The effect of alkali upon Portland cement ..

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Tantver0tt£ of Cbicago

THE EFFECT OF ALKALI UPON
PORTLAND CEMENT

A DISSERTATION

SUBMITTED TO THE FACULTY

OF THE OGDEN GRADUATE SCHOOL OF SCIENCE

IN CANDIDACY FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

DEPARTMENT OF CHEMISTRY

BY

KARL THEODOR STEIK

Private Edition, Distributed By

THE UNIVERSITY OF CHICAGO LIBRARIES

CHICAGO, ILLINOIS

Reprinted from
UNIVERSITY OF WYOMING BULLETIN, No. 122

"dniwrsitp of Gbicago

THE EFFECT OF ALKALI UPON
PORTLAND CEMENT

A DISSERTATION

SUBMITTED TO THE FACULTY

OF THE OGDEN GRADUATE SCHOOL OF SCIENCE

IN CANDIDACY FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

DEPARTMENT OF CHEMISTRY

BY

KARL THEODOR STEIK

Private Edition, Distributed By

THE UNIVERSITY OF CHICAGO LIBRARIES

CHICAGO, ILLINOIS

Reprinted from
UNIVERSITY OF WYOMING BULLETIN, No. 122

BULLETIN NO. 122

DECEMBER, 1919

UNIVERSITY OF WYOMING

AGRICULTURAL
EXPERIMENT STATION

Cement in different stages of disintegration.

THE EFFECT OF ALKALI UPON
PORTLAND CEMENT— II

Bulletins will be sent free upon request.
Address : Director of Experiment Station, Laramie, Wyoming.

713

UNIVERSITY OF WYOMING

Agricultural Experiment Station

LARAMIE, WYOMING

BOARD OF TRUSTEES

Officers

ALEXANDER B. HAMILTON, M. D President

W. C. DEMING, M. A.... .'.. Vice President

C. D SPALDING Treasurer

F. S. BURRAGE, B. A Secretary

Executive Committee

A. B. HAMILTON C. P. ARNOLD C. D. SPALDING

Members Term

Appointed Expires

1911 .....ALEXANDER B. HAMILTON, M. D... 1923

1911 LYMAN H. BROOKS .1923

1913 CHARLES S. BEACH, B. S ! 1. .1923

1913 C. D. SPALDING. 1921

1914. MARY N. BROOKS. .1925

1915... ....... J. M. CAREY, LL. B V. 1921

1918 .C. P. ARNOLD, M. A 1919

1919 . ...E. W. CROFT, M. D 1925

1919 W. C. DEMING, M. A.. 1925

KATHARINE A. MORTON, State Superintendent of Public Instruc-
tion Ex Officio

A. NELSON, Ph. D. , . .... Ex Officio

% STATION STAFF

A. ^NELSON, Ph. D. President

A. D. FAVILLE, M. S.. . . . . . . .... .-". -.-. . . . : . \ .....'... Director

F. S. BURRAGE, B. A Secretary

O. A. BEATH, M. A Research Chemist

C. ELDER, D. V. M Assistant Veterinarian

J. C. FITTERER, M. S., C. E Irrigation Engineer

F. A. HAYS, Ph. D Associate Animal Husbandman

F. E. HEPNER, M. S Research Chemist

J. A. HILL, B. S Wool Specialist

E. H. LEHNERT, D. V. S Veterinarian

P. T. MILLER, M. A Associate Station Chemist

E. C. O'ROKE, M. A Assistant Parasitologist

J. P. POOLE, A. M Botanist and Horticulturist

J. L. ROBINSON, M. S Assistant Agronomist

*J. W. SCOTT, Ph. D . .Parasitologist

K. T. STEIK, M. A Engineering Chemist

A. F. VASS, Ph. D Associate Agronomist

MARION V. HIGGINS Librarian

F. M. LONG.. ..Clerk

*On leave.

The Effect of Alkali Upon Portland Cement-II

KARL STEIK

INTRODUCTION.*

Of the salts which constitute the so-called "alkali", the fol-
lowing were used in the determination of their effect on Portland
cement: The sulfates of sodium and magnesium, chlorides of
sodium and magnesium and the carbonate of sodium. The nitrates
occur only in very small quantities and therefore are not detri-
mental to any extent in regard to the cement problems. Cases
are mentioned in the literature where concrete is supposed to have
been damaged by water which had percolated through gypsum
beds, therefore, effects of solution of calcium sulphate, too, were
investigated.

In the Western States the number of different salts present in
the so-called "alkali" varies according to local conditions. The
two most abundant and frequent salts are the sulfates of sodium
and magnesium. The carbonate of sodium is present in the black
alkali. The concentration of the salts in waters varies accord-
ing to the localities and seasons of the year. Some of the alkali
lakes are filled with saturated solutions during dry seasons and
in many of them solid deposits occur on the lake bottoms.

Experiments were conducted with solutions of only one salt
at different concentrations in order to determine the effect of each
salt separately. Solutions were also used which contained two,
three and four different salts at different concentrations. In order
to determine the relative merits in regard to resisting the action
of alkali, neat cement and mortars of different concentration were
used. For comparison, several brands of cement were tried, but
most of the experiments were carried out on "Ideal" cement. In
all cases the amount of solution per gram of cement or mortar
was the same.

Experience showed that the reaction of alkali on neat Port-
land cement was very slow ; consequently, for the purpose of ob-

*A progress report on this problem was made in Bulletin 113 of the Wyoming Station.
Much of the work outlined on the following pages appeared in the earlier publication but
is included at this time to round out and complete the final report.

4 Wyoming Agricultural Experiment Station. Bui, 122

taining more marked results, some experiments were conducted
with solutions kept at temperature of boiling water during eight
hours a day for eighteen months. In connection with these ex-
periments, the effect of periodical wetting and drying was tested
and also the effect of treating the cement with large quantities of
hot distilled water.

CHEMICAL CHANGES

The chemical reactions which take place between the con-
stituents of the alkali were judged from the reaction products.
In solutions of sodium sulfate, or magnesium sulfate singly
or combined, deposits of crystalline calcium sulfate were obtained
as shown in Figures I and 2. In dilute solutions, single crystals
were more likely to form, as in Figure i ; in more concentrated
solutions crystalline rosette-like aggregates were formed, as in
Figure 2.

Fig. 1.

On cement kept in water, crystalline and amorphous deposits
of Ca(OH)., — calcium hydroxide — were obtained, as shown in
Figures 3 and 4. The surfaces of cement kept in a solution of
sodium carbonate were either entirely or partially covered with
amorphous calcium carbonate, CaCO;!, as shown in Figure 5.

Dec.

Effect of Alkali Upon Portland Cement — //.

The magnesium hydroxide which was formed in solutions of
magnesium sulfate was amorphous, and, usually, mixed with
amorphous calcium sulfate. Deposits of crystalline magnesium
hydroxide were obtained on surfaces of cement kept in hot solu-
tions of magnesium chloride. The crystals formed small nodules,
as shown in Figure 6.

Wyoming Agricultural Experiment Station. Bui. 122

Fig. 4.

Dec. 1919 Effect of Alkali Upon Portland Cement— II.

Fig. 5.

Fig. 6.

Besides these products of reaction, one more was obtained
from cement which was kept in a 5 per cent solution of sodium
chloride. This solution was not changed during the entire time
of experiments and the crystals appeared after a period of about
3 years. In other cases, fresh solutions were used after each
testing of the compression and tension strength of the cement.
The crystals, after cleaning off the adhering matter from their
surfaces, gave the following analytical results: SiO,, 40.14 per

8

Wyoming Agricultural Experiment Station. Bui. 122

cent; A12O3, 31.48 per cent; FeL,O:!, o.n per cent; CaO, 10.09
per cent; 'Na2O, 14.13 per cent; Cl, 4.32 per cent. Figure 7
shows these crystals.

Fig. 7.

Dec.

Effect of Alkali Upon Portland Cement— II.

From the above results, it appears that the following re-
actions took place in different solutions used :

Ca(OH)2 + MgSO4 + aq. -» CaSO4.2H2O + Mg(OH)2 + aq. ;
Ca(OH)2 + Na2CO;t + aq. -» CaCO, + 2NaOH + aq.

The analysis of the calcium sulfate crystals gave the follow-
ing, showing it to be CaSO4.2H,O : Water, 21.0% ; CaO, 32.5% ;
SO,,, 46.3%.

PHYSICAL CHANGES.

The reaction of sodium and magnesium sulfates produced
characteristic changes, which were especially apparent in the case
of mortars. From the appearance of the mortar, it was possible

Fig. 9.

IO

Wyoming Agricultural Experiment Station. Bui. 122

to tell which of the salts had been acting. Figure 8 shows the
cracks formed on a i 14 mortar which was immersed in a solution
of sodium sulfate. Notice that every cu'be in the set has been
affected in the same manner. In figure 9 is demonstrated the
effect of a magnesium sulfate solution on T 14 mortar. The solu-
tion of sodium sulfate and the solution of magnesium sulfate
were of the same normality. Figure 10 also shows the effect of
magnesium sulfate, but at a somewhat earlier stage than in figure
9. The little clumps of needles are crystals of calcium sulfate.

As the concentration of cement in the mortar increases, the
cracks appear nearer the edges of the briquets and cubes and
thin layers gradually fall off, as shown in figure n. In figure
12, from left to right is shown a cube as it looks when the first
layer is nearly off, the thickness of the layer and the cube with
first layer removed.

Cement which was immersed in o. 5 N. sulfuric acid showed

Fig. 10.

Dec. 1919 Effect of Alkali Upon Portland Cement — //.

i i

the same kind of results as cement in a solution of sodium sulfate.
In this experiment the acid was renewed when it became neu-
tralized. The effects of hydrochloric acid of the equivalent con-

12

Wyoming Agricultural Experiment Station. Bui. 122

centration of the sulfuric acid used were somewhat different.. In-
stead of parallel cracks produced along the edges of cubes, as
•in case of sulphuric acid, minute cracks in large numbers, were
produced all over the surfaces. Figures 13 and 14 repr_esent_jhe
results of the action of sulfuric and hydrochloric acid respec-
tively.

Fij?. 13.

Dec. /p/p Effect of Alkali Upon Portland Cement — //.

Fig. 14.

Figure 15 shows the results produced by the following treat-
ment : The cubes were covered with distilled water and warmed
on a water-bath. The water was allowed to evaporate and the
cement dried. Then it was covered with water again and the
process repeated. After a sufficient length of time cracks were
formed which extended from edge to edge. No cracks were
formed on cubes which were treated in the same way, except that
they were always covered with water. Consequently the cracking
was due to alternate wetting and drying of the cement.

In order to test the alkali resisting quality of mortars with
varying proportions of sand, mortars were made up containing as
many as 10 parts of sand to one part of cement. Figure 16 shows
a comparison between neat cement and mortars of different dilu-
tions which were placed in a normal solution of sodium chloride
and sodium sulfate.

14 Wyoming Agricultural Experiment Station. BuL 122

Dec. /p/p Effect of Alkali Upon Portland Cement — //. 15

Top row left to right: Neat cement in distilled water; neat
cement which was heated on water bath and was periodically
either covered with water, or dry ; the next ones are in order :
neat cement ; i :i ; 1:2; 1:3; 1:4; 1:5; i :6, and i 7 mortars, all
in a normal solution of normal sodium chloride and sodium sul-
fate for a period of 6 months. Notice the characteristic cracking
produced by sodium sulfate. All specimens, except the first and
third show the effects of treatment. The neat cement in the
solution looks as well as the neat cement in distilled water.

Fig. 17.

1 6 Wyoming Agricultural Experiment Station. Bui. 122

Figure 17 represents the effects produced in a normal solu-
tion of magnesium chloride and magnesium sulfate. Except for
the first cube on the left in the top row, which is neat cement in
distilled water, the following cubes from left to right had composi-
tions: neat cement; i :i ; 1:2; 1:3; 1:4; 1:5; 1:6; 1:7. Dur-
ing the entire period of 6 months the specimens were not dis-
turbed, but even then the i 7 mortar had crumbled away. Notice
the bulging which is characteristic of the action of magnesium
sulfate.

In figure 18 cubes 15, 17 and 19 are i :i, i :2 and i 13 mortars
respectively, placed in a' normal solution of sodium chloride and
sodium sulfate. Numbers 16, 18 and 20 have the same respective

Fig. 18.

composition as the ones above, but these were in a normal solu-
tion of magnesium chloride and magnesium sulfate, for a period
of 6 months. Notice how the cubes in the solution of magnesium
salts have expanded and, judging from appearance, have disinte-
grated more. Numbers i and 9 are neat cement in distilled
water. All the above illustrations go to show that as the sand

Dec. 1919 Effect of Alkali Upon Portland Cement-^II. i?

content of the mortar increases, its resistance against the action
of alkali decreases.

Of the different brands of cement only two were claimed to
be alkali-resisting, the "Iron ore" cement, and the "Alkali-proof"
cement. In regard to the first one, it was impossible to tell from
the appearance whether or not it had been affected. The first
five briquets and cubes in figure 19 were made of "alkali-proof"
cement. It is apparent that a 5 per cent magnesium sulfate solu-
tion (first) and a 5 per cent sodium carbonate solution (second)
had some deteriorating effects. Briquet marked 59 was coated
with Toch's No. 232 R. I. W. ; the next to the right was coated
with Toch's No. 44 R. I. W. This coating was almost gone after
24 months, after which the above picture was taken.

Fig. 19.

CHANGES IN STRENGTH OF NEAT CEMENT AND MORTARS.

The tables on the following pages set forth clearly some of
the results obtained in the cement investigational work. Addi-
tional detailed data may be found in Wyoming Bulletin 113.

1 8 Wyoming Agricultural Experiment Station. Bui. 122

TABLE I — Showing the Average Strength of Cement Blocks Before

14

SOLUTION

Neat Ideal in various solutions:

(1) In distilled water for comparison.

Distilled water

(2) In solutions of jingle salts.

(a) 7 days in water before immersion.

Sol. 1, NaCl, 5 per cent

Sol. 2, MgSO4, 5 per cent

Sol. 3, Na2S04, 1 per cent

Sol. 4, Na2SO4, 5 per cent

Sol. 5, Na2S04, 10 per cent

NaOH 5 per cent

(b) 14 days in water before immersion.

Sol. 4, Na2SO4, 5 per cent

Sol. 1, NaCl, 5 per cent

Sol. 6, Na2COs, 5 per cent

Sol. 7, NaHCOs, 5 per cent

Sol. 8, NaCl, 7 per cent

(c) 14 days in water and 3 months in air before im>-

mersion.

Sol. 8, NaCl. 1 per cent

Sol. 6, Na2CO3, 5 per cent

(3) Neat Ideal in solutions of mixed salts.

(a) 7 days in water before immersion.

Sol. 11, CaClo, MgCl, 1.33 per cent each

Sol. 10, NaCl, Na2SO4, MgCl2, MgSOi, 1.25 per cent
each -

(b) 3 months in water before immersion.

Sol. 10, (See No. 16)

(c) 48 hours in damp oven before immersion.

Sol. 10, NaCl, Na2SO4, MgCl2, MgSO«, 1.25 per cent
each

(4) Neat Ideal to show effects of titn>tion.

In water. Titrated with H2SO4*

Sol. 14 NaCl, Na2SO4, 2.5 per cent each. Titrated

weeklyt

In water. Titrated dailyj

Sol. 4, Na2SO4, 5 per cent. Titrated weekly§

Before
immersion

Com-
press

Ibs.
7826

6745

7939
8827
7708
8031
5802

10815
8950
9663
9453

11700

5791
10467

5723
8552
7090

4035

7162
4760
6174

Ten-
sion

Ibs.
494

284
664
455
588
688
594

525
662
423
437

774
712

400
337
455

340
32«

261

387
276

Dec. 1919 Effect of Alkali Upon Portland Cement — //. 19

and After Being in Salt Solutions for Various Periods.

After being in solution:

12 months

24 months

30 months

40 months

84 months

Com-
press

Ten-
sion

Com-
press

Ten-
sion

Com-
press

Ten-
sion

Com-
press

Ten-
sion

Com-
press

Ten-
sion

Ibs.

Ibs.

Ibs.

Jbs.

Ibs.

Ibs.

Ibs.

Ibs.

Ibs. Ibs.

7145

716

9560

7-15

10907

677

9877

678

16970

252

9675
11615
10687
8457
11577
8685

994
482
400
644
660
905

10185
11310
10712
7045
11597
9965

1017
289
-,03
716
409
920

10452
10030
10282
6482
11265
8515

910
651
725
701
280
920

7527
8073
9047
6523
11460
7383

747
612
698
632
377
768

13057
9472
11742
8525
13887
16107

197
202
231
297
350

9342
8597
10660
8942
9922

669 5500
905 10295
830 10327
847 8882
779 11390

297
j-46
717

757
948

4415

8030
9907
9750
10217

655
762
720
729
892

5050

10393
12270
9503

455

"685
712
793

4325

"15375 "
10632
16017

305

629 "
220

8740
11540

619
701

9215

;49

8505
11235

640

672

7950
10833

593

11052
10732

231
332

7837
11167
10355

336
802
916

8860
8300

.

7680

844
849
794

7960
8120

8085

797
745
807

8703
7850
7553

672
773

860

10147

282
120
34

5252

10440

297

9880

1105

7325

1131

7920

1175

10100

211

9622

726

10165

P67

10650

679

10640

255

12570
10240
10522

581
475
902

11330
10565

9885

876
836
804

10827
12100
9287

720
821
860

10020
10607
9660

980
805
740

13380
16600

371
214

2O

Wyoming Agricultural Experiment Station. Bui 122

TABLE II — Showing Change of Strength of Cement Blocks During a Period

Same Cement at the

1

d

S3

SOLUTION

1

2 months

js

M

«.

Comp.

Tens'n

Ave.

Comp.

I. Neat Ideal in various solutions:

%

%

%

%

(1) In distilled water for cu-mparisou.

15

Distilled water

—8.7

+44.8

+18.0

+35.1

(2) In solutions of jingle salts.

(a) 7 days ?n water before immersion.

1

Sol. 1, NaCl, 5 per cent

+43.4

+250 0

+146 7

+5 2

2

Sol. 2, MgSO4, 5 per cent

+46.3

-27 is

+9^2

—2.' 6

3

Sol. 3, Na2SO4, 1 per cent

+21.0

—12.0

+5.5

+0.2

4

Sol. 4, .Na2SO4, 5 per cent

+9.7

+9.5

+9.6

—16.6

5

Sol. 5, Na2S04, 10 per cent

+44.1

—4.0

+20.0

+0.2

3S

5 per cent NaOH

+49.6

+52.3

+50.9

+14. 7

(b) 14 days in water before immersion.

6

Sol. 4, Na2SO4, 5 per cent

—13.6

+4.8

—4.4

—41.1

7

Sol. 1, NaCl, 5 per cent

—3.9

+72.3

+34 2

+19 7

8

Sol. 6, Na2CO3

+10.3

+25.3

+17.8

— 3J

9

Sol. 7, '\7aHCO3, 5 per cent

—5.4

+100.2

+47.4

—0.6

12

Sol. 8, NaCl, 1 per cent

—15.1

+78.2

+31.5

+14.7

(c) 14 days in water and 3 months in air

before immersion.

10

Sol. 8, NaCl, 1 per cent

+50.9

—20.0

+15.4'

+5.4

11

Sol. 6, NTa2CO3, 5 per cent ;

+20.2

—1.5

+9.3

(3) Neat Ideal in solutions of mixed salts.

(a) 7 days in water before immersion.

17

Sol. 11, CaCl2, Mg€l2, NaCl, 1.33 per

cent each

+36.9

—16.0

+10.4

+13.0

10

Sol. 10, NaCl, Na2S04, MgCI2,

MgSO4, 1.25 per cent earn

+30.5

-j-137.9

+84.2

-25.6

(b) 3 months in water before immersion.

11

Sol. 10, NaCl, Na2S04, MgCl2,

M?;S04, 1.25 per cent each .'

+46.5

+101.3

+73.9

—25.7

(c) 48 hours in damp oven before im-

mersion.

33

Sol. 10, NaCl, Na2S04. MgCl2,

M2rSO4, 1.25 per cent each

4-158.7

—12.3

+73.2

—5.3

(4) Neat Ideal to show effects of titration.

37

In water. Titrated with H2SO4*

+81.9

+133.7

+107.8

+5.6

43

Sol. 14, NaCl, Na«S04, 2.5 per cent each.

Titrated weeklyf

+74 6

+122 3

+98 4

- -9 4

39

In water. Titrated dailyj

+115J

+22^7

+68.9

+s!i

15

Sol. 4, Na2S04, 5 per cent. Titrated

weekly§ .

+70.3

+226.8

+148.5

—6.0

*Titrated daily; water changed weekly.
t Water not changed.

tWater changed after each test for strength.
iWater changed after each test for strength.

Dec. /p/p Effect of Alkali Upon Portland Cement — //.

21

in Salt Solutions Expressed as Per Cent, Computed on the Strength of the
Last Preceding Test.

After being in solution:

24 mon
Tens'n

ths

30 months

40 months

84 months

Ave.

Comp.

Tpns'n

Ave.

Comp.

Tens'n

Ave.

Comp.

Tens'n.

Are.

%
+4.0

+19.5

+14.1

—9.1

+2.4

—20.2

+0.1

—10.0

+71.6

—62.8

+4.4

+2.3
—40.0
+101.0
+11.1
—38.0
+1.5

+3.7
—21.3
+50.6
—2.7
—18.9
+8.1

+2.6
—11.2
—4.0
—7.9
—2.8
-4.5

—10.5
+125.2
—10.0
—2.0
—31.5
0

—3.9
+57.0
—7.0
—4.9
—17.1
—2.2

—27.9
—19.5
—11.9
-J-0.6
—7.1
-15.3

—16.8
—5.9
—3.7

—9.8
+34.6
—16.5

—22.3
—20.9
—7.8
—4.6
+13.7
—15.9

+73.4
+17.2
+29.7
+30.6
+21.1
-118.1

—73.8
—66.9
—66.9
—53.0
—7.1

—0.1

—29.8
—18.6
—11.2

+7.0

—55.6
—6.5
—13.6
—10.6
+21.6

—48.3 —19.7
+6.6li —22.0
—8.3 || —4.0
—5.6 +9.7
+18.6 —10.2
I

+123.9
—9.9
+0.4
—3.7
—5.9

+52.1
—15.8
—1.8
+3.0
—8.0

+14.3

—30.5

—8.1

—14.3

—33.6

—33.6

+4.9
+25.8
—6.9

—4.8
—2.3
—11.1

0
+11.7
—9.0

+47.3
—13.3

+68.5

—72 '.2

•™—

—1.8

+21.0

+13.2

-7.7
—2.6

—14.5
—4.1

—11.1
—3.3

—6.5
—5.3

—7.3
—18.1

—6.9
—11.7

+39.2
+5.9

—61.0
—31.6

—0.9
—18.3

+151.1

+82.0

—10.0

—5.5

—11.8

+8.5

—15.6

—3.5

+20.0

—58.0

—19.0

—5.8

—9.9

—2.1

—12.2

—7.7

—3.3

+3.7

+0.2

—84.4

—13.3

—19.5

+5.2

•H.i

+3.4

—6.5

+6.5

0

—23.4

—18.0

—36.3

+272.0
—12.4

+.50.7
+76.0

—10.8

+133.3
—3.9

+20.6
+34.5

—8.4

—5.6

+4.7

—4.4

+14.4

—6.0

+2.3
+1.7

—17.8
—1.7

+6.9

—1.6
+3.2

—11.1
+6.3

+0.4

+8.1
—0.1

—7.4
—12.3

+4.0

+3.9
—62.4

+22.2
—1.9

—13.9

+6.0
—31.2

+7.4
—7.1

—4.9

+27.5

—82.0

—27.2

+33.5

+56.5

&L'

—62.1
—73.4

— w'.s

—8.4

22

Wyoming Agricultural Experiment Station. Bui. 122

TABLE III — Showing the Strength of Cement Blocks Before and After

of Cement Blocks in Water

Lab No.

SOLUTION

Before Immersion

12

d

.U

Tension

Average

d

S

0

O

15

1

2
3
4
5

38

6
7
8

9
12

10
11

17
16

14

33

37
43

39
45

I. Neat Ideal in various solutions:
(1) In distilled water for comparison.
Neat Ideal. In distilled water
(2) In solutions of single salts,
(a) 7 days in water before immersion.
Sol. 1, NaCl, 5 per cent

%
100

86.1
101.4
112.7
98.4
102.6
74.1

138.1
114.2
123.5
120.8
149.5

74*0
133.7

73.1
109.3

90.6

51.6
65.0

91.5

68.2

78.8

%
100

57.4
134.4
92.1
119.0
139.2
120.2

129.1
106.3
134.0
85.6
95.7

156.7
144.1

81.0
68.2

92.1

68.8
66.0

52.8
78.3

55.8

%
100

71.7
117.9
102.4
108.7
120.9
97.1

133.6
110.2
128.8
108.2
122.6

115.3
138.9

77.0
88.7

91.3

60.2
65.5

72.1
73.2

67.3

%
100

135.4
162.5
149.5
118.0
162.2
121.5

130.7
120.3
149.2
125.4
138.8

122.3
161.5

109.6
156.1

144.9

146.1
134.6

175.0
143.3

147.1

Sol 2, MgSO4, 5 per cent

Sol. 3, Na2SO4, 1 per cent
Sol 4 Na2SO4 5 per cent

Sol. 5, Na2SO4, 10 per cent
5 per cent NaOH

(b) 14 days in water before immersion.
Sol. 4, Na2SO4, 5 per cent
Sol 1, NaCl, 5 per cent

Sol. 6, Na->CO3, 5 per cent
Sol. 7, NaHCO3, 5 per cent

Sol 8 NaCl 1 per cent

(c) 14 days in water and 3 months in air before
immersion.
Sol. 8, NaCl, 1 per cent
Sol. 6, Na2CO3, 1 per cent
(3) Neat Ideal in solutions of mixed salts,
(a) 7 days in water before immersion.
Sol. 11, CaCl2, MgCl2, NaCl, 1.33 per cent
each
Sol. 10, NaCl, Na2S04, MgCl2, MgSO4, 1.25
per cent each

(b) 3 months in water before immersion.
Sol. 10, NaCl, Na2S04, MgCl2, MgSO4, 1.25
per cent each

(c) 48 hours in damp oven before immersion.
Sol. 10, NaCl, Na2SO4, MgCl2, MgSO4, 1.25
per cent each
(4) Neat Ideal to show effects of titration.
In water. Titrated daily with HoSO4*
Sol. 14, NaCl, Na2SO4, 2.5 per cent each. Titrated
weeklv with H2SO4f

In water. Titrated daily with H2SO4J
Sol. 4, Na2SO4, 5 per cent. Titrated weekly with
H2S04t

*Water changed weekly.
tSolution not changed.
$Water changed after each test for strength.

Dec. 1919 Effect of Alkali Upon Portland Cement — //.

Given Periods in Salt Solutions Expressed as Per Cent of the Strength
for a Similar Length of Time.

After being in solution:

month

1

z

d

s

24 months

30 months

40 months

84 months

a

£

0

jt

1

\\

a
£

0

a

o

1

1

i

a
£
o

3

5

I

a
I

o
a
d
9

EH

tt

C3

— :

°

"£

~

—

100

100

100 100

100

100

100

100

100

100

100

100

too

100

138.8
67.3
55.8
89.9
92.1
126.3

93.4
126.3
115.9
118.2
108.8

137.1
114.9
102.6
103.9
127.1
123.9

112.0
122.3
132.5
121.8
123.8

106.5
118.3
112.0
73.6
121.3
104.2

57.5

136.5
38.7
108.1
96.1
54.9
123.4

39.8

121.5

78.5
110.0
84.9
83.1
113.8

48.6

95.8
91.9
94.2
59.4
103.2
80.8

40.5

134.4
96.1
107.0
103.5
41.3
35.8

96.7

115.1

94.0
100.6
81.4
72.2
103.3

68.6

76.2

81.7
91.6
66.0
105.8
74.7

51.1

110.1
90.2
102.9
93.1
55.6
113.2

67.1

93.1

85.9
97.2
79.5
80.7
93.1

59.1

76.8
55.7
69.1
50.2
81.8
94.9

25.4

78.1
80.1
91.6
117.8
138.9

121.0

77.8
67.9
80.3
84.0
110.3

73.2

107.7
108.0
92.9
t!9.1

113.5
96.2
101.6
127.2

110.6
102.1
97.2
123.1

73.6
90.8
89.3
93.6

112.5
106.3
107.6
131.7

93.0
98.5
98.4
112.6

105.2
124.2
96.2

100.2
105.0
116.9

102.6
114.6
106.5

90.5
62.6
94.3

249.6
87.3

156.1
90.8

186.4
97.8

104.3
129.6

96.3

100.5

98.4

77.9
103.0

94.5
99.2

86.2
101. 1

80.4
107.6

87.4
81.1

83.7
94.3

65.1
63.2

91.6
131.7

78.3
97.4

46.9

78.2

92.6

119.9

102.2

72.9

117.7

95.3

88.1

99.1

93.6

61.5

111.9

86.7

112.0

134.0

86.9

113.9

100.4

74.4

110.0

92.2

79.4

114.0

96.7

47.6

127.9

136.4

80.3

106.5

93.4

74.1

119.2

91.6

76.4

126.8

101.6

34.7

13.1

23.9

41.4

93.7

103.3

148.3

120.8

67.1

167.0

117.0

80.1

174.7

122.4

59.5

83.7

71.6

101.3

117.9

106.3

89.5

97.9

97.1

102.2

98.6

107.7

37.6

72.6

81.1
66.2

125.9

123.0
104.7

136.5

118.5
101.5

103.3

117.5
112.2

107.9

118.0
111.3

105.6

99.3
110.9

84.3

106.3
121.2

127.0

102.3
116.0

105.6

101.4
107.3

97.8

144.5
118.7

109.1

122.9
113.0

103.4

78.8
97.8

147.2
84.9

113.0
91.3

Wyoming Agricultural Experiment Station. Bui. 122

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Dec. 1919 Effect of Alkali Upon Portland Cement— II. 29

DISCUSSION OF THE DATA.

The chief reacting substance in the cement is lime, in the
form of calcium hydroxide. It may be formed either from the
hydration of the calcium oxide present in the clinker, or may be
formed during the setting of cement. With the sulfate salts of
sodium and magnesium it forms calcium sulfate, CaSO4.2H2O,
and sodium hydroxide with the former and magnesium hydroxide
with the latter. The ratio of the molecular volume of calcium
sulfate formed in the reaction to the molecular volume of calcium
hydroxide is as 1.98:1. The sodium hydroxide formed in re-
action with sodium sulfate remains in solution. In the case of
magnesium sulfate, the ratio of the molecular volume of calcium
sulphate, plus the magnesium hydroxide formed in the reaction to
the molecular volume of calcium hydroxide originally in the
cement is as 2.78:1. In Bulletin 81 of Montana Experiment Sta-
tion, the disintegration of cement is ascribed as being due to this
formation of compounds with larger molecular volumes, causing
expansion and consequent cracking. Another theory, similar to
the above, is held by several experimenters. According to this
theory, tricalcium-aluminium sulfate is formed, and this then
causes the expansion and disintegration of cement. In Tech-
nologic Paper No. 12 of the Bureau of Standards, by Messrs.
Bates, Phillips, and Wig, data is produced to disprove this
theory.

Turning to the data given in tables i and 2, based on an
84 month period of action, we find that the changes in com-
pression strength and changes in tension strength do not always
go parallel ; one may increase while the other may decrease,
and vice versa. The 5% solution of sodium sulfate affected
the compression strength more than any other solution of one
salt only, cement thus treated having only 25.4% of the com-
pression strength of cement in distilled water for the same
length of time. The next lowest compression strength was shown
by cement in following solutions: Magnesium sulfate (557%)>
sodium bicarbonate (62.6%), sodium chloride (76.8%), and
sodium carbonate (90.5%). The solution of sodium sulfate was
used in 3 different concentrations: i%, 5% and 10%, and the
compression strength of cement kept in these solutions was 69.1%,

30 Wyoming Agricultural Experiment Station. Bui. 122

$0.2% and 81.8% respectively at the end of 84 months. It also
appears that cement which has been in ordinary or distilled water
for a longer period was affected more strongly, thus cement 14
days in water before immersion in a 5% solution of sodium sul-
fate only had a compression strength equal to 25.4%.

It is a noticeable fact that the compression strength after 84
months is rather high in most cases, but that the tension strength
is low, even for cement which was kept in distilled wrater. On
the average, it is only 50 per cent of the tension strength which
the cement had before immersion. This difference between com-
pression and tension strength becomes more noticeable when
considering the effects of solutions which contained more than
one salt. In the case of solution No. 10, which contained the
sulfates and chlorides of sodium and magnesium, when the ten-
sion strength of cement, which was in water 14 days and 3 months
before immersion in solution, was only 120 and 34 Ibs. respective-
ly. The tension strength of cement which was only 48 hours in
a damp oven before immersion in solution No. 10 at the end of
84 months still was 211 Ibs., thus showing again that younger
cement is less affected.

The compression and tension strength of cement in different
sets recorded in the table was not the same for all sets before
immersion in solutions. Regardless of what the strength was
before immersion, in all cases the maximum was reached some-
time during the experiment, and this maximum is very nearly the
same. In every case recorded, even in the case of cement which
was in water 3 months previous to immersion in a solution, the
compression as well as the tension strength always increased after
the immersion in a solution until the maximum was reached. If
the formation of molecules which have larger volumes than the
original compounds of set cement is the cause of the disintegration
of cement, then this would be more pronounced soon after im-
mersion, for then the formation of CaSO.4.2H2O would be faster
than it would be later. Consequently, the decrease of strength
should be most noticeable during the reaction. The tacts do not
show this to be true. The progress of the formation of hydrated
calcium sulfate from lime and sodium sulfate can be followed by
determining the amount of sodium hydroxide formed in the re-

Dec. 1919 Effect of Alkali Upon Portland Cement — //. 31

action. This was done by titrating the solution to neutral with
sulfuric acid. The procedure was carried on until no more
sodium hydroxide was formed, which was after 24 months. At
this time the cement should be the weakest. Figure 20 represents
graphically the change of compression strength and the amount
of acid required to neutralize the sodium hydroxide formed, the
neutralizing being done every day. Instead of the expected de-
crease of strength during this reaction, there was an increase.

Fig. 20.

Besides, the cement in magnesium sulfate solution should have
a lower strength than cement in sodium sulfate solution. The
results show that this is not the case. This does not mean that
the formation of reaction products, which have larger molecular
volumes than the reagents in the cement, does not contribute
towards disintegration. But it is not the chief cause or the only
cause of disintegration.

In tables 6, 7 and 8 are given the strength values of cement
kept in solution at the temperature of boiling water. The results

32 Wyoming Agricultural Experiment Station. Bui. 122

after a period of 18 months are characteristic. The set which was
completely disintegrated is the one which was in a solution of
magnesium chloride, while the cement in a solution of magnesium
sulfate had an average compression strength of 9775 Ibs., and
cement in a solution of sodium sulfate, 6122 Ibs. Noteworthy is
the fact that cement kept in solution containing both magnesium
chloride and sulfate still had a strength of 2365 Ibs., and cement
in a solution containing magnesium sulfate and sodium chloride,
4797 Ibs. Evidently the solution of sodium chloride did not pro-
duce any bad effect, since the strength of cement in it was 12735
Ibs., while the strength in hot distilled water was only 10922 Ibs.
These results suggest the following questions: Why did mag-
nesium chloride have the strongest disintegrating effect? Why
did the solution of magnesium chloride containing also magnesium
sulfate produce a slower decrease in strength than the solution
containing magnesium chloride alone ? Why was the strength of
cement kept in the solution of magnesium sulfate containing also
sodium chloride 50 per cent less than the strength of cement in the
solution of magnesium sulfate alone, although the solution of
sodium chloride did not produce any bad effects ?

The answer to the first question is the fact that magnesium
chloride in solution undergoes hydrolysis, the result of which is
the formation of hydrochloric acid. It is then this hydrochloric
acid which attacks the cement. The hydrolysis of magnesium
chloride in solution goes on to a lesser extent when magnesium
sulfate is also present in solution. For this reason the disinte-
grating effect of a solution containing both salts is less severe for
equal periods.

When magnesium sulfate and sodium chloride are dissolved
together in water, the solution contains 4 salts instead of two.
This may be expressed by the following equation: MgSO4+
2Na€l*=$MgCl2+ Na,SO4. The magnesium chloride thus pro-
duced hydrolizes and the result of this reaction is the formation
of hydrochloric acid: MgCl2+H2O±?Mg(OH)2+HCl. As the
dydrochloric acid reacts with the components of the cement, it is
being removed, so to speak, and the result of this is that the above
reactions gradually progress toward the right.

Dec. 1919 Effect of Alkali Upon Portland Cement — //. 33

Results analogous to those obtained in hot solutions were
also obtained from experiments on mortars with various propor-
tions of sand. Again, the magnesium chloride solution had the
most rapid disintegrating effect and other solutions in the same
order as above. But the results in this table show also that as
the proportion of sand in the mortar increases the disintegration
is hastened. The data in these tables are in agreement with con-
clusions from figures 16, 17 and 18. Although for numbers 60,
61 and 62 the strength after 18 months in solution is higher than
the strength which the mortars had before immersion, neverthe-
less there is a decided decrease of strength after the maximum
had been reached.

The data recorded in table 9 were meant to give a compari-
son of the resistance to action of alkali by i :i mortars prepared
with cements of different brands. The comparison of sets 22
and 23 is interesting. Apparently the presence of sodium car-
bonate in the solution counteracted the disintegrating effect. No.
22 in a solution containing sodium carbonate, sulfate and chloride
after 84 months had higher compression strength (11830 Ibs.)
than the cement No. 60 in solution of sodium chloride and sulfate
had, after 18 months (7612 Ibs). The same is also true for
tensile strength. These results are graphically represented in
figures 21 and 22 for compression and tension strength respec-
tively.

The cements, of brands tried, do not show very much differ-
ence in compression strength. The "Alkali-proof" cement had the
lowest compression, below normal, while the others did not show
any decrease. The tensile strength of all of them, although still
higher than the tensile strength of cement in distilled water, show
distinctly a decrease after the maximum had been reached. It is
noteworthy that the cements which were made up with solutions
of sulfuric acid of various concentrations and also kept in the
above solution (containing sodium carbonate, sulfate and chlo-
ride) had normal compression strength, but the tensile strength
also had decreased during the last period. The cement which
w^s mixed with a solution containing one per cent of sulfuric
acid and di-sodium-hydrogen phosphate, at the end of 84 months
in the above solution had normal compression strength and the

34

yoming Agricultural £.r/>m"iwrwf Station. Bnl. 122

Fig. 21.

/ -TUT- tt«^

^ B». ^ <wl not

The

it is snfc 204
i0r vixiocr op

*• ^

54

& 53, 54

- -

Effect of Alkali Upon Portland CYimW— //. 35

a solution was used for mixing which contained an organic sub-
stance, a distinctly inferior cement was obtained. The results with
the " Alkali-proof" cement are represented in table 10. It is evi-
dent that its tensile strength suffered greatly after the maximum
had been reached, regardless of what the solution was. Here, too,
a comparison between the results in this table and No. 51 in table
9 distinctly show that the solution which contained sodium car-

.ie was less harmful.

For testing out the value as surface protectors against the
action of alkali of different commercial paints recommended as
waterproofers, t :^ mortar was covered with them. The mortar
of each set received 2 coatings of some one paint. After 24
months in a solution of sodium carfaonate-sul fate-chloride the
paints were off. Tint the paints after that did no* offer resist-
ance to penetration of solutions is shown by the marked dyf^my
of tensile strength during the last period of 60 months. Although
ico C paint was off after 12 months, some of the "yfl^K
of the paint must have had a beneficial effect as ptoteclofs, since
in this even the tensile strength did not decrease liming the las*
period of 50 months.

In actual practice cement fuequently is only periodically ex-
posed to the action of alkali. This change of conditions from
wet and dry itself has a deteriorating effect on the cement. in
set Ho. ?i the cement was periodically wet and dry and the result
was that its compression strength was 2$% less than that off
cement which was under water constantly. Ttae solvent effect of
large volumes of water also conies in pb\\ as seen Iran No, 72,
This cement was trailed with 3 liters of *i^ distilled water even?
day daring a period of i& months and the result is uhat its com-
pression strength at the end of tthiis period was 3*-$% less than
the compression strength of cement which was undtef the
conditbr- >i nhat the water never was cliinffji. In

the dismtegration of cement is Kne result of aH the
causes combined, and besides it is aocetetmled % fimjung and

The entire prooectare mqjMt he described as Mows; Ce-

. . .; .! i ' ! .. : , v ..^c v\ !:; . . . •; . . v, :.:: , .. ,v , ; s;4 ;:> . ; ,.,^, io ...;

as a rofe, shows an increase of jJuenfUh, Tins

36 Wyoming Agricultural Experiment Station. Bui. 122

until a maximum is reached. During this period the reaction
between the salts and the calcium hydroxide takes place and if
any bad effects are produced from these reactions, they are not
marked by a decrease in the strength of the cement. The cause of
this may be that the increase in strength during this period is
greater than the decrease. The calcium sulfate or calcium car-
bonate, as the case may be, increases the density of cement and
makes it less pervious to the solutions. Besides, the calcium sul-
fate has a binding value, which may reach 200-300 Ibs. This was
tried out on halves of a broken briquet ; they were cemented to-
gether and it took that much force to full them apart. When the
compounds of the cement other than the calcium hydroxide are
attacked, then the decrease of strength begins to show. As the
table of analyses shows, the extent of chemical changes is com-
paratively small. What the changes may be can to some extent
be judged from the analysis of the crystals shown in figure 7.
The effect of magnesium chloride is more marked than the effect
of the other salts because the hydrochloric acid formed due to
hydrolysis reacts with the fundamental compounds of cement.
In the case of chlorides, the calcium chloride formed is removed
from the cement, while in the case of sulfates, the calcium sulfate
is deposited. The experiments with equivalent solutions of hydro-
chloric and sulfuric acids show that the former is more harmful.
After 6 months the strength of cement in hydrochloric acid de-
creased 22%, in sulphuric acid only 16%. The difference may
be due to the fact that the calcium sulfate formed makes the
cement less permeable. That the mortars are more rapidly de-
stroyed than the neat cement is to be expected. For the same
jweight, they contain less of the reacting material, but expose as
much surface to the action of solutions as neat cement. Conse-
quently, a greater proportion of their cement content has been
jreached in shorter time. The effects from the reactions are
augmented by the dissolving action which increases the porosity
of cement, by the friction of particles carried in suspension, by
the wearing away of the weakened surface layers, thus exposing
deeper layers of cement, and, finally, by the formation of cracks
due to uneven expansion and contraction, through which the solu-
tion also penetrates deeper into the cement. Any process which

Dec. ip/p Effect of Alkali Upon Portland Cement — //. 37

will make the cement less porous and less permeable to the solu4
tions will also increase its resistance to the action of alkali. In
this connection, attention may be called to the behavior of cement
which was not mixed with water but with solutions containing
ions forming insoluble calcium salts. Results with oxalic acid
(5%) used for mixing the cement and which, after setting, was
put in a hot solution of N. sodium sulfate and N. sodium chlo-
ride were as follows : Compression strength before immersion,
8502 ; after 6 months in solution, 10742 ; after 12 months, 10280,
and after 18 months, 13685 Ibs. Cement mixed with a solution of
magnesium flouride had a compression strength before immersion
6087 Ibs ; after 6 months in the above sodium-chloride-sulfate
solution, 9499 Ibs., and after 18 months, 15580. Since these sub-
sta'nces and also the sodium phosphate and sulfuric acid are not
very expensive, their solutions could be used in cement practice.

The results with a hot saturated calcium sulfate solution are
not recorded in the tables. The compression strength of cement
varied as follows: Before immersion, 7240; after 6 months,
9452; 12 months, 8745 ; 18 months, 11710.

Evidently the calcium sulfate solution did not have any bad
effect upon the strength of cement.

38 Wyoming Agricultural Experiment Station. Bui. 122

SUMMARY

Cement put in solutions of salts which constitute the "alkali"
sets as well as in water.

In solutions of sodium sulfate, or magnesium sulfate CaSO4.
2H.,O is formed and NaOH and Mg(OH)a respectively.

A solution of magnesium chloride had the greatest disinte-
grating effect, due to the action of hydrochloric acid produced by
the hydrolysis of this salt.

A sodium sulfate solution was more harmful than a solution
of magnesium sulfate, other conditions being equal.

The presence of sodium chloride in solutions of sulfates of
sodium and magnesium increased their harmful effect on cement.

A five per cent solution of sodium sulfate had a stronger
effect than either the i per cent or 10 per cent solutions.

The presence of sodium carbonate in solutions of the other
salts retards the disintegrating effects.

Compression strength and tensile strength are not affected
in the same degree ; tensile strength decreases more rapidly in all
solutions, even when compression strength increases.

Solutions of calcium sulfate had no bad effects

Water-proofing paints offer protection only for short periods

The "iron-ore" cement resisted the action of sodium car-
bonate-sulfate-chloride solution ; the other cements tried had
somewhat lower tensile strength.

The mixing of cement in weak solutions of sulfuric acid,
di-sodium phosphate, magnesium flouride and oxalic acid is of ad-
vantage and increases the alkali resisting qualities.

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