Quality Aspects of Cement Milling

Bob M
c
Quillan
2 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
How does milling effect product performance ?

2 Factors
Physical Parameters
- Surface Area
- Particle size distribution

Chemical Parameters
- Cement SO
3

level
- Form of SO
3


3 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
Surface area and PSD

Fine Ground cement
Higher SSA
Less Coarse Particles



More Reactive Cement
Higher Strengths

Coarse Ground cement
Lower SSA
More Coarse Particles



Less Reactive Cement
Lower Strengths
4 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
PSD and mill type
5 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
Effect of Mill type on Product quality
General rule - more coarse particles = less
complete hydration and lower strengths.

Mill Type % Hydrated 28 Day
strength

Open Circuit 81.3 56

Closed circuit 86.1 59

HES 92.5 63
6 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
ABERTHAW PC-RM grind
45um
0
5
10
15
20
25
22/05/92 11/10/93 02/03/95 21/07/96 10/12/97
%
8 old open circuit mills replaced
by single mill with high efficiency
separator
7 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
CHARACTERISTICS OF ABERTHAW OPEN AND CLOSED
CIRCUIT CEMENTS
OPEN
CIRCUIT
CLOSED CIRCUIT
SSA m2/kg
45 micron residue %
SO3 %
Initial set(mins)
Compressive
strength N/mm2
EN 196 mortar
2 day
7 day
28 day
349
19.9
2.7
120
25.2
43.5
58.8
340
3.5
2.9
175
26
46
64
280
12.4
2.9
230
23
40
59
8 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
SSA and Bleeding
Bleeding is separation of cement particles and water
Bleeding is higher at lower SSA
250 300 350 400 450 500
20
40
60
80
100
SSA m2/kg
BLEEDING RATE cm/min x 10
9 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
Chemical parameters
Cement Sulfate
clinker SO
3
- raw materials, fuel (insoluble)

Gypsum - Calcium Sulfate
- CaSO
4
.2H
2
O (dihydrate)
- CaSO
4
(anhydrite - can be soluble or insol)
- CaSO
4
.1/2H
2
O (hemihydrate)

10 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
Why add Gypsum ?
Soluble sulfate controls C
3
A reactivity - Without it cement
paste would be unworkable
Addition of sulfate increases strength of cement
Makes cement easier to grind, mill throughput
Extends cement, gypsum is cheaper than clinker
11 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
What is soluble SO
3
?
Not clinker SO
3

(alkali sulfate)
Not natural anhydride CaSO
4

- insoluble

Soluble SO
3
comes from dehydration of dihydrate

CaSO
4
.2H
2
O CaSO
4
.1/2H
2
O CaSO
4
(soluble)
12 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
HOT MILLING CONDITIONS (130 DEG C)
0
0.5
1
1.5
2
2.5
3
% BY WEIGHT
GYPSUM
HEMI-
HYDRATE
SOLUBLE
ANHYDRITE
NATURAL
ANHYDRITE
MODERATE TEMPERATURE MILLING CONDITIONS (110 DEG C)
0
0.5
1
1.5
2
2.5
3
% BY WEIGHT
COOL MILLING CONDITIONS (90 DEG C)
0
0.5
1
1.5
2
2.5
3
% BY WEIGHT
INFLUENCE OF MILL TEMPERATURE ON FORMS
OF CALCIUM SULFATE IN CEMENT
GYPSUM COMPOSITION : CaSO4.2H2O 63%, CaSO4 14%
CLINKER SO3 0.34%, CEMENT SO3 3.1%
13 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
Types of gypsum
Natural Gypsum - contains varying levels of insoluble
anhydride and soluble dihydrate
Synthetic Gypsum - does not normally contain insoluble
anhydride, but may also have impurities such as P
2
O
5

BCI target cement SO
3
sd 0.1% - requires consistent
clinker SO
3
and uniform quality easy to handle gypsum
14 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
Optimum gypsum content
Depends on C
3
A content and reactivity
Too much soluble SO
3
- FALSE SET

Recrystallisation of SO
3
- cement loses workability

Too little soluble SO
3
- FLASH SET
C
3
A reactivity is uncontrolled - cement loses workability

Optimum level is determined experimentally in lab - normally
in range 0.8 - 1.2 % (dehydrated gypsum)
15 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
0.5 1 1.5 2
0.60
0.62
0.64
0.66
0.68
INFLUENCE OF LEVEL OF DEHYDRATED GYPSUM
(D.SO3) ON WATER REQUIREMENT
W/C
Required
for 40mm
Slump
D.SO3
CLINKER
B
(C3A 14%)
CLINKER
A
(C3A 8%)
16 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
False Set
Most likely to occur if
- low clinker SO
3

- high cement SO
3

- high dihydrate concentration in gypsum
- high mill temp
- low C
3
A content, reactivity



17 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
Flash set
Most likely to occur if

- high C
3
A content or reactivity
- low mill temps (HES)
- high natural CaSO
4
in gypsum
- coarse ground gypsum
- XS alks over sulfur in clinker

18 Cement Technology Course Preparedand originaaly presented by Lafarge UK -June 2001 (EX BCTC)
Grinding Aids
Consist of chemicals such as glycols and amine
acetates
Most likely to be effective:
at SSAs above 380 m
2
/kg
in closed circuit mills
normal dosage rates 0.02% to 0.03%
HEA2 shortens set and improves early strengths
CBA (tri - isopropanolamine is particularly effective
with high iron (low C
3
A) cements and cements
containing limestone filler