Académique Documents
Professionnel Documents
Culture Documents
Volume 28 Issue 7
Acid resistance of calcium aluminate
cementfly ash F blends
Pyatina and Sugama
Toshifumi Sugama
The short-term resistance to sulfuric acid at 90C of four calcium aluminate cement (CAC)fly ash class F (FAF) blends
activated with sodium metasilicate (thermal shock resistant cements (TSRCs)), cured at 300C, was compared to that of
a calcium phosphate cement (CPC) (CACFAF blend activated with sodium hexametaphosphate) and a Portland cement
class G/silica blend. The mechanical properties and compositions of the acid-exposed samples were evaluated by
measuring their compressive strength and by means of x-ray diffraction, EDX (energy-dispersive x-ray spectrometry),
thermogravimetric and Fourier transform infrared analyses. All calcium-containing hydrates were sensitive to the
conditions of acid exposure. In the TSRC blends, these hydrates included hydrogrossular, feldspar family minerals and
zeolites; in CPC, feldspar minerals and phosphate phases; and in the class G/silica blend, portlandite and tobermorite.
Crystalline calcium sulfates formed in the acid-exposed surfaces with the exception of the most aluminium-rich TSRC
samples where only potassium(sodium) aluminium sulfate, alunite, was detected. This sample underwent the least
changes in weight, compressive strength and had the lowest sulfur permeation into the sample core. Calcium sulfates
precipitated on sample surfaces limited sulfur penetration into the core of calcium-rich TSRC, CPC and G/silica blends.
Introduction
In geothermal wells, strongly acidic environments come from
the dissolution of hydrogen sulfide (H2S) with the formation
of sulfuric acid (H2SO4). This leads to a very low pH (<1)
hot-acid attack on the cement sheath (Alexander et al., 2013;
Lichti and Yanagisawa, 2015; Villasenor and Vicedo, 2010).
The degradation of Portland cement by acid proceeds through
decalcification of portlandite followed by calcium loss from
calcium-silicate hydrate phases at a pH below about 124, causing an increase in porosity and decrease in mechanical strength
(Beddoe and Dorner, 2005; Glasser et al., 2008; Gutberlet
et al., 2015; Kudowski, 2004; Puertas et al., 2012; Zivica,
2004). The acid diffusivity through the calcium-depleted
hydrates is of an order of magnitude higher than that through
the original material (Bentz and Garboczi, 1992). The calcium
is replaced by acid protons linking the silicate chains and
leaving just a silica residue at a pH below about 2 (Beddoe
and Dorner, 2005; Chen et al., 2004; Haga et al., 2002). In the
geothermal industry, silica polymerisation caused by low-pH
environments is a known problem (Lichti and Yanagisawa,
2015). The precipitation of calciumacid anions reaction products may either slow down acid attack (Zivica and Bajza,
2002) or enhance erosion and compromise the matrix integrity
(Larreur-Cayol et al., 2011).
The iron- and aluminium-containing hydrates of Portland
cement dissolve slower and at lower pH values than calcium
hydrates (Beddoe and Dorner, 2005), so the addition of supplementary cementitious materials (SCMs) to Portland cement
has been tested and shown to improve the cements acid resistance by lowering the calcium content and decreasing porosity
(Al-Akhras, 2006; Bakharev 2005; Bakharev et al., 2002;
Lee et al., 2005; Ouyang et al., 1988). In the case of attack by
sulfate ions, SCMs also help to preserve matrix integrity
since they do not form expanding reaction products. Using
solely alkali-activated SCMs (Chindaprasirt et al., 2014) and
incorporating them in reactive aluminium (Kandasamy and
Shehata, 2014) has been reported to decrease ion diffusion and
help enhance sulfate resistance. However, the gel hydration products of cements with alkali-activated SCMs such as fly ash
undergo dealumination of aluminosilcates with the formation
of the same final amorphous silica gel (Allahverdi and Skvara,
2001; Allahverdi and Skvara, 2005; Donatello et al., 2013).
Geopolymers with crystalline zeolites in the structure formed
from activated fly ash were also shown to lose strength at 95C
in acidic media (Bakharev, 2005).
Calcium aluminate cement (CAC) has the advantage of a
lower calcium content than Portland cement. The nature of its
hydrates and the products of sulfuric acid reactions also help
to slow down the degradation of CAC with sulfuric acid at pH
levels of above 3 (Lamberet et al., 2008). At lower pH levels,
however although slowly aluminium hydroxide dissolves in
acid and eventually the acid degradation of cement proceeds.
433
To the authors knowledge the performance of hightemperature hydration products of blends based on CAC and
SCMs in strong acids is not known.
Experimental procedure
Table 1 lists the mix proportions of the tested blends and
Table 2 gives the oxide compositions of their components
determined by energy-dispersive x-ray spectrometry (EDX).
The CACs for use in the TSRC blends were supplied by
Kerneos Inc. The class G cement used was a Dyckerhoff
North type.
TSRC-1
TSRC-2
TSRC-3
TSRC-4
Class G
CPC
Cement: wt %
566 (CAC#80)
566 (CAC#51)
377 (CAC#80)
377 (CAC#51)
700
472 (CAC#51)
377
377
566
566
472
(sodium
(sodium
(sodium
(sodium
(silica)
(sodium
metasilicate)
metasilicate)
metasilicate)
metasilicate)
hexametaphosphate)
Aluminium
oxide
(Al2O3)
Calcium
oxide
(CaO)
Silicon
dioxide
(SiO2)
Iron
oxide
(Fe2O3)
Sodium
oxide
(Na2O)
Potassium
oxide
(K2O)
Titanium
dioxide
(TiO2)
Sulfur
trioxide
(SO3)
10
752
451
35
71
247
497
27
17
50
466
50
01
28
71
034
030
505
12
31
24
16
36
434
(a)
(b)
(c)
(d)
Weight change: %
TSRC-1
TSRC-2
TSRC-3
TSRC-4
Class G/silica
CPC
03
112
179
317
+383
320
Diameter change: %
079
002
165
085
+188
17
180 07
139 13
112 19
127 21
174 07
253 16
180 20
163 17
147 23
212 45
205 06
246 65
Corrosion depth: mm
068
044
<05
<05
197
086
435
AI
C
TSRC-1
A
C
A
MQ B
AI
B
Intensity
Acid, surface
AI M
QA
AI
B AI M
D Ga
DQ
YeGa
Ye
D
D
Q
C A
HS
Ga
Control
100
125
150
175
200
HS
225
M
H
Ye
250
Q
K
CC
275
K
HS CC
300
CB
M
C
HS
Q
K
C
Q
M
HS
K
Ga
A K
B
75
M
D C
Acid, core
50
Ye D
D MD
350
DB
HS
C
HS
D
H A
H
BB
K
CC
M
K
325
375
400
425
450
475
500
2: degrees
AI
Ba
TSRC-2
Ba
B AI
Acid, surface
CS
AI Ba
Q
AI
AI Ba
Intensity
Acid, core
B An
Ba
K An
An
P D Ba
K
B
K
CC An
Ba
An
H
K
P
G
H
K
100
125
150
175
200
225
250
275
300
325
D
P B
CC CC
B B
K
G
375
B Ba
K
350
Ba
M
75
K
BCC
K
Control
AI Ba
QK
BQ
50
D
D
P
AI
AI
400
K CC
H
425
450
475
500
2: degrees
The CPC sample had the largest losses in weight and diameter,
and experienced a 3% decrease in compressive strength. The
class G/silica sample increased in both weight and diameter by
forming a large external layer that proved to be calcium sulfate
in the XRD tests; the compressive strength of this sample
increased by about 19%.
Analyses of degraded samples crystalline phases,
XRD patterns
Figures 24 show the XRD patterns of the tested cement
formulations cured at 300C before and after acid exposure.
436
Crystalline phases of the control TSRC samples included nonhydrated reactants (corundum, quartz, mullite, perovskite,
gehlenite, hematite and some calcium carbonates), hydration
products of CAC such as boehmite and hydrogrossular minerals (katoite silician and katoite), and hydration and reaction
products from FAF alone or from both FAF and CAC
B Ba Go
Acid, surface
AI
Intensity
A
Ga
Ga
Ga
AI
K
Acid, core
Ha
Ga
B
Control
50
75
100
125
150
175
225
Acid, surface
Ba Go
Q Ga
325
B AI
Ba
C
M
C
B
C
Ga
K
M
K
C
M
A
250
275
300
2: degrees
Q
M
An
AI
AI
K
A A Ha
TSRC-4
Ga
350
Go Ba
AI
Go
B
Ha
Ga
M
Q
C
200
Ba
AI
He
CC
Ga
H K
Ba
Ha
Q
Ga
Q
Ga
Ha
Ga
C
AI M
A
Ga
Ba
He Go
AI
Ba Go
M
Go
Ba
AI
TSRC-3
H
Ba Q
M
B
Q
Q
M Ha M
K
375
AI M
A Q
BM
400
425
450
475
500
AI
Go Ba
Go
Ba Ba
Ga
Go
AI
M
Ba
AI Ba
Go Go
Intensity
Ga
Ga
Ph Ba
Acid, core
An
Ph
Ph
Ga
An Q Ph
Ba
Ph
Gy Ga
Ga
M
Ba An Ba
M
An
M
Ba
K
Q
Ga
P Ba Ga
CC
CC
Ga
An
Ga
An
Ga
Control
50
M Q
K
Ga
Ga
An
An
75
100
125
150
175
200
225
250
275
300
Ga
G
K
An
325
M
Ga
An
350
375
400
425
Ga
K
Ga
450
475
500
2: degrees
During the 18 d acid treatment, curing of the samples continued but at a lower temperature of 90C, causing changes
mostly in compositions of the sample cores, and the acid
reacted with the cement, mostly altering the surface layers. The
following changes occurred in the cores of TSRC samples.
437
Gy
CPC
Acid, surface
Gy
M
Q
Gy
D
Gy
Gy
Gy
A
B
DGy
A
M
Gy
BM
M
D Gy
Gy
Gy B Q
Intensity
QD
Ph D
D Ph Ph Ba
Acid, core
D
D
HA D CP
Control
50
75
100
125
150
175
Gy
200
225
D
C
HA
CA
CP An
B
D CA
C
AnCP ACP
HA CP
HS Ph CA
Ba K A HS Ba Q
K Ph
Ph CA
K Ph
CP
A
325
Ba
350
375
K
An
HA
HS
CA Ba
HS
K
Ph
HS
An A
400
CP
425
450
HA
CP B D
D CP CA
475
500
Q
Gy
Gy
Q
Gy
Gy
Intensity
Gy
Br
Gy
Acid, surface
Gy
Gy
Gy
Gy
Gy
Gy Gy
Gy
Gy
Gy
Gy
Q
Gy
T FH
Acid, core
Control
50
Br
75
100
125
150
175
200
T
Br Br CC
225
CC
Gy
T
CC
T
CC Pr
T CCFH
FH
Q
FH
Q
T
Q CC
FH
Gy
T
CC
T Pr
Br CC Br
Pr
325
T
Q
CC
350
Pr
CC
375
400
T
Q CC T
425
Q CC T
BrCC
450
475
500
Non-reacted phases
439
Table 4. Crystalline phase compositions of cements before and after sulfuric acid exposure; ICDD numbers in
parentheses (continued on next page)
Secondary phases
Principal phases
Non-reacted phases
Table 4. Continued
Secondary phases
440
Principal phases
Non-reacted phases
Table 4. Continued
441
Downloaded by [] on [22/06/16]. Copyright ICE Publishing, all rights reserved.
Secondary phases
Principal phases
2: degrees
Control
TSRC-1
1458
1762
2014
2038
2574
2632
2698
2816
2829
2886
295
3238
3328
3522
361
3706
379
Identified phase
(see Table 4 for ICDD numbers)
1444
1746
2018
2020
2622
2686
2818
2823
2876
294
3140
3224
3312
354
361
3688
TSRC-1
TSRC-2
TSRC-1
TSRC-2
1205
1247
1456
1648
1802
2010
2018
215
2202
2348
2418
2574
2608
2632
2662
2698
278
2812
2829
295
3163
3326
3360
3516
3522
3578
377
1207
1446
1475
1586
163
1756
1834
2008/2011
201
2020
2338
2412
2550
2586
2605
262
2699
281
2814
289/2884
2934
2948
3064/303
3134
3140
3158
317
3239
3314
3514
352
359/3568
3708
1247
1455
1541
1635
1788
201
215
2202
234
240
2556
2619/2632
2662
2818
2829
2990
3136
3308/3328
3360
3522
377
1459
1475
1554
1635
1798
2008
2016
2350
241/2416
2542
2548
2576260
259263
266
2818
2822
298302
301
3036
3136
3137
314
3162
318
3312/333
3520
362
359358
442
Dminsteinbergite
Garronite
Boehmite
Bassanite
Alunite
Analcime
Mullite
Katoite
Garronite/alunite
Analcime
Dminsteinbergite/gypsum
Quartz
Katoite
Garronite
Garronite
Dminsteinbergite
Dminsteinbergite/hematite
Anhydrate
Corundum/alunite
Bassanite
Analcime
Quartz/mullite
Quartz
Katoite
Garronite
Quartz
Garronite/boehmite
Katoite/gypsum/quartz
Calcium carbonate
Bassanite
Alunite
Analcime/hematite
Anhydrate
Alunite
Gehlenite
Dminsteinbergite
Bassanite
Katoite
Perovskite/iron oxide/mullite
Garronite
Dminsteinbergite
Corundum/mullite
Dminsteinbergite/hematite
Katoite
Corundum
2: degrees
Control
TSRC-1
Identified phase
(see Table 4 for ICDD numbers)
TSRC-1
TSRC-2
TSRC-1
TSRC-2
3842
395
3985
410
383
3936
3972
4115
3842
394
3982
408/4087
3833
394
3958
3988
3995
408/409
3842
3973
400
4075
3836
394398/396
397
3972
4075/408
4347
4511
4899
4947
4501
4759
4887
4921
4210
4271
4331
49274940
4200
4263
4295
4522
4751/47244755
4889
4933
4331
4765
4927
421
4275
423428
473474
4780
489492
492493
Boehmite
Alunite/calcium carbonate
Bassanite
Dminsteinbergite
Katoite
Iron oxide/calcium carbonate/
mullite/anhydrate
Dminsteinbergite
Dminsteinbergite
Bassanite
Corundum
Katoite
Perovskite/calcium carbonate
Alunite
Boehmite
Dminsteinbergite/quartz/boehmite
Table 5. Continued
2: degrees
Control
Identified phase
(See Table 4 for ICDD numbers)
TSRC-3
TSRC-4
TSRC-3
TSRC-4
TSRC-3
TSRC-4
1227
1247
1227
1248
1221
1243
1221
1247
122
124
1449
1583
1643
1784
1583
1648
177/179
1442
1473
1593
1632
1782
1484
1574
1638
178
1449
1473
1589
1642
1792
1471
1579
1638
1784
1804
1820
2088/2094
2164
1804
1830
2094
2168
1806
1834
2086/2092
2158
1806
1826
2074
2084
2154
1832
2074
2086
2164
1828
2078
2086
2174
256
259/262
2668
278
2786
2812
283
2599
267
278
2800
256
2554
2616
2662
278
2804
2568
2594
266
277
2804
2546
2568
259/260
2664
2798
2538
2568
2597
2668
278
2806
2836
2816
2822
2812/2822/2824
282
2942/2944
294
295
294298 2942/2973
294298
3054
3096
3286
3060
3104
3132
3270
3046
3096
3186
326
305
3092
3126
3194
3268
2994
3062
3099
3188/3192
299
3092
3128
3182
3324/333
3343352
3520
3527
3558
3574
366371
378
333
334
3522
3587
369
332/333
335
3504
353
355
3567
3701
3784
332/333
334
3523
3568
3694
332
3514
3526
3576
370
3776
331
335
3518
3568
3691
444
Gismondine
Garronite/harmotome/gobbinsite/
phillipsite
Boehmite
Bassanite
Analcime/gorgeyite
Mullite/phillipsite
Phillipsite/garronite/harmotome/
gobbinsite/katoite/alunite
Gismondine
Analcime
Bassanite
Quartz/gismondine
Garronite/harmotome/gobbinsite/
phillipsite
Alunite/anhydrate/corundum
Bassanite
Mullite/analcime/calcium carbonate
Quartz/gobbinsite/gismondine
Garronite
Anorthite/phillipsite/gismondine
Garronite/gobbinsite/harmotome/
boehmite/gorgeyite
Gobbinsite/katoite/katoite silician
bassanite/calcium carbonate/
gorgeyite/hedenbergite
Alunite
Analcime
Mullite
Gehlenite
Gorgeyite/bassanite
Gobbinsite/phillipsite/gismondine/
perovskite/katoite/katoite silician/
calcium carbonate
Mullite/hematite/phillipsite
Garronite/harmotome/gobbinsite
Hedenbergite/corundum
Mullite
Gobbinsite
Hematite/analcime
Gobbinsite/mullite
Corundum/gobbinsite/calcium
carbonate
2: degrees
Control
Identified phase
(See Table 4 for ICDD numbers)
TSRC-3
TSRC-4
TSRC-3
TSRC-4
TSRC-3
TSRC-4
383
3843
3840
3843
383
383
3934
3946
4057
4085
4098
4251
3922
4055
4089
408
4261
4335
4591463
4597
489495
493
5011
4772
5011/5027
Boehmite/gobbinsite/calcium
carbonate
3936
393
3924
3911
Mullite
395
394
394
394
Quartz
3964
396
3966
396
Bassanite
3976
3970
Alunite
4058
4041
Katoite/katoite silician/analcime
4083
4081
4077
4077
Mullite/gobbinsite
408
408
4081/4097
408
Bassanite/hematite
4221/4245 420427 4223/4249/4267 420427 Hedenbergite/diopside/bassanite/
mullite/gobbinsite
4337
4333
Corundum
45894591 4581
4575
4577
Katoite/katoite silician/gobbinsite/
garronite/calcium carbonate
4759
476
4765/4791
4775
Bassanite/alunite/gorgeyite/perovskite
4893
4879
Anhydrate/boehmite/gobbinsite
4929
4927
48814949/4951 4923/494 Bassanite/boehmite/gorgeyite
5007
501
50095027
5007
Gismondine/quartz/bassanite
Table 6. Continued
2: degrees
Control
Identified phase
(see Table 4 for ICDD numbers)
CPC
G/silica
CPC
1196
1452
1622
1754
2000
1219
1804
2088
1198
1464
2024
2338
241
2312
2494/2496
2592/266
G/silica
G/silica
1234
1778
2106/2112
1166
1452
163
2006
2078
1161
2068
2362
2432
2312
2516
2337
2418
2338
2614
2602
266/2682
2634
2666
2684
2664
2664
2788/281
2893
26922722
2834
289
2716276
2816/2814
292
2916
2916
2924
2911/2912 2812/2911
2922
2944
296
2956
3018
3128
315
316
3194
319
3136
3147
3176
3112
3159
3118
3218
3202
321
3248/328
322/3236
3264
3246
3244
3215
446
Gypsum
Dmisteinbergite
Brownmillerite
Boehmite
Mullite
Katoite silician
Iron oxide hydroxide
Tobermorite 9A
Dmisteinbergite
Gypsum/quartz/iron oxide
hydroxide
Brownmillerite
Dmisteinbergite/quartz/gypsum
Dmisteinbergite/hematite
Tobermorite 9A/calcium
carbonate
Mullite/hydroxylapatite/analcime/
carbonated hydroxylapatite/
hydroxylapatite sulfonated
Portlandite
Anorthite/calcium hydrogen
phosphate/quartz
Calcium carbonate
Anorthite/boehmite
Hydroxylapatite/katoite silician/
portlandite
Hydroxylapatite sulfonated/
gypsum/calcium carbonate
Boehmite/tobermorite 9A/calcium
carbonate/quartz
Anorthite/calcium hydrogen
phosphate
Gypsum
Gehlenite
Dmisteinbergite
Hydroxylapatite/dmisteinbergite
Carbonated hydroxylapatite/
portlandite
Hydroxylapatite/carbonated
hydroxylapatite/hydroxylapatite
sulfonated/gypsum
Tobermorite 9A/brownmillerite
Calcium hydrogen phosphate/
katoite silician/portlandite
2: degrees
Control
Identified phase
(see Table 4 for ICDD numbers)
CPC
G/silica
CPC
3316
3268330
3321
3506
356/357
3358
3388/341
3342
3528
3586
334
3370
337/341
3341
3520
3574
359/383
3606
3734/3843
368
3836
3923
396
3968
3923
3976
3998/4016
398
4083
4195
4093
4221
4074
423
4259
4515
4325/439
4405
4699
4745
4281
4515
443
440
457
4699
474
4253
433436
4755
477
4777
4779
4807/4821
489
4779
4837
489
4783
4787
4849/4891 487
G/silica
33336/3318
CPC
G/silica
3323
4903
4927
4905
4939/4951
4953
494
4995/5015
4993/5035 5027
Carbonated hydroxylapatite/
perovskite/hematite/calcium
carbonate/iron oxide hydroxide
3334
Gypsum
Tobermorite 9A
3352
Brownmillerite
Mullite/dmisteinbergite
Boehmite/quartz/calcium
carbonate/iron oxide hydroxide
Portlandite
Dmisteinbergite
Hydroxylapatite/hydroxylapatite
sulfonated
4073
Mullite/gypsum
Dmisteinbergite/calcium
carbonate
Mullite/dmisteinbergite
43394357
Gypsum
4423
Calcium carbonate/gypsum
Tobermorite 9A
Katoite silician
4547
Gypsum
Portlandite
475
Brownmillerite/iron oxide
hydroxide
Boehmite/quartz/calcium
carbonate
Hydroxylapatite/carbonated
Hydroxylapatite
Dmisteinbergite/hydroxylapatite/
calcium carbonate/hematite
5023
Tobermorite 9A/Gypsum/quartz/
calcium carbonate/
brownmillerite
Table 7. Continued
agreement with the XRD data, this peak was absent from the
TSRC-2 thermogram. Both TSRC-1 and TSRC-2 showed
DTG peaks at 236C from various zeolites. The katoite peak
Control
Core
Surface
Control
TSRC-1
Aluminium oxide
Silicon dioxide
Calcium oxide
Iron oxide
Potassium oxide
Titanium dioxide
Sulfur trioxide
48
25
19
43
20
080
49
24
21
48
10
41
35
13
66
27
13
41
31
12
62
23
11
70
48
28
15
49
33
10
14
35
23
32
61
13
23
29
18
29
15
51
19
20
35
21
32
26
55
08
22
32
24
33
60
27
27
21
36
11
76
27
32
18
TSRC-4
38
35
64
55
26
10
11
29
35
24
74
30
21
CPC
Aluminium oxide
Silicon dioxide
Calcium oxide
Phosphorus pentoxide
Iron oxide
Potassium oxide
Titanium dioxide
Sulfur trioxide
Surface
TSRC-2
TSRC-3
Aluminium oxide
Silicon dioxide
Calcium oxide
Iron oxide
Potassium oxide
Titanium dioxide
Sulfur trioxide
Core
30
32
25
81
25
25
23
18
48
13
65
19
28
13
Class G/silica
27
31
17
40
63
27
12
29
29
59
55
09
02
28
30
60
57
03
43
15
38
12
46
TSRC-1
50
TSRC-2
250
450
650
850
50
250
450
650
850
50
650
850
250
250
450
650
850
450
650
850
Class G/Silica
CPC
50
450
TSRC-4
TSRC-3
50
250
450
650
850
50
250
Temperature: C
678
Control
1228
1482
868
986
903
TSRC-1
023
0
026
1622
1158
1073
664
Acid, core
0
023
Acid, surface
0
2000
1800
1600
1400
1200
1000
800
650
989
TSRC-3
1159
0
015
1074
660
1459
Control
1633
868
017
903
Wavenumber: cm1
Acid, core
0
022
Acid, surface
0
2000
1800
1600
1400
1200
1000
800
650
Wavenumber: cm1
silica gel at 1228 cm1 and C,N-A-S hydrates at 986 cm1 and
903 cm1. The spectrum of the core sample was similar to the
control, while the chemical composition of the surface layer
mostly consisted of some major sulfate phase, and minor
C,N-A-S hydrates along with silica gel. An increased fly ash
content (TSRC-3) (Figure 6) engendered a shift of the most prominent MO (M: silicon or aluminium) asymmetric (Vas M-O)
band of C,N-A-S hydrates to a higher frequency, from 903 cm1
for TSRC-1 to 989 cm1 for TSRC-3, and the absence of a
silica-gel-related band around 1220 cm1. The major bands of
the TSRC-3 components were at 1034 cm1 from Vas M-O stretching in Al2O3SiO2 in FAF and at 770 cm1 for aluminium
oxygen in the condensed aluminate (AlO4) tetrahedra network
Control
854
1225
1800
1600
1400
1200
Wavenumber: cm1
660
1000
983
TSRC-4
1477
1639
A
A
1068
660
Control
1144
0
022
650
860
024
800
901
Acid, surface
0
2000
1622
1149
Acid, core
0
03
1072
0
023
1451
980
016
675
901
TSRC-2
Acid, core
0
020
Acid, surface
0
2000
1800
1600
1400
1200
1000
800
650
Wavenumber: cm1
1220
1066
014
1031
905
CPC
676
Control
Acid, core
1000
965
1080
650
011
1411
1478
Class G/silica
800
714
693
1400
1200
Wavenumber: cm1
799
777
1600
873
Acid, surface
0
2000
1800
1622
1143
0
027
669
1048
0
017
Control
1619
A
Acid, surface
0
2000
1800
660
1144
Acid, core
0
05
1088
0
014
1600
1400
1200
Wavenumber: cm1
1000
800
650
Figure 8. FTIR spectra of CPC and class G/silica blends before and
after sulfuric acid exposure
TSRC-1 surface
2
3
1
30 m
Fe
O
1
AI
AI
Si
S
Si
Fe
O
AI
Si
AI
Na
Si S
TSRC-1 core
4
30 m
Fe
O
Fe
O
Si
Ca
O
AI
AI
S
Si
4
AI
Si
AI
Ca
O
Si
Ca
TSRC-2 surface
1
20 m
30 m
Ca
Fe
O
Ca
Fe
O
Si
AI
Ca
Fe
Si
AI
Si
Ca
S
Ca
Ca
Fe
AI
Si
AI
4 0
4 0
453
Conclusions
Blends of thermal shock resistant cement (TSRC) composed
of calcium aluminate cement (CAC) and class F fly ash (FAF)
activated with sodium metasilicate were hydrated for 24 h at
300C and tested for their resistance to sulfuric acid solutions
at 90C for 18 d. Four blends were prepared with CAC of
varied calcium and aluminium contents and different CAC to
fly ash ratios. Their short-term resistance to acid attack was
compared to that of a Portland cement class G/silica blend
and to a calcium phosphate cement (CPC) made of CAC,
FAF and sodium hexametaphosphate.
The following general conclusions can be drawn from the
study.
(a) After 18 d of sulfuric acid exposure at 90C, all the
TSRC formulations lost weight and decreased in diameter
while keeping or increasing their compressive strength
and forming only a thin rim layer. The changes were the
smallest for the aluminium-rich blend (TSRC-1) and the
most significant for the silicon- and calcium-rich blend
454
Acknowledgements
This publication was based on work supported by the
Geothermal Technologies Office in the US Department of
Energy (DOE) Office of Energy Efficiency and Renewable
Energy (EERE), under the auspices of the US DOE,
REFERENCES
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457