles (surface forces, zetapotential) and lumps. These parameters will
influence the BRW like described below:
Assumption 1: Strong forces between particles (bad fluidity):
Denser package due to strong forces between particles; Therefore the distance
between centre of mass and centre of rotation is larger; Higher turning moment
leading to a higher energy consumption.
The relative movement of the particles consumes higher energy.
Shorter BRW for low fluidity.

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Assumption 2: Lump formation:

When cement particles stick together to form lumps they will act like bigger
particles. The sum of surfaces will decrease and therefore the sum of surface
forces acting between cement layers will decrease lower energy consumption.
The sum of distances between centre of mass to the geometric centre will be
shorter reduce of energy consumption.
Bigger BRW for lump formation.
Remark: A similar effect can be achieved by bad preparation; if the cement compacts
it wont get into a relative movement. Rotation consumes only little energy. BRW will
be about twice as wide as usually (compare Fig. 9: measures >50cm).
Resume: For each type of cement the band width for normal fluidity has to be
defined. Exceeding as well as not achieving this range indicates possible problems.
Though usually further BRW will be observed as forces between particles will lead to
lump formation.

4. Resume
The BRW indicates low fluidity of a tested cement. It
decreases if the fluidity becomes worse and
increases if there is lump formation.
This was shown for complained cements as well as for artificial produced samples.
Obviously there is a linear correlation between BRW and sulphate phases.
This correlation fits very well for cements after artificial storage.
For dispatch samples the correlation is ok. considering that there are more
influence factors on fluidity.
The BRT is a simple and cheap method. There are no requirements for its usage
except that the ramp has to stand on a horizontal basis.
Further the results of BRT depend on
the bottle and
BRW and standard deviation depend on preparation.
Results of BRT depend on the user.
The accuracy of the method (standard deviation of measuring) is 8%.
It is shown that by training of the user the standard deviation can be improved.
For the monitored cements (PZ 375(H) MAN) the normal range for the BRT was
determined:
Results depend on the silo/mill shop. This correlates to what was expected.
Silo 12:
15 3 cm
Silo 17:
17,5 3 cm.

LAFARGE CTEC
Department Product - Quality - Development
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