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Ettringite Formation and The Performance of Concrete
Ettringite Formation and The Performance of Concrete
What Is Ettringite?
Ettringite is the mineral name for calcium sulfoaluminate
(3CaOAl2O33CaSO432H2O), which is normally found in
portland cement concretes. Calcium sulfate sources, such as
gypsum, are intentionally added to portland cement to regulate
early hydration reactions to prevent flash setting, improve
strength development, and reduce drying shrinkage. Sulfate and
aluminate are also present in supplementary cementitious
materials and admixtures. Gypsum and other sulfate compounds
react with calcium aluminate in the cement to form ettringite
within the first few hours after mixing with water. Most of the
sulfate in the cement is normally consumed to form ettringite at
early ages. The formation of ettringite in the fresh, plastic
concrete is the mechanism that controls stiffening. At this stage
ettringite is uniformly and discretely dispersed throughout the
Portland Cement Association, 2001
All rights reserved
IS417
The potential impact of excessive gypsum has thus been known for
some time, and is the reason ASTM C 150, Standard Specification
for Portland Cement contains provisions for control of sulfates in
portland cement. Using requirements of ASTM C 150, one can
optimize the level of sulfates in cements to maximize strength
and/or minimize shrinkage, without excessive expansion potential.
Cements are optimized prior to production by testing at various
sulfate levels to achieve maximum strengths in mortar cubes
(and/or minimum shrinkage of mortar prisms). ASTM C 150
contains numerical limits on sulfate levels that are a function of
cement type. In cases where the optimum sulfate level exceeds
table limits, the standard includes an option for a performance test
that measures expansion of mortar bars stored in water. This
provides the opportunity to optimize cements for sulfates, while
protecting against the potential for deleterious expansions.
-anhydrite is often referred to as hard burned anhydrite, which is a term used in the
gypsum plaster industry. It is commonly misperceived that -anhydrite is insoluble.
However, while its rate of solubility is less than other forms, it is sufficient to act as an
effective set controller [Hansen et al., 1988, and Michaud and Suderman, 1999]
10
8
Mass
loss,
%
4
A
2
0
0
200
400
600
Cycles
800
1000
0.10
0.06
Length 0.02
change,
% -0.02
A
B
-0.06
-0.10
0
200
400
600
Cycles
800
1000
120
100
80
Relative
dynamic
60
modulus,
%
40
A
20
0
0
200
400
600
Cycles
800
1000
The potential for slowly soluble sulfates in clinker has been associated with increased levels of total clinker sulfate. The concern
expressed is that changes in cement manufacturing technology
(changes in fuels, recycling of cement kiln dustCKDor use of
alternative fuels such as tires) have resulted in increased levels of
sulfates and the potential for slowly soluble sulfates. Concern has
also been expressed that moving from wet process production to
dry process and preheater, precalciner systems has increased
potential for sulfates in alite and belite.
Changes have occurred in cement manufacture with movement
toward more energy efficient dry process production and
environmental controls. There are four primary types of kiln
systems: wet, long dry, preheater, and precalciner. The latter
three are dry process systems that do not use a water slurry of
raw materials. The preheater and precalciner are the most energy
efficient kiln types, and generally are newer. However, dry
process kilns have been used for many years (Appendix A). There
is no basis to assume that the kiln system in itself would govern
sulfate levels or potential for slowly soluble sulfate.
On average, clinker sulfate levels have increased.3 The change
from natural gas to coal as a fuel source, which the industry made
as a result of the energy crisis of the early 1970s, led to some
increase. Also, since the original Clean Air Act in the 1970s
mandated collection systems for particulate emissions, there has
been a relative increase in CKD available as a raw material source.
CKD is composed of fine particles that consist predominantly of
partially calcined forms of the original raw materials introduced
into the kiln [Klemm, 1994]. CKD also contains alkali sulfates,
which are incorporated into the dust as they volatilize off the kiln
feed during calcination. Relative to cement performance, alkali
sulfates react readily during early hydration reactions. Reuse of
CKD varies from plant to plant because of kiln operating
conditions. In addition, since CKD can contribute to increased
alkali levels of cement, the amount that can be used as a raw feed
source may be limited.4 It should also be noted that recycling of
CKD as kiln feed is not new or unique. It has been a normal,
environmentally beneficial operating practice in many plants
worldwide. In fact many plants in the U.S. recycle all of their CKD,
without detriment to the final product. There are no data to indicate
that CKD use as a raw material contributes to potentially
detrimental slowly soluble sulfates, nor is there any identified
relationship between CKD use as raw feed in cement manufacture
and observed field problems with concrete made from that cement.
Questions have also arisen regarding use of alternative fuels such
as liquid solvents or tires. Liquid solvents are normally lower in
sulfur than the fuel they replace. Published data on sulfur in tires
indicate a range from about 0.9% to 1.8% by mass, with an
3
See Appendix A.
Contrary to a perception often expressed, CKD use as a raw material is not the
primary source of cement alkalies. Alkali levels in cement are strongly dependent
on the alkali content of the original raw materials.
4
The hypothesis that clinker sulfates are slowly soluble has been
criticized on the basis that the dominant form of sulfate in clinker,
alkali sulfates, are in fact rapidly soluble, as are the forms of
calcium sulfate added to make portland cement: gypsum,
hemihydrate, and anhydrite. Michaud and Suderman (1999) have
demonstrated that even anhydrite is sufficiently soluble to act as a
set control agent as it dissolves and reacts quickly. The amount of
calcium sulfate added to the mill with the clinker to control
cement setting is adjusted to account for sulfates present in clinker.
0.50
5
Cured: 70C,
stored 23C.
0.40
C 01
C 03
C 09
C 19
C 22
0.30
C 03-III
C 09-III
Expansion,
0.20
%
0.10
0.00
-0.10
0
0
200
400
600
Time, days
800
1000
0.40
C 09
C 19
Cured: 90C,
stored 23C.
C 22
C 03-III
0.30
C 09-III
0.10
0.00
-0.10
0
200
400
600
Time, days
0.0
0.2
0.4
f' 1/f'28
0.6
0.8
Expansion,
0.20
%
800
1000
3
SO3 ,
%
0.50
k-09 Arm
k-09 A55
k-09 A85
0.40
k-09 Brm
k-09 B55
0.30
k-09 B85
k-09 Crm
Expansion,
0.20
%
k-09 C55
k-09 C85
0.10
0.00
-0.10
0
200
400
600
Time, days
800
1000
ACKNOWLEDGMENTS
This document was prepared under the auspices of the PCAs
Sulfate Task Group:
G. S. Barger, Ash Grove Cement Company
J. Bayles, Essroc Cement Corp.
B. Blair, Lafarge Corporation
D. Brown, Lone Star Industries Inc.
H. Chen, Southdown, Inc.
T. Conway, Holnam Inc.
P. Hawkins, California Portland Cement Company
R. A. Helinski, Blue Circle Inc.
F. A. Innis, Lafarge Corporation
M. D. Luther, Holnam Inc.
W. C. McCall, Blue Circle Inc.
D. Moore, Blue Circle Inc.
W. OBrien, Essroc Cement Corporation
E. R. Orsini, St. Lawrence Cement Inc.
M. F. Pistilli, Dixon-Marquette Cement Company
D. Suchorski, Lehigh Portland Cement Company
O. Tavares, Lafarge Corporation
7
Appendix A:
A Primer on Cement
Brief Overview of Cement Manufacture6
Portland cement is produced by pulverizing clinker consisting
essentially of hydraulic calcium silicates along with some
calcium aluminates and calcium aluminoferrites and usually
containing one or more forms of calcium sulfate (gypsum) as an
interground addition.
Materials used in the manufacture of portland cement must
contain appropriate proportions of calcium oxide, silica,
alumina, and iron oxide components. During manufacture,
analyses of all materials are made frequently to ensure a
uniformly high quality cement.
Steps in the manufacture of cement are illustrated in the flow
charts in Figs. A-1 and A-2. While the operations of all cement
plants are basically the same, no flow diagram can adequately
illustrate all plants. There is no typical portland cement manufacturing plant; every plant has significant differences in layout,
equipment, or general appearance. Following is an approximate
distribution of current cement capacity by primary kiln type:
Process type
Wet
Long dry
Preheater
Precalciner
Percent of
total capacity
Avg. age
(yr.)
28
22
21
29
36
38
24
14
tional speed of the kiln. Burning fuel (powdered coal, oil, or gas,
sometimes supplemented with alternative fuels such as tires) is
forced into the lower (discharge) end of the kiln where
temperatures of about 1450 C (2640 F) change the raw
material chemically into cement clinker, grayish-black pellets
predominantly the size of 13-mm (1/2-in.)-diameter nodules.
The clinker is cooled and then pulverized. During this operation
a small amount of gypsum (approximately 5%) is added to
regulate the setting time of the cement. The clinker is ground so
that most of it passes through a No. 325 mesh (45 micron) sieve.
This fine gray powder is portland cement.
3CaOSiO2
2CaOSiO2
3CaOAl2O3
4CaOAl2O3Fe2O3
= C3S
= C2S
= C3A
= C4AF
Drilling rig
Overburden
;;
;
;
;;
;
;
;;
;
;;
;;
;
;
;;
;;
;
;;
;
;
;;
;;
;
;
;;
;;
;
;
;;
;;
;
;
;;
;
;
;;
;
;;;
;;
;
;
;;
;
;;
;;
;
;;
;
;
To Crusher
Shale
Limestone
sc
To
vib
en
re
in
at
;
;
;
;
;;
;
;
;;
;
;;
;
;
;
;
;
;
;
;
;
;
;;
;
;
;;
;
;
;
;;
;;
;;
;;
;
;;;
Primary crusher
Secondary crusher
Hot air
furnace
;
;
To
Kiln
Raw mix
Fines
Clay
Sand
Iron ore
Grinding mill
Dust
collector
;;;
;;;
Air
To pneumatic pump
Ground raw
material storage
;;;
;;;;;;
;;;
;;;;;;
;;;
;;;;;
;;;;
;;;;
;;;;;
;
;;;;;;
;;;
;;;;;;
;;;;
;;;;
;;;
;;;;;
;;;;;;
;;;;;;;;
;;;
;;;;;;
Grinding mill
Fines
To
Kiln
Ov
Water
added
here
ersize
Slurry
Iron ore
Clay
Vibrating
screen
Sand
We t P ro c e s s
OR
siz
er
Ov
Raw materials
areproportioned
Limestone
Dry Process
;;
;;
;
;;
;;
;
Limestone
To air separator
Slurry
pumps
Raw materials
are proportioned
Slurry
pump
Storage basins
2. Raw materials are ground, mixed with water to form slurry, and blended.
;;
;
Materials are
stored separately
To
Kiln
Dust
collector
Fan
Dust bin
Clinker
Coal, oil, gas,
or other fuel
Gypsum
Air
Clinker cooler
Rotating kiln
Gypsum
Clinker
Air
separator
Overs
ize
Dust
collector
Fine
s
Materials are
proportioned
Grinding mill
Cement
pump
;;;;
Bulk storage
Bulk
truck
Bulk
car
Box
car
Packaging
machine
;;;
Truck
;;
Drilling rig
Overburden
;;
;;
;;;
;;;
;;
;;
;
;;;
;
;;
;
;
;;
;
;
;
;;
;
;;
;
;;
;;;
;;
;
;
;;
;;
;
;;;
;
;;
;
;;
;
;;
;
;;;
;;
;
;
;
;
;;;;;;
;;;;
;;
;
;;
;
;;
;
;
;;
;;
;
;;
;
;;
;
;;
;;
;;
;;
;
;
;;
;
;;
;
;
;;
;;
;
;;
;
;;
;
;;
;
;
;;
;;
;;
;
;
;
;
;;
;
;;
;
;
;;
;
;
;;
;
;
;;
;
;;
;
;
;;
;
;;
;;
;
;;
;
;;;
;
;;
;;
To Crusher
Shale
en
re
tin
sc
ra
Limestone
To
vib
Primary crusher
Secondary crusher
To
preheater
Discharge
Raw mix
Clay
Iron ore
Sand
Limestone
Feed
Dust
collector
Raw materials
are proportioned
Roller mill
;;;;
Product
discharge
port
Raw material
Classifier
blade
Air
To pneumatic pump
Ground raw
material storage
Feed sprout
Grinding roller
Gas intake
port
Hot gas from
kiln, preheater
or cooler
Materials are
stored separately
Clinker
Gypsum
Fan
Dust bin
Rotating kiln
Air
Clinker cooler
Clinker and gypsum conveyed
to grinding mills
3. Burning changes raw mix chemically into cement clinker. Note four-stage preheater, flash furnaces, and shorter kiln.
Exhaust
gas
High
efficiency
dust
collector
Cement
product
and air
to dust
collector
High efficiency
separator
Mill product
and air
Materials are
proportioned
Gypsum
Clinker
Fan
Secondary
Air
k
Clin
nd g
er a
yps
um
Ambient
air
Separator rejects
(tails) return to mill
Finished cement
product to silo
Air
Mill
discharge
Grinding mill
Bucket
elevator
to separator
Solids
Cement
pump
;;;;
Bulk storage
Bulk
truck
Bulk
car
Box
car
Packaging
machine
;;
Truck
6H2O
(Water)
3CaO2SiO23H2O
(C-S-H)
3Ca(OH)2
(Calcium hydroxide)
2(2CaOSiO2)
(Dicalcium silicate)
4H2O
(Water)
3CaO2SiO23H2O
(C-S-H)
Ca(OH)2
(Calcium hydroxide)
3CaOAl2O3
(Tricalcium aluminate)
12H2O
(Water)
Ca(OH)2
(Calcium hydroxide)
3CaOAI2O3Ca(OH)212H2O
(Tetracalcium aluminate hydrate)
4CaOAI2O3Fe2O3
(Tetracalcium
aluminoferrite)
10H2O
(Water)
2Ca(OH)2
(Calcium hydroxide)
6CaOAI2O3Fe2O312H2O
(Calcium aluminoferrite hydrate)
3CaOAI2O3
(Tricalcium aluminate)
26H2O
(Water)
3CaSO42H2O
(Gypsum)
3CaOAI2O33CaSO432H2O
(Calcium trisulfoaluminate hydrate - ettringite)
2(3CaOAI2O3)
(Tricalcium aluminate)
4 H2O
(Water)
3CaOAI2O33CaSO432H2O =
(Ettringite)
3CaOAI2O3CaSO412H2O
(Calcium monosulfoaluminate hydrate)
Note: Table A-1 illustrates only primary transformations and not the several minor transformations.
11
Type of
portland
Loss on
SiO2
Al2O3
Fe2O3
CaO
MgO
SO3
cement
I (min-max)
I (mean)
III (min-max)
III (mean)
IV (min-max)
IV (mean)
V (min-max)
V (mean)
Blaine
Na2O eq
C3S
C2S
C3A
C4AF
fineness,
m2/kg
%
18.7-22.0
4.7-6.3
1.6-4.4
60.6-66.3
0.7-4.2
1.8-4.6
0.6-2.9
0.11-1.20
40-63
9-31
6-14
5-13
300-421
20.5
5.4
2.6
63.9
2.1
3.0
1.4
0.61
54
18
10
369
ignition,
3.4-5.5
2.4-4.8
60.2-65.9
0.6-4.8
2.1-4.0
0.0-3.1
0.05-1.12
37-68
6-32
2-8
7-15
318-480
21.2
4.6
3.5
63.8
2.1
2.7
1.2
0.51
55
19
11
377
18.6-22.2
2.8-6.3
1.3-4.9
60.6-65.9
0.6-4.6
2.5-4.6
0.1-2.3
0.14-1.20
46-71
4-27
0-13
4-14
390-644
20.6
4.9
2.8
63.4
2.2
3.5
1.3
0.56
55
17
548
21.5-22.8
3.5-5.3
3.7-5.9
62.0-63.4
1.0-3.8
1.7-2.5
0.9-1.4
0.29-0.42
37-49
27-36
3-4
11-18
319-362
22.2
4.6
5.0
62.5
1.9
2.2
1.2
0.36
42
32
15
340
20.3-23.4
2.4-5.5
3.2-6.1
61.8-66.3
0.6-4.6
1.8-3.6
0.4-1.7
0.24-0.76
43-70
11-31
0-5
10-19
275-430
21.9
3.9
4.2
63.8
2.2
2.3
1.0
0.48
54
22
13
373
*Values represent a summary of combined statistics. Air-entraining cements are not included. Adapted from Gebhardt, 1995.
**Includes fine grind cements.
12
Table A-2. Chemical and Compound Composition and Fineness of 1990s Cements*
Table A-3. Chemical and Compound Composition and Fineness of 1950s Cements*
Range of chemical composition, %
Type of
portland
Loss on
SiO2
Al2O3
Fe2O3
CaO
MgO
SO3
cement
I (min-max)
I (mean)
II (min-max)
II (mean)
III (min-max)
III (mean)
IV (min-max)
IV (mean)
V (min-max)
V (mean)
ignition,
Blaine
Na2O eq
C3S
C2S
C3A
C4AF
fineness,
m2/kg
%
19.2-24.6
2.9-7.8
0.4-4.2
53.2-66.8
0.3-4.8
1.2-2.8
0.5-8.0
0.06-1.28
20-68
9-49
3-15
1-13
288-439
21.4
5.7
2.7
63.9
2.3
1.9
1.3
0.53
51
23
10
332
21.0-24.5
4.0-5.9
2.6-5.2
61.1-65.0
0.3-4.7
1.3-2.3
0.4-2.4
0.14-0.73
39-50
24-39
4-8
8-16
298-406
22.3
4.8
3.8
63.3
2.4
1.7
1.1
0.48
45
30
12
338
19.5-23.5
3.3-6.3
1.3-4.7
62.5-67.4
0.8-4.0
1.8-3.5
1.0-3.4
0.11-0.69
45-68
8-28
4-12
4-14
396-590
20.9
5.0
3.0
64.5
2.0
2.3
1.8
0.40
59
16
477
23.2-25.2
3.3-5.2
3.3-4.5
62.5-64.0
0.9-1.7
1.5-1.8
0.6-0.9
0.34-0.51
31-37
40-45
3-7
10-14
292-343
24.0
4.4
4.0
63.2
1.2
1.7
0.8
0.42
35
43
12
317
22.5-25.3
2.7-4.2
2.5-4.7
62.2-65.0
0.8-3.9
1.4-2.0
0.6-1.5
0.19-0.80
36-49
30-44
1-5
8-14
291-366
24.1
3.5
3.5
63.9
1.9
1.6
1.0
0.38
44
36
11
327
*Air-entraining cements are not included. Adapted from Clifton and Mathey, 1971.
13
C-S-H
Ca(OH)
Amount
C (A, F)H
4
13
Monosulphate
Ettringite
Age:
Minutes
30 1
2
Hours
28
90
Days
180
100
160
90
140
80
120
Type I
Type II
Type III
Type V
100
80
60
40
% of 28-day strength
% Change
70
60
1950s
1994
1998
50
40
30
20
20
10
0
1-day
3-day
28-day
1-Day
3-Day
7-Day
28-Day
APPENDIX B:
REFERENCES
ACI Committee 225, Guide to the Selection and Use of
Hydraulic Cements, American Concrete Institute, Farmington
Hills, Michigan,1991, 29 pp.
IS417.01