CEMENT and CONCRETE RESEARCH. Vol. 18, pp. 545-553, 1988. Printed in the USA. 0008-8846/88 $3.00+00.

Copyright (c) 1988 Pergamon Press plc

T H E P E R F O R M A N C E OF C E M E N T P A S T E AND C O N C R E T E S U B J E C T E D T O S U L P H U R I C ACID A T T A C K N.I. Fattuhi* and B.P. Hughes Department of Civil Engineering, University of Birmingham, England.
(Communicated by C.D. Pomeroy) (Received Nov. 6, 1987)

ABSTRACT Different cement pastes and concrete mixes were prepared using ordinary Portland cement and subjected to sulphuric acid attack. The main parameters investigated included w/c ratio (and cement content) and age of the cementitious materials. 102 mm cubes were immersed in a channel containing an approximately 2% solution of continuously flowing sulphuric acid. The changes in weight with time for each cube were determined continuously up to a maximum exposure period of 50 days. The results indicated that the deterioration of the cubes for this high acid concentration decreased with a decrease in the cement content. The effect of age was slightly more significant for cement paste than for concrete cubes. Introduction Concrete can be subjected to attack by various mineral acids which include sulphuric, nitric, hydrochloric and phosphoric. In natural groundwaters, only sulphuric acid is likely to be found as a result of the oxidation of sulphide minerals such as pyrites and marcasite, a process which is catalysed by the presence of the aerobic bacterium, thiobacillus ferro-oxidans (1) . When concrete is in contact with such acidic waters, the calcium hydroxide reacts with the sulphuric acid to form gypsum, which can be readily washed away. Sulphuric acid is also one of the main acidifying agents of acid rain. Much higher concentrations of sulphuric acid attack on concrete can occur in industrial environments. The most common forms of such attack are random spillage and unscheduled washing down (2), varying from a steady long-term drip, to a sudden and brief dousing with the acid. Leakage or the irresponsible dumpinz of chemical waste from industrial processes can also lead to sulphuric acid attack on concrete (r). Another source of severe su!phuric acid attack which is very common worldwide is that generated by bacteria in concrete sewage systems. The anaerobic bacteria generate hydrogen sulphide gas which can dissolve in water condensed on the walls of the concrete conduits, pipes and manholes above the sewage line level where aerobic bacteria, such as thiobacillus thio-oxydans can produce sulphuric acid(1~,3,4). Due to the above mentioned forms of sulphuric acid attack on concrete structures, some basic data concerning the effect of the concrete mix constituents on the rate of deterioration is *Permanent address : University of Kuwait.
545

546 N.I. Fattuhi and B.P. Hughes

Vol. 18, No. 4

necessary for the satisfactory design of such structures. It is often assumed in the literature that durability, in general, will be improved when concrete is made with a low w/c ratio and a fairly high cement content, provided that it is compacted and cured properly. An earlier paper(5) conftrrned this result for up to 0.02% acid for siliceous aggregate concrete and to a much lesser extent for limestone aggregate concrete. However, data on the significance of these parameters in the literature for a wide range of concentrations is lacking, hence this investigation was undertaken to study the effects of mix proportions of Ordinary Portland Cement based mixtures on durability when subjected to sulphuric acid attack using an accelerated test with a high concentration. TABLE 1 Concrete Mix Proportions Gravel: Sand: 1.95: 2.60: 3.25: 3.90:
. . . . . . . . . . . . . . . . . . .

Cement: Water* 1.00: 1.00: 1.00: 1.00:

. . . . . . . . . . . . . . . . .

1.05: 1.40: 1.75: 2.10:

. . . . . .

0.40 0.50 0.60 0.70

. . . . . . . . . .

3.81:

1.97:

1.00:

0.47

* ratios by weight
Materials and Soecimen Preparation

Cement paste mixes with w/c ratios ranging between 0.260 and 0.417 were used in Series I, and concrete mixes with different compositions (see Table 1) and with w/c ratios ranging between 0.40 and 0.70 were used in Series II. Ordinary Portland cement and dry siliceous aggregates were used for all the mixes. The concrete mix with w/c = 0.47 used a separate batch of OPC and is shown separately in Tables 1 & 2. A typical grading analysis for the gravel showed that the percentages passing sieves 19.0, 9.5 and 4.75 mm were 100, 38 and 2%, while that for the sand showed that the percentages passing sieves 4.75, 2.36, 1.18, 0.60, 0.30 and 0.15 mm were 99, 85, 75, 60, 15 and 4% respectively. All the mixes from Series I and II were prepared by hand, using trowels in galvanised steel trays, except for one concrete mix from Series II, which was prepared in a counterflow pan-type mixer to investigate the effect of concrete age on resistance to acid attack. For the concrete mixes, dry materials were first mixed thoroughly, then water was added, and mixing continued until uniformity was assumed. Three cubes were made (unless otherwise indicated) for density and crushing strength determinations and two cubes for the acid test, for each condition examined during the investigations. The 100 or 102 mm concrete cubes were all cast in steel moulds and compacted in one layer on a small table vibrator. Polypropylene twine was cast centrally in each cube for suspending and handling the cubes in the acid test. Two or three cubes were compacted at a time, covered with polythene sheets and either stored in the curing room at 18C + 2C and at least 90% RH (Series I), or left in the laboratory overnight (Series II). All cubes were demoulded the following day and stored in a water curing tank maintained at 18C + 2C, until due for testing.

The densities of the cubes were determined by weighing in air and in water. The cube crushing strengths were determined using a 2500 kN capacity Avery testing machine. The hydraulic channel used for the acid attack test is described elsewhere (5,6,7). Continuous circulation of the liquid in the channel was maintained throughout the test period. The solution of sulphuric acid in tap water had an average acid concentration of 2.01%

Vol. 18, No. 4 SULFURIC ACID ATTACK, PASTE, CONCRETE

547

TABLE 2 Density and Compressive Strength of Cement Paste and Concrete Mixes w/c Ratio Age (days) Density (k~m 3) Average s.d Strength (MPa) Average s.d

(a) Cement Paste

0.260 0.300 0.350 0.400 0.417 0.417 0.417 0.417 0.417 32 32 32 32 1 3 7 14 28 2151 2106 2079 2021 1998 2011 2008 2010" 2011 0.9 0.8 0.9 0.0 3.3 3.7 1.3 2.5 85.5 81.5 75.8 61.5 17.5 33.0 47.2 53.4* 58.5 4.51 1.68 1.93 3.60 0.40 0.67 1.84 3.92

(b) Concrete 0.50 0.50 0.50 0.50 0.40 0.50 0.60 0.70
. . . . . . . . . . . . . . . . . . . . . . . . .

3 7 14 28 28 28 28 28
. . . . . . . . . . . . . .

2349 2352 2358 2349 2380 2347 2340 2348

. . . . . . . . . . . . .

11.9 2.5 4.6 5.4 3.6 8.3 5.4 0.8

. . . . . . . . . . . . . . . . . . . . . .

21.6 28.2 34.5 38.7 59.2 36.2 25.4 17.5

. . . . . . . . . . . .

0.42 0.56 0.24 0.57 0.50 1.59 0.78 0.68 0.19

0.47

28

2434

3.1

58.7

* Average of two cubes only

(0.07% sd) and an average pH value of 1.78 (0.16 sd) throughout the testing period. The acid concentration was checked regularly and the depleted acid was replenished to maintain the concentration as close as possible to that required. In the volumetric analysis, sodium hydroxide of a predetermined strength was used to determine the strength of the acid in the channel (with phenolphthalein solution as an indicator). The temperature of the solution in the channel was maintained between 22 and 26C. During the testing period, the channel was cleaned once and the acid solution replenished. The cubes were suspended in the channel at ages ranging between 1 and 32 days, and were kept continuously immersed in the acid except when removed for weighing, photographing or repairing (Series I). Cubes from Series I were vigorously brushed under water with a nylon-brist!e brush, to remove debris from the surface, before weighing and returning to the acid channel. Cubes from Series II were lightly brushed.

548
N.I. Fattuhi and B.P. Hughes

Vol. 18, So.

Test Results and Discussion Series I (Cement Paste) Table 2 shows the average densities and compressive strengths for the different cubes. As expected, the density and compressive strength of the cement paste increased as the w/c ratio decreased. Figure I and Table 3 show percentage changes in weight with time for cement paste cubes (w/c = 0.417) of different ages, when immersed in the acid channel for up to 48 days. It can be seen that when the age of the cement paste cubes increased from 7 to 28 days (before immersion), the loss in weight after an acid exposure period of 48 days was reduced to 75%. However the results also show that the loss in weight can be significantly affected by the adopted brushing regime. Cubes were brushed each time they were weighed unless otherwise indicated in Table 3. When cement paste cubes of 7 days of age were not brushed, the loss in weight almost ceased after 4 weeks. This is attributed to the formation of a thick whitish-yellowish layer on the surfaces of the cubes which considerably reduced the penetration of the acid. X-ray diffraction analysis showed that the layer was gypsum. During the test period, it was observed that the gypsum layer started to form on the upper part of the cubes (as cast), and then progressed slowly to the bottom. This was thought to be due to the non-homogeneity of the cement paste cubes, where bleeding possibly resulted in a more porous matrix in the upper parts of the cubes. In an attempt to clarify this phenomenon, four cubes were made from a batch of cement paste (w/c = 0.417) and were placed in the acid channel at the age of 7 days. Two of these cubes were hung in the upside down position. The results showed that the difference between the loss in weight for cubes hung in the normal manner (i..e. in the as-cast position) and cubes hung in the upside-down position was negligible (see Table 3). This indicated that bleeding had little effect (if any) on the way gypsum formed on the surface of the cubes. Figure 2 and Table 3 show percentage changes in weight with time for cement paste cubes made with different w/c ratios, when immersed in the acid channel for a period of up to 46 days. It can be seen that apart from cubes with w/c ratio of 0.26, an increase in w/c resulted in a

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Changes in cube weight with time for cement paste at different w/c ratios.

Vol. 18, No. 4 SL~FURIC ACID ATTACK, PASTE, CONCRETE

549

TABLE 3 Changes in Weight for Cement Paste and Concrete Cu'ces Immersed in Acid. w/c Ratio Age (days) Exposure duration (days) Average change in weight (%) Range (%)

(a) Cement Paste 0.26 0.30 0.35 0.40 0.417" 0.417 0.417 0.417 0.417 0.417"* 32 32 32 32 7 7 14 28 7 7 46 46 46 46 48 48 48 48 46 46 46.4 50.0 46.6 22.5 26.3 45.9 43.4 34.6 34.0 34.7 2.0 1.1 1.8 1.8 7.1 0.9 3.0 1.1 0.1 1.5

(b) Concrete 0.50 0.50 0.50 0.50 0.40 0.50 0.60 0.70 0.47* 0.47+ 0.47++ * ** + ++ 3 7 14 28 28 28 28 28 28 28 28 47 47 46 49 49 49 49 49 50 50 50 17.6 18.3 17.1 18.0 25.0 17.4 12.0 7.9 19.6 20.6 21.1 0.3 0.1 1.4 0.2 0.9 1.0 0.6 1.5 0.6 0.7 0.2

No brushing Hung upside down Brushed once perweek Brushed twice per week

smaller loss in weight. This is attributed to the formation of gypsum layers which were thicker and more difficult to brush from the surfaces of cubes with higher w/c ratios (see Figure 3). Also, the sulphuric acid attacks the calcium hydroxide, which has a higher content in cement pastes with lower w/c ratios. At a very low w/c ratio (0.26) the greatly reduced porosity appears to have a ve~, marginal effect in reducing the loss in weight, compared with the w/c ratio of 0.30 which gave the highest loss in weight. One interesting observation was the unusual cracking patterns that were exhibited by some cubes during the testing period. One cube (w/c = 0.26) split horizontally near the centre after an acid immersion period of 3 days. The two parts were glued together with an Araldite adhesive, and tests continued. Also, a second cube which was made from the same cement paste mix, and two cement paste cubes with w/c ratio of 0.30, cracked and fell apart after acid immersion periods

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Appearance of cement paste after 24 days immersion

of 31 and 38 days respectively (see Figure 4). The crack formation was first observed after an acid immersion period of 24 days, and this can be noticed when Figure 3 is examined closely. All cracked cubes were glued, weighed and then returned to the channel. No further cracking was observed until the end of the testing period. Finally, one cube with w/c = 0.417 (age 28 days) cracked vertically after an acid immersion period of 38 days, although the two parts of the cube were held together by the gypsum layer on the surface. Volume distortions presumably cause the cracking but no specific explanations can be offered for the formation of the different cracks. It is worth mentioning that the maximum rise in temperature that can be expected due to the hydration process soon after casting is 14C for cubes with w/c = 0.30 and 1 l C for cubes with w/c = 0.40, respectively. These temperatures are not thought to be high enough to produce early cracking in the cubes prior to immersion in the acid channel. Series II ( C o n c r e t e ) Table 2 shows that density and compressive strength of the concrete cubes increased with a decrease in the w/c ratio. Figure 5 and Table 3 show percentage changes in weight with time for concrete cubes (w/c = 0.50) of different ages, when immersed in the acid channel for periods of up to 49 days. It can be seen that the loss in weight of the concrete cubes was only slightly affected by the age of the concrete. Also, the brushing regime adopted had a relatively smaJl effect on the loss in weight due to acid attack. Figure 6 and Table 3 show that the loss in weight was nearly 7% greater when cubes were brushed twice per week during the acid immersion period, compared with cubes not so brushed. Figure 7 and Table 3 show percentage changes in weight with time for concrete cubes made with different w/c ratios, when immersed in the acid channel for a period of up to 49 days, The results indicated that the loss in weight for cubes made from concrete with high w/c ratios was lower than that for cubes made with lower w/c ratios. The loss in weight at the end of the tests for concrete with w/c = 0.40 was, surprisingly, over three times that for concrete with w/c = 0.70. The main reason for this is considered to be the higher cement contents o f the concrete cubes with lower w/c ratios which were readily attacked by the acid. An approximately linear relation is obtained between change in weight and either volume fraction of cement (see Figure 8) or

Vol. 18, No. 4 SULFURIC ACID ATTACK, PASTE, CONCRETE

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FIG. 9 Appearance of concrete cubes after 27 days immersion.

loosening of the fines as the paste was eroded. Figure 9 shows the appearance of the concrete cubes after they were immersed in the acid channel for 27 days. These limited results appear to indicate that the generally accepted requirement, of using a relatively high quantity of cement for concrete mixes subjected to sulphate attack, will produce a negative effect when concrete is subjected to sulphuric acid solutions in the manner described in the paper. Volume distortions in the matrix were sufficiently restrained and distributed by the aggregate to preclude any major cracking as experienced for the cement paste cubes. Conclusions The results of tests carried out on cement paste and concrete cubes subjected to very severe sulphuric acid attack indicate that when the cement content of the cubes increased, the loss in weight due to acid attack also increased. For example, an increase of more than threefold in the loss in weight was measured for cubes made from concrete with w/c = 0.40 when compared to cubes made from concrete with w/c = 0.70. These results indicate that the generally accepted requirement of using a relatively high cement content for more durable concrete with low concentrations of sulphuric acid does not apply and is surprisingly counter-productive when concrete is subjected to water containing high concentrations of sulphuric acid. Acknowledgement The authors wish to thank the University of Kuwait for granting the sabbatical leave which enabled Dr. Fattuhi to undertake the research at Birmingham University. References 1. 2. 3. 4. 5. 6. 7. Harrison, W.H., Concrete, 21 (2), 18-24, [1987]. Plum, D.R. and Hammersley, G.P., Concrete, 18 (5), 8-11, [1984]. Thornton, H.T., Proceedings, American Concrete Institute Journal, 7, (11), 577-584, [1978]. Doran, S.R., Robery, P., Ong, H. and Robinson, S.A., Construction & Building Materials, 1, (2), 88-97, [1987]. Hughes, B.P. and Guest, J.E., Magazine of Concrete Research, 30 (102), 11-18, [1978]. Fattuhi, N.I. and Hughes, B.P., Cement and Concrete Research, 13 (5), 655-665, [1983]. Fattuhi, N.I. and Hughes, B.P., The International Journal of Cement Composites and Lightweight Concrete, _8 (4), 223-230, [1986].