Construction and Building Materials 24 (2010) 19751983

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Deterioration of compressive property of concrete under simulated acid rain environment

Y.F. Fan a,*, Z.Q. Hu b, Y.Z. Zhang a, J.L. Liu a
a b

Institute of Road and Bridge Engineering, Dalian Maritime University, Dalian, Liaoning, PR China Institute of Civil and Hydraulic Engineering, Dalian University of Technology, PR China

a r t i c l e

i n f o

a b s t r a c t
This research was carried out to discover material property of concrete under acid rain environment quantitatively. Concrete prism samples were used in the experimental program. Ultrasonic nondestructive technique and computed tomography (CT) scanning technique, were conducted to determine damage depth of concrete. Compressive strength and elastic modulus tests were conducted to determine axial compressive strength and elastic modulus. Results of concrete corrosion depth, mass loss, compressive strength and elastic modulus were statistically analyzed and modeled. This study shows that ultrasonic testing is a reliable nondestructive method to measure the damage depth. Three damage indices corresponding to relative mass loss ratio, compressive strength variation, and elastic modulus variation are dened and calculated. The trends for the damage indices to the acidity of the solution are achieved. It is concluded that the damage index corresponding to relative compressive strength variation is more suitable for the damage description of deteriorated state of the concrete attacked by acid rain. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 1 June 2009 Received in revised form 2 February 2010 Accepted 1 April 2010

Keywords: Concrete Deterioration Simulated acid rain environment Mass loss Compressive strength variation Elastic modulus variation

1. Introduction Since British chemist R.A. Smith rst observed the pollution of acid rain in 1852, it has attracted a lot of attention from environmentalists and researchers all over the world. This problem becomes more serious during the last two decades [15]. For example, it was reported that acid rain falls cover at least one third of Chinese territory. Concrete has been used as one of predominant building materials since last century. The pore solution in the concrete typically has a pH value ranging from 12 to 13.5. In the acid rain environment, physical and chemical reactions occur on the concrete structure, which results in a reduction of the pH value. When the reactions continue, the concrete structure gradually loses its mechanical strength, resulting in cracking, mass loss, and eventually structural failure. On that account, although concrete structures are typically designed to last for over 50 years, failure sometimes happens after a short time. Many well-known structures, including Emei MountainLeshan Grand Buddha, Acropolis monument in Greece, the Statue of Liberty in the United States, have been severely damaged by acid rain in the past decades. Repair or complete replacement becomes necessary, which is expensive and causes great inconvenience to the community. Based on his experiences and Uhlig method, Zhang et al. [6] estimated that the direct material loss due to acid rain in China in

1999 alone was around three billion Chinese yuan. Although some control strategies have been recommended to reduce the emission quantity of the acid medium, the frequency of acid rain precipitation at a particular place keeps increasing and the damage is still very severe [7]. Therefore, it is necessary to study the mechanism of acid rain attack on concrete structures to minimize its impact. Some studies have been devoted to this topic, but mainly focused on qualitative analyses of the results from simulation tests [814]. It is the objective of this study, as a step further, to quantitatively evaluate the effect of acid rain on concrete properties, using testing results from 354 concrete prism specimens with a dimension of 150 150 300 mm. The specimens were divided into four groups, with three groups conditioned in acid solutions and one in the water. The acid solutions have pH values of 3.5, 2.5, and 1.5, respectively, through mixing sulfate and nitric acid solutions to simulate acid rain environment with different acidity. A series of tests, including nondestructive ultrasonic test, weighing and compressive tests were conducted at different conditioned stages to determine damage depth, compressive strength, elastic modulus, mass loss, etc.
2. Experimental program 2.1. Materials and specimen preparation About 354 prism specimens (150 150 300 mm) were cast using readymixed commercial concrete to reduce variances caused by hand mixing. Details of the concrete mix are shown in Table 1.

* Corresponding author. Tel./fax: +86 411 84724279. E-mail address: fanyf72@yahoo.com.cn (Y.F. Fan). 0950-0618/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.conbuildmat.2010.04.002

1976 Table 1 Mix proportion of the concrete mixtures. Cement (kg/m3) Concrete 450 Sand (kg/m3) 678

Y.F. Fan et al. / Construction and Building Materials 24 (2010) 19751983

Coarse aggregate (kg/m3) 1040

Water (kg/m3) 159

Ratio (w/c) 0.353

w/b 0.304

Undisturbed y ash (kg) 60.0

Reducing-water agent (kg) 12.8

Table 2 Conditioning details. Designation Series 1 Series 2 Series 3 Series 4 Exposing condition Pure water H2SO4 + HNO3 (molar ratio is 9:1) H2SO4 + HNO3 (molar ratio is 9:1) H2SO4 + HNO3 (molar ratio is 9:1) Solution acidity pH 7.0 pH 3.5 pH 2.5 pH 1.5 Specimen grouping Six specimens in a group, 18 groups Six specimens in a group, 15 groups Six specimens in a group, 15 groups Six specimens in a group, 11 groups Immersion time (days) 5, 10, 15, 20, 25, 30, 35, 40, 45, 55, 65, 75, 100, 105, 130, 180 5, 10, 15, 20, 25, 30, 35, 40, 45, 55, 65, 75, 100, 130, 180 5, 10, 15, 20, 25, 30, 35, 40, 45, 55, 65, 75, 100, 130, 180 5, 10, 25, 35, 45, 55, 65, 80, 90, 105, 130

2.2. Techniques and procedures 2.2.1. Simulated acid rain environment Two types of tests are usually used to simulate concrete structures attacked by environmental conditions: site and accelerated tests. Although long-term exposure site test [15] can best simulate eld conditions, it takes much longer time to achieve desired deterioration. Therefore, accelerated test was used in most of the past studies and is also adopted herein. Wang et al. [7] pointed out that the acid rain is due to sulfuric acid in most parts of China. Therefore, only sulfuric acid type acid rain is simulated in this study, which was achieved by mixing sulfate and nitric acid solutions. The specimens were divided into four groups denoted by series 1, series 2, series 3, and series 4 (Table 2). Series 1 acted as control specimen, which was conditioned in water with a pH value of 7.0. Series 2 through 4 were conditioned in solutions with pH values of 3.5, 2.5, and 1.5, respectively, which covers practical range of the acidity of acid rain worldwide. Ageing effect was considered for all groups.

Fig. 2. PB-10 Sartorius Acidometer.

2.2.2. Test procedure Submerging and spraying are two major methods to accelerate concrete deterioration caused by acid rain in the laboratory. Based the study by Xie et al. [11], although the two methods are comparable and both give reliable results, the submerging method is more suitable for cement concrete, and is therefore adopted for accelerated ageing in this study. A corrosion-resisting rectangular tank was used to contain acid solution and concrete specimens. After curing in water for 28 days, the specimens were divided into 4 groups, as explained above. One group remained to be cured in water, while the other three groups were submerged in solutions with pH values of 3.5, 2.5, and 1.5, respectively (Fig. 1). Since pH values of the solutions were changing as the conditioning continued, acid were added to the solution periodically and mixed well with the solution so that a constant pH value was guaranteed. The solution acidity was recorded by PB-10 Sartorius Acidometer (Fig. 2). After being submerged in the solutions, six specimens as one batch were taken out for testing at different times, as shown in Table 1. The specimens were rst dried for about 23 days, followed by weighting, ultrasonic nondestructive and

compressive tests, to determine mass loss, damage depth, compressive strength, and elastic modulus, respectively. After surfaces of the prisms were cleaned, loose material were removed, and the upper and bottom surfaces were grinded to be parallel planes, the compressive test was carried out on an electro-hydraulic servo compressive testing system (YAW-YAW2000A, Fig. 3) with a capacity of 2000 kN. Following present Chinese code for concrete compressive testing (GB/T500812002), the loading rate was 0.3 MPa/s. Elastic modulus was obtained using an elastic modules testing system, which is shown in Fig. 3.

3. Results and discussion 3.1. Visual observations During the test, specimens were periodically retrieved from the acid solutions for visual inspection. It was observed that as conditioning continued, surface color gradually changed from gray to gray-black, and then yellow, and nally yellow-brown. Honeycomb voids were formed and coarse aggregates were exposed. Damage initiated from the prism corners, and the specimens became loose and powdery. The deterioration was more signicant for specimens conditioned in the solution with higher acidity, which is similar to what observed by Xie et al. [16]. Detailed descriptions are given in Table 3. 3.2. Corrosion depth 3.2.1. Establishment of a regression model to evaluate the damage depth The chemical reaction between H+ in the acid environment and calcium hydroxide in concrete can lower the pH value, resulting in mass loss and strength degradation. For reinforced concrete (RC)

Fig. 1. Concrete specimens exposed to the mixed acid solution.

Y.F. Fan et al. / Construction and Building Materials 24 (2010) 19751983

1977

Fig. 3. YAW-YAW2000A electro-hydraulic servo testing system and elastic modules testing system.

Table 3 Surface description of concrete specimens immersed in acid solution for different periods. Visual observation Descriptions of failure process State: little damage Color: brown Process description: the corroded surface become soft and white

State: slight damage Color: color of the surface turns from gray to gray-black, and then become to be yellow, and then turns into white gray gradually Process description: some white needle like crystals are formed and covered on the surface of the specimen. The corroded surface becomes to be soft and white

State: severe damage Color: yellow-brown Process description: After being immersed in the acid solution for 35 days, dissolve corrosion occurred and powder layer is formed on the concrete surface, surface voids and sand grains appears after the removal of powder, slight damage initiated at the prism corners; at 45 days, minor honeycomb voids appears, some coarse aggregates can be seen, and concrete at the prism corners become to be loose; up to 90 days, the surface become to be honeycomb, large amounts of coarse aggregates can be seen, and concrete at the prism corners become to be powdery

structure, the reaction also results in the depassivation of steel and subsequent corrosion. Phenolphthalein test is usually used to detect the damage depth of concrete, but will interfere the specimen integrity. In order to determine the damage depth of the deteriorated concrete specimens while still keeping their structural integrity, ultrasonic testing was performed at different stages using a NM-4 nonmetal ultrasonic tester (Fig. 4). As required by ultrasonic tester, ve testing points were selected on one surface the specimen, where the sonic traveling times between different points were recorded, based on which the sound velocity for undamaged

concrete, V a , and damaged concrete, V f ; could be calculated. The damage depth of concrete specimens can be calculated as

l0 dfc 2

s Va Vf Va Vf

where dfc is the damage depth; l0 is the distance between two measured points; V a is the sound velocity for undamaged concrete; and V f is the sound velocity for damaged concrete. Relations between the damage depth and immersion time under different acid

1978

Y.F. Fan et al. / Construction and Building Materials 24 (2010) 19751983

Fig. 4. NM-4 nonmetal ultrasonic tester.

1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1

1
Series 2 Series 3 Series 4

0.9 0.8 5 25 45 65 85 105 125 145 165 185

technique was used to determine the damage depth of the concrete specimen using Simens Somatom Sensation 16-slice CT scanner with the setting to be 140 kV and 200 mA (X-ray tube current). Each scan was 1 mm thick and the total number of the scans was about 300. A companion batch of concrete prism specimens was cast for CT test. After being cured in water for 28 days, the specimen was taken out and scanned to describe the internal mesco-structure based on 300 scanning images along the axis of specimen. The specimens were then conditioned in the acid solution with a pH value of 1.5 for another 120 days and scanned again. The appearances for pre- and post-conditioning of the concrete specimens are compared in Fig. 6, where the damage depth is estimated to be 1.5 cm, which is in good correlation with the results calculated from Eq. (2), 1.498 cm.

Corrosion depth / cm

Immersion time / days

Fig. 5. Corrosion depth of concrete specimens immersed in acid solution.

3.3. Mass change Based on visual observations described above, it was obvious that honeycomb voids were formed as conditioning continued, causing the mass change, which could be measured by an electronic scale with an accuracy of 0.1 g (Fig. 7). Mass change vs. immersion time for the four groups of specimens is shown in Fig. 8. It is illustrated that specimens submerged in water, pH 3.5 and pH 2.5 acid solutions show a slight mass gain at the initial immersion period, which is resulted from the effect of cement hydrated heat. It can be seen that the hydration of the cement is approximately completed after 130 days and the mass remains constant. As conditioning continues, the specimens assume a steady rate of mass loss. However, for specimens conditioned in the acid solution with a pH value of 1.5, dramatic mass loss can be seen from the beginning. The mass change of concrete specimen is dened as

solutions are shown in Fig. 5, following typical bilinear relationship. The damage depth increases much faster at the rst stage than the second one. Specimens conditioned in the solution with lower pH value (higher acidity) has larger damage depth, which was the same as the results from obtained from long-term exposure test [15], illustrating the reliability of the ultrasonic testing. Regression analyses were performed on the testing results and a simple bilinear model is proposed as

a1 t b1 a2 t b2

t 6 t1 t > t1

where y is the damage depth; t is the immersion time; a and b are regression constants; r1 and r2 are correlation coefcients; and t1 is the critical immersion time corresponding to the point where slope changes. The regression results are shown in Table 4, where strong correlation between damage depth and immersion time can be observed. 3.2.2. Validation of the proposed model using computerized tomography (CT) technology To verify the accuracy and reliability of the proposed model shown in Eq. (2), computerized tomography (CT) scanning

Dm Dmacid Dmwater

Table 4 Regression analysis. a1 pH 3.5 pH 2.5 pH 1.5 0.53456 0.72544 1.02944 b1 0.01021 0.01211 0.00730 r1 0.97 0.90 0.98 a2 1.04109 1.32113 0.78430 b2 0.00150 0.00102 0.03569 r2 0.84 0.91 1.00 t1/day 60 55 10

where Dm and Dmacid are net mass change and mass change of concrete specimens conditioned in solutions with pH values of 2.5 and 3.5, respectively; and Dmwater is the mass change of the specimens cured in water. It is noted that the mass change caused by effect of cement hydrated heat is eliminated in Eq. (3) to better understand the effect of acid attack on the mass change. Relation between mass loss of concrete specimen Dm and immersion time is shown in Fig. 9. From Fig. 9, it is clear that regardless of the acidity, the specimens show a steady rate of mass loss when exposed to the acid solutions. The rate of mass loss goes up gradually as the immersion time increases.

Y.F. Fan et al. / Construction and Building Materials 24 (2010) 19751983

1979

a. surface appearance b.reconstructed surface a. surface appearance b. reconstructed surface c. scanned surface (1) Concrete specimen before corrosion (2) Concrete specimen after being corroded for 120days
Fig. 6. The change of surface appearance beforeafter being corroded.

0.05 0 -0.05
Series 3 Series 2

mass loss /kg

-0.1 -0.15 -0.2 -0.25 -0.3 -0.35 5 25 45 65 85 105 125 145 165 185

Immersion time /days

Fig. 9. Relation between mass loss of concrete specimen and immersion time eliminating hydrated heat.

Fig. 7. Electronic scale.

Table 5 Compressive strength of concrete corroded by acid solution. Immersion time/days Compressive strength / MPa Water pH 3.5 39.4 41.0 41.1 41.0 42.5 44.2 45.4 47.1 46.2 43.9 43.7 42.9 41.6 pH 2.5 38.3 39.4 39.2 39.4 39.2 42.2 43.0 44.2 45.8 44.9 44.7 41.7 43.0 pH 1.5 45.7 46.7 47.2 43.6 42.2 43.0 42.1 40.0 -

0.2 0 -0.2

-0.4 -0.6 -0.8 -1 -1.2 -1.4 5 25 45 65 85 105 125 145 165 185
Series 1 Series 2 Series 3 Series 4

5 10 15 20 25 30 35 45 55 65 75 130 180

40.8 41.6 41.7 41.9 41.3 43.9 44.5 44.9 46.8 45.6 45.7 48.1 49.3

mass loss /kg

immersion time /days

Fig. 8. Relation between mass loss of concrete specimen and immersion time.

value, the compressive strength of the sample start decreasing. The critical time is determined by the acidity of the solution, which decreases with the increase of acidity.

3.4. Compressive strength 3.5. Failure behavior of the corroded concrete Table 5 reports mean values for compressive strength of six concrete specimens tested at different immersion times, which shows that control specimens conditioned in water are gaining strength with the increase of the immersion time. However, the trend is different from those conditioned in the acid solutions. Strength of the concrete samples takes a slight increase at the initial stage. However, once the immersion time reaches a critical 3.5.1. Failure process Failure processes under compressive test for the specimens deteriorated by different acid solutions are listed in Table 6, from which it can be seen that at the initial stage, cracks are ne and short and parallel to the load; as the deterioration continues, more discontinuous short cracks appear. For severely deteriorated

1980

Y.F. Fan et al. / Construction and Building Materials 24 (2010) 19751983

Table 6 Failure behavior of concrete corroded by acid solution. Visual observation Descriptions of failure process Little difference was observed between the failure process of the deteriorated specimen and the control specimens. As the loading increased, longitudinal penetrating cracks appeared, and the specimens were broken into small cylinders

When the stress reached 6070% of the compressive strength, the rst visible crack appeared. As the loading increased, some discontinuous longitudinal short cracks appeared, and the cracks extended and became wider. Finally the specimen was crushed

When the stress reached 6070% of the compressive strength, the rst visible crack appeared. With the loading increased, many discontinuous longitudinal short cracks appeared, and the cracks extended and become wider. Finally the specimen is crushed. For slight deteriorated corroded specimens, they failed in cylindrical shape which is similar to the failure shape of nondeteriorated specimens. However, for severely deteriorated specimen, the longitudinal cracks developed rapidly, and some transverse cracks were observed and the specimen was completely crushed in brittle

specimens, the short cracks become wider and longer to form one or two major penetrating cracks. Longer immersion time and higher acidity of the solution cause more damage and wider cracks to appear at the failure. 3.5.2. Fracture surface The fracture surfaces at failure for concrete specimens exposed to different pH acid solutions are plotted in Fig. 10. During the test, it was observed that at the initiation stage, cracks appeared at the interface between the cement and coarse aggregate, and eventually a relative rough surface was formed at failure. However, for severe

deterioration, under the chemical effect of H+ and physical effect of expansion caused by SO2 , the fracture surface changed from the 4 interfacial surface between the cement and aggregate to the internal surface of coarse aggregate, and the fracture surface became at. With the increase of acidity of acid solution and immersion time, the amount of cracks increased and also cracks became wider and longer, and the range of the fracture surface was expanded. To better understand the internal cracks in the specimen, microstructure of the deteriorated concrete specimen was studied using scanning electron microscopy (SEM). Micro cracks in the specimen are shown in Fig. 11.

pH3.5,20d

pH3.5,65d

pH3.5,130d

pH3.5,180d

pH2.5,25d

pH2.5,55d

pH2.5,100d

pH1.5,5d

pH1.5,80d

pH1.5,105d

a. longitudinal section

pH1.5,45d

pH1.5,105d

pH1.5,130d

b. transversal section
Fig. 10. Load surface of concrete specimens immersed in acid solutions for different periods.

Y.F. Fan et al. / Construction and Building Materials 24 (2010) 19751983

1981

cracks

cracks

a. cracking exist in the cement paste

b.cracking exist in the interfacial surface between cement and aggregate

Fig. 11. SEM image of cracking formed in corroded concrete specimen.

3.6. Elastic modulus 3.6.1. Static elastic modulus According to the present general code for concrete compressive testing method (GB/T50081-2002) in China, compressive elastic modulus of corroded concrete specimens were tested using elastic modules testing system as shown in Fig. 3. Dial gages were used to measure the displacement on both sides of the specimen, with gauge length of 150 mm. Six concrete specimens representing the same deteriorated condition at different times were tested and the mean values are reported in Table 7, from which it can be seen that the elastic modulus of the specimens submerged in acid solutions have a slight increase at the initial stage regardless of the solutions acidity. Once the immersion time reach to a critical value, the elastic modulus start to decrease. The critical value is dependent on the solutions acidity. 3.6.2. Dynamic elastic modulus Damage in concrete impedes the propagation of sound wave. Therefore, the wave velocity obtained from the ultrasonic testing as described before can detect local damage as well as the elastic modulus. Based on the ultrasonic time achieved from the ultrasonic testing on the corroded concrete, dynamic elastic modulus can be calculated using the following expressions

Ed

1 m1 2mqV 2 1 m1 2mqL2 1m 1 mt 2

where Ed is the dynamic elastic modulus, L is the specimen length (m), q is the density (kg/m3), t is the ultrasonic time (ls), and m is Poisson ratio. Relative dynamic elastic modulus can be dened as

Erd

Edt V 2 t Ed0 V 2 0

where Erd is the relative dynamic elastic modulus, Edt and Ed0 are dynamic elastic modulus of concrete specimen submerged in acid solutions and water for t days, respectively; and V t and V 0 are the ultrasonic velocities before and after conditioning (m/s). The relation between relative dynamic elastic modulus and immersion time can be calculated and shown in Fig. 12. From Fig. 12, it can seen that relative elastic modulus of the specimens are unstable at the initial stage and become stable as the conditioning continues. Higher acidity (lower pH value) of the solution results in higher decrease. For example, the relative elastic modulus is 75% and 66% for specimens submerged in acid solutions with pH values of 3.5 and 2.5 for 180 days, while for those in the acid solutions with a pH value of 1.5, relative elastic modulus after 105 days is 50%.

Relative dynamic elastic modulus Ecd

1.3 1.2 1.1 1 0.9 0.8 0.7 0.6 0.5 15 35 55 75 95 115 135 155 175 195
Series 2 Series 3 Series 4

Table 7 Elastic modulus of concrete deteriorated by acid solutions at different immersion times. Immersion time/days Elastic modulus/GPa Water 5 10 15 20 25 30 35 45 55 65 75 130 180 381 381 383 399 397 392 404 409 399 394 383 419 388 pH 3.5 392 353 375 389 403 391 381 387 384 384 378 413 371 pH 2.5 372 371 419 410 412 414 412 371 381 376 373 389 375 pH 1.5 427 432 435 426 417 413 412 367 -

Immersion time /days

Fig. 12. Relation between relative dynamic elastic modulus and corrosion duration.

1982

Y.F. Fan et al. / Construction and Building Materials 24 (2010) 19751983

3.7. Damage index 3.7.1. Deterioration ratio of mass loss Mass loss is another parameter to indicate concrete deterioration. Relative mass loss can be dened as

1.1 1.05 1
Series 2 Series 3 Series 4

Dcc

DmC

  mcr;t 1 100% mcn;t

0.95 0.9 0.85 0.8

where DmC is the relative mass loss ratio; mcr,t is the mass of specimen submerged conditioned for t days; and mcn,t is the mass of control nonconditioned specimen. Fig. 13 plots the relation between DmC and the immersion time. After 180 days, relative mass losses are 0.40% and 1.58%, respectively, for specimens submerged in the solutions with pH values of 3.5 and 2.5, respectively. For those in the solution with a pH value of 1.5, relative mass loss ratio of the specimens after the 105 day immersion is 7.5%. Therefore, mass loss of concrete specimen is very sensitive to acid environment. 3.7.2. Deterioration ratio of compressive strength To compare the strength deterioration trend of the concrete specimen submerged in acid solutions, relative axial compressive strength variation ratio is dened as

25

45

65

85

105

125

145

165

185

Immersion time / days

Fig. 14. Relation between immersion time and compressive strength of corroded concrete.

 DEC 1

Ect Ec0

 100% 8

DCC

fcr;t fcn;t

where DCC is the relative strength degradation ratio of axial compressive strength for deteriorated concrete specimen, fcr,t is the axial compressive strength of concrete exposed to the acid solution for t days; and fcn,t is the axial compressive strength of control specimens cured in the water at the same age. Relation between DCC and the immersion time is plotted in Fig. 14. Irrespective of the acidity of the solutions, at the initial stage, the strength of deteriorated specimens increases slightly and then gradually decreases as conditioning continue. The variance is more signicant for specimens conditioned in the solution with a pH value of 1.5 than those conditioned in the solutions with pH value of 2.5 and 3.5. For example, after 180 days of exposure, compressive strength decreases 13% and 16%, respectively, for specimens conditioned in solutions with pH values of 3.5 and 2.5. For those submerged in pH 1.5 acid solutions, compressive strength decreases 14% after 130 days. 3.7.3. Deterioration ratio of elastic modulus Based on the assumption of strain equivalence, elastic modulus variation expressed below is proposed as the damage index of deteriorated concrete specimens.
8 7 6 5
Series 1 Series 2 Series 3 Series 4

where DEC is the damage variation of elastic modulus; Ect is the elastic modulus of concrete specimen conditioned for t days; and Ec0 is the elastic modulus of control specimen cured in water. Based on the testing results, relation between DEC and immersion time is shown in Fig. 15. The same tendency can be observed on DEC for specimens exposed to the three solutions. After being submerged in acid solutions with pH values of 3.5 and 1.5 up to 25 days, damage variation of elastic modulus of the concrete specimen increase 2.21% and 2.74%, respectively. For specimens exposed to pH 2.5 solution, damage variation of elastic modulus of the concrete specimen increase 5.49%. After the immersion of 35 days for pH 1.5 and 45 days for acid solutions with pH 3.5 and 2.5, the variation becomes more signicant. Some random uctuations of DEC could be observed during the test, probably caused by some construction variances during casting and conditioning process.

4. Conclusion This study is focused on quantitative evaluation of the effect of acid rain on concrete properties based on testing results from

15 10 5

Dmc / %

4 3 2 1

DEC /%

0 -5
Series 1 Series 2 Series 3

-10 0 -1 5 25 45 65 85 105 125 145 165 185 -15 5 25 45 65 85 105 125 145 165 185

Immersion time /days

Fig. 13. Relation between mass loss and corrosion duration.

Immersion time /days

Fig. 15. Relation between damage variable D and corrosion duration.

Y.F. Fan et al. / Construction and Building Materials 24 (2010) 19751983

1983

354 concrete prism specimens with a dimension of 150 150 300 mm, which were submerged in pure water and acid solutions with pH values of 3.5, 2.5, and 1.5, for accelerated conditioning. Different acidity was achieved by varying the component of sulfate and nitric acid solutions during the mixing. A series of tests, including ultrasonic nondestructive, compressive strength, and elastic modulus tests, were conducted at different conditioned states to determine damage depth, mass loss, axial compressive strength, and elastic modulus. The following conclusions can be drawn: (1) It was shown that ultrasonic testing, which has an obvious advantage of not affect the concrete integrity, is a reliable method to measure the damage depth of concrete attacked by acid rain. A bilinear regression model is proposed to predict the damage depth under different acidities, which is in good correlation with testing results from both ultrasonic testing and CT scanning. (2) Three damage indices, DmC, DCC, and DEC, corresponding to relative mass loss ratio, compressive strength variation, and elastic modulus variation are dened and calculated using the testing results. It is concluded that for the three damage indices, the trend is the same irrespective of the acidity of the acid solutions. DCC is more suitable for the damage description of deteriorated concrete attacked by acid rain. (3) The specimens show a steady rate of mass loss when exposed to the acid solutions. The rate of mass loss goes up gradually with the increase of immersion time. The effect of cement hydrated heat shall be eliminated in order to more accurately calculate the mass change from acid attack. (4) At the initial stage, the strength of deteriorated specimens increases slightly, and then decreased gradually. The variation was more signicant for specimens conditioned in the solution with a pH value of 1.5 that those conditioned in the solutions with pH values of 2.5 and 3.5. (5) At the initial stage, elastic modulus variation ratio of the specimen is not stable. Once the immersing period exceed 35 days for specimens conditioned in the solution with a pH value of 1.5 and 45 days for those conditioned in the solutions with pH values of 3.5 and 2.5, the variations become more signicant.

Acknowledgements This paper is funded by a National Natural Science Foundation of PR China (Grant No. 50708010), Liaoning Provincial Funded project (Grant No. 1050259), Liaoning Provincial Funded project (20092149), and supported by a Foundation for Youth Key Teacher of Dalian Maritime University. Contributions from Dr. A. Chen (West Virginia University, USA) for reviewing of the paper are acknowledged as well. References
[1] Neuman K. Trends in public opinion on acid rain: a comprehensive review of existing data. Water Air Soil Pollut 1985;31(34):104759. [2] Eney AB, Petzold DE. The problem of acid rain: an overview. Environmentalist 1987;7(2):95103. [3] Mansfeld F, Vijayakumar R. Atmospheric corrosion behavior in Southern California. Corr Sci 1988;28(9):93946. [4] Larssen T, Seip HM, Semb A, Mulder J, et al. Acid deposition and its effects in China: an overview. Environ Sci Policy 1999;2:924. [5] Zhao YX. Spatial-temporal distribution of acid rain in China during 2005. Adv Clim Change Res 2006;2(5):2425 [in Chinese]. [6] Zhang X, Han E, Li H. Estimation of the corrosion loss by the acid rain in China. J Chin Soc Corr Protect 2002;22(15):3169 [in Chinese]. [7] Wang TJ, Jin LS, Li ZK, Lam KS. A modeling study on acid rain and recommended emission control strategies in China. Atmos Environ 2000;34:446777 [in Chinese]. [8] Sato T, Takewaka K, Kamata S. Experimental study on deterioration of concrete structures due to acid-rain. In: Proceedings of the second international conference on concrete under severe conditions. Norway; 1999. p. 55564. [9] Kishimoto Y, Hokoi S, Harada K, Watanabe F, Takada S. Inuences of acid rain on the neutralization process. In: Proceedings of the 3rd international building physics conference, research in building physics and building engineering, Canada; 2006. p. 20916. [10] Hu X. Analysis for simulation test on acid rain attacking concrete. J Chin Ceram Soc 2008;36(Suppl.):14752 [in Chinese]. [11] Xie S, Qi L, Zhou D. Investigation of the effects of acid rain on the deterioration of cement concrete using accelerated tests established in laboratory. Atmos Environ 2004;38:445766. [12] Okochi H, Kameda H, Hasegawa S, Saito N, Kubota K, Igawa M. Deterioration of concrete structures by acid deposition an assessment of the role of rainwater on deterioration by laboratory and eld exposure experiments using mortar specimens. Atmos Environ 2000;34:293745. [13] Kong LH, James G. Concrete deterioration due to acid precipitation. ACI Mater J 1987;84(2):1106. [14] Fattuhi NI, Hughes BP. The performance of cement paste and concrete subjected to sulphuric acid attack. Cement Concrete Res 1988;18(4):54553. [15] Kanazu T, Matsumura T, Nishiuchi T, Yamamoto T. Effect of simulated acid rain on deterioration of concrete. Water Air Soil Pollut 2001;130(14 III):14816. [16] Xie S, Zhou D, Yue Q. Research on mechanism of corrosion of non-metal building materials by acid deposition. Res Environ Sci 1998;11(2):157 [in Chinese].