C. Vipulanandan
J. Liu
Center for Innovative Grouting Materials and Technology (CIGMAT), Department of Civil and Environmental Engineering,
University of Houston, Houston, Texas


21.1 INTRODUCTION would have wide use in the wastewater industry
(Redner et al., 1994). Redner et al. (1994) evaluated
Cement concrete is a highly alkaline material that more than 20 different coating systems in an accel-
can easily deteriorate in acidic environments. There- erated test program (in 10% sulfuric acid). Their test
fore, concrete structures in food factories, chemical results showed that there were no fail-safe coatings.
plants and wastewater facilities are usually protected Even coatings that survived the accelerated test had
using various types of coating materials. In sewage failed in the field (Redner et al., 1994). Liu and
facilities, sewer pipes and wastewater treatment Vipulanandan (1999) studied concrete specimens
plants are corroded by sulfuric acid from sulfuric- coated with an epoxy coating and immersed in 3%
acid-producing bacteria (Soebbing, 1996 and Sand, sulfuric acid. The results showed that for specimens
1994). The sulfuric-acid-producing bacteria found without holidays in the coating film, the mass gain
in sewer crowns thrive at low pH, which is inhibitory was only about 1% after three years, and the proba-
to most competitors. Islander (1991) reported that bility of failure increased with the increase in mass
the concentration of sulfuric acid for the worst case for coated concrete in 3% sulfuric acid. Hence, pre-
in sewer environments was pH of 0.5 (close to the dicting the mass change in test specimens of coated
pH of a 3% sulfuric acid solution). Fattuhi and concrete is very important in determining the service
Hughes (1988) immersed concrete specimens in a life of coated concrete and evaluating the effective-
channel containing an approximately 2% solution of ness of coating materials.
continuously flowing sulfuric acid. Their results When cement concrete was submerged in aggres-
showed that after 48 days of exposure, the average sive solutions, the mass change of the concrete was
mass change was 34.6%. Ehrich et al. (1999) studied a key factor that indicated the degree of deterioration
biogenic and chemical sulfuric acid corrosion of of concrete. Many researchers have developed mod-
mortars. For ordinary Portland cement mortar, the els to predict the solution uptake of concrete. For ex-
mass loss of the samples in the biogenic sulfuric acid ample, Tang (1992) theoretically analyzed the fluid
environment was about 20% after 100 days, and the flow through hardened cement paste and derived the
mass loss of the samples in the pH 2 chemical sulfu- quantitative relationship between permeability and
ric acid environment was more than 15% after 25 re- pore size distribution. Hinsenveld (1995) used the
newals (every one to three days to renew the solution shrinking core model to predict the leaching process
according to the pH of the solution). in cement-stabilized waste in acid. The relation be-
A coating system that bonds to concrete and pro- tween the amount of leached substances and expo-
vides protection from microbial sulfuric acid attack sure time was obtained. Mebarkia and Vipulanandan


(1995) developed a cylindrical model to predict in modeling the coated concrete behavior. In field
mass increase of polymer concrete. Martys et al. applications, a coating system cannot be applied
(1997) analyzed sorption properties of mortars and without holidays (pinholes) on concrete substrate
concrete in water and suggested an empirical equa- and, hence, performance of the coated concrete
tion to predict water uptake in mortars and concrete. should be evaluated with holidays. Liu and Vipu-
Gospodinove (1999) developed a model to numeri- lanandan (2003) developed models to predict the
cally describe the concentration distribution of sul- mass change of coated concrete. The pinhole effect
fate ion in concrete. Mainguy (2000) analyzed has been considered in the models. This chapter
leaching of cement-based materials and modeled the presents a combination of test methods and models
process with the mass balance equation of calcium. to predict mass change and pinhole effect for coated
In this study, the relationship between the effective concrete. Test and analytical results for epoxy and
diffusion coefficient and calcium concentration in polyurethane coatings are discussed.
solid/liquid phase was developed.
The penetrability of liquids through coating films
was an important factor in protecting substrates 21.2 MATERIALS
from corrosion. Many studies on the transport of
liquids in organic coatings were focused on water In this study, several commercially available poly-
penetrating through free and applied coating films. mer and cement-based coatings were used. Proper-
Corti et al. (1982) studied the effect of steel and ties of some of the polymer based coatings are sum-
glass substrates on water absorption in epoxy- marized in Table 21.1. It must be cautioned that the
polyamide coating, and concluded that the free films results from this study cannot be generalized to all
showed a tendency toward greater water uptake. coatings available in the market place.
Thomas (1991) used Fick’s first and second laws
under the steady state condition, and studied water
and gases penetrating through free coating films.
Nguyen (1995) studied water diffusion in both free
and applied (on metal and silicone) coating films
21.3.1 (a) Hydrostatic Test
based on Fick’s second law under non-steady state
conditions. In order to simulate hydrostatic pressure on concrete
For concrete coatings, because of the porous na- structures due to the ground water table, concentri-
ture of the substrate, the penetration of coatings into cally placed concrete pipes are used to develop the
the concrete is a very important factor, and the inter- necessary full-scale testing conditions (Figure 21.1).
face properties may have affected the penetration of This is achieved by using 900-mm (36-in.) inner
liquids. Therefore, it was necessary to incorporate pipes and 1,600-mm (64-in.) outer pipes with two
the interface properties related to coating-concrete concrete end plates. Based on the input from con-

TABLE 21.1 Properties of Coatings

Density Pulse Velocity Hardness Thickness Application
Coating Material kg/m3 (m/sec) (Shore*) mm** Condition

Epoxy-1 Pure epoxy 1,190 2,512 70 2.0 dry and wet surfaces
Epoxy-2 Pure epoxy 1,530 2,730 73 1.5 dry and wet surfaces
Epoxy-3 Pure epoxy 1,200 2,532 71 2.0 dry and wet surfaces
Epoxy-4 Glass fiber reinforced 1,635 2,863 72 1.5 dry and wet surfaces
Polyurethane-1 Polyurethane 1,130 2,283 67 1.1 dry and wet surfaces
Polyurethane-2 Polyurethane 1,355 3,165 78 4.7 dry and wet surfaces
Remarks All are epoxy-based Varied from Increase with Similar Varied from Physical properties of
coatings. 1,190 to density hardness. 1.5 to 2.0 mm coatings are similar
1,635 kg/m3

*Durometer Type D
**Ultrasonic Multi-Layer Coating Thickness Gage (PosiTector 100)

FIGURE 21.1 Hydrostatic test configuration: (a) elevation; (b) cross-section; (c) outside view.

tractors, 900-mm (36-in.) diameter pipe is the small- Wet Test
est man-entry pipe in which a coating applicator
The 900-mm (36-in.) concrete pipe was installed in
could operate with reasonable ease. Steel elements
the test chamber and pressurized at 105 kPa (32 feet
are used to support the entire setup. The inner con-
of water head) for at least two weeks before applying
crete pipe surface represents a concrete surface
the coating. The coatings were applied after water jet
under hydrostatic pressure, and coating a pipe sur-
blasting or sand blasting the surface. The average ap-
face (laid horizontally) represents most of the diffi-
plication temperature was 650 ºF. The moisture emis-
cult conditions encountered in coating structures,
sion rate was 536 µg/(m2.sec) (9.49 lb/1,000 ft2.
such as in lift stations. The total area available for
24 h, ASTM E 1907) on the concrete surface.
coating is 14 sq. m (150 sq. ft). Dry Test Measurements
Coating was applied to new 900-mm (36-in.) diam- Visual Inspection: The coated surfaces was visu-
eter concrete pipes. The coated pipes were then ally inspected regularly and information on blister-
placed in the pressure chamber for hydrostatic pres- ing, spalling, discoloring and cracking was noted
sure testing. and photographed.

In Situ Bonding Test (CIGMAT CT-2, Modified this case, the coatings were cured without free sur-
ASTM D 4541): In situ bonding tests on the coat- faces. Both dry and wet specimens were used to sim-
ing materials were performed at the end of six ulate the dry and wet coating conditions. The bonded
months. A 51-mm (2-in.) diameter core drill was specimens were cured under water up to the time of
used to core into the concrete surface and isolate the testing. Compared to CIGMAT CT-2 test, this was
test area, and a metal piece was glued to the coating an easier test to perform, since no coring or gluing of
with an epoxy (see Figure 21.2(a) and (b)). After 24 metal fixture was required.
hours of curing, the test was performed, using a
portable bonding strength tester (Figure 21.2 (c)).
The performance rating criteria were as follows: Failure Types
(i) Overall condition (appearance): good, satisfac- In order to understand the failure mechanism, the
tory, bad; (ii) Surface texture: smooth, rough; (iii) observed failure types in the CIGMAT CT-2 and
Blistering: yes, no; (iv) Cracking: yes, no; (v) Change CIGMAT CT-3 tests are defined and summarized in
in color: yes, no; (vi) Overall finish (quality of the Table 21.2.
job): good, satisfactory, bad; (vii) Overall Rating:
Pass, Satisfactory, Fail.
Over twenty different coatings have been evalu- 1. Type B1 failure is concrete failure. The failure oc-
ated and 90% of the coatings passed the test. The curred in concrete due to tension in the CIGMAT
typical coating defects in the test included cracks on CT-2 test or bending in the CIGMAT CT-3 test.
the coating surface, hard and soft blisters, and dis- This type of failure is the most desired failure
colored spots (Figure 21.3). type because the bonding strength between coat-
ing and concrete is higher than the tensile strength
or flexure strength of concrete.
21.3.2 (b) Bonding Test 2. Type B2 failure is coating failure, which is cohe-
sive failure of coating. This type of failure indi-
In the bonding tests, CIGMAT CT-2 test (modified cates that the tensile strength of the coating is
ASTM D 4541) and CIGMAT CT-3 test (modified lower than the bonding strength and the tensile
ASTM C 321) were used to determine the bonding strength of concrete.
strength of coatings to concrete (Figure 21.2). Dry 3. Type B3 failure is bonding failure where the fail-
concrete specimens are stored in the room environ- ure occurs between coating and substrate. This
ment (temperature 23  2 °C and humidity 50  type of failure indicates that the coating has poor
5%), and wet concrete specimens were saturated in bonding strength to concrete substrate.
water at least seven days before coating.
The three failure types above are the most com- CIGMAT CT-2 mon observed failure types in the bonding tests. In
(Modified ASTM D 4541) addition to these three failure types, some other fail-
ure types can also occur in the tests.
In this test, a 51-mm (2-in.) diameter circular area
was used for testing (Figure 21.2(a)). In this case,
the coatings were cured with one free surface. Dry 1. Type B4 failure is a combined bonding and con-
and wet coated concrete blocks were cored using a crete failure, where the bonding strength of coat-
diamond core drill to predetermined depth to isolate ing to concrete is close to the tensile/flexure
the coating. A metal fixture was then glued to the strength of concrete.
isolated coating section using a rapid-setting epoxy. 2. Type B5 failure is a combined bonding and coat-
Bonding strength was determined by pulling the ing failure, where the bonding strength of coating
metal fixture off the substrate. to concrete is close to the tensile/flexure strength
of coating. CIGMAT CT-3 The failure types observed in the bonding tests are
(Modified ASTM C 321) shown in Figure 21.4. Through these bonding tests,
the variation of the bonding strength of the coatings
In this test, the coating was sandwiched between a can be investigated. Typical variations of bonding
pair of rectangular concrete block specimens and strength with dry and wet concrete surfaces for some
then tested for bonding strength (Figure 21.2(b)). In epoxy coatings are shown in Figs. 21.5 and 21.6.

(a) (b)


In-situ test setup

FIGURE 21.2 Defects observed in the hydrostatic test.

FIGURE 21.3 CIGMAT CT-2 and CIGMAT CT-3 test setups: (a) CIGMAT CT-2 test (modified ASTM D 4541 test);
(b) CIGMAT CT-3 test (modified ASTM C 321 test); (c) CIGMAT CT-2 test (in situ bonding test).

and (2) 3% sulfuric acid solution (pH = 0.45, repre-
21.3.3 (c) Pinhole Test—Chemical senting the worst reported condition in the waste-
Resistance (CIGMAT CT-1, water system). Control tests were performed with-
modified ASTM G 20) out pinholes.
In order to study the chemical resistance of coated The weight changes of uncoated dry and wet con-
cement concrete, the ASTM G 20 test was modified crete (immersed in water for seven days) in DI water
to use with coated concrete. As shown in Figure and 3% sulfuric acid are shown in Figure 21.8.
21.7, the specimens were immersed in a selected Based on rate of weight change, the dry and wet con-
test reagent to half the specimen height in a closed crete specimens became almost saturated in 84 days
bottle, so that the specimens are exposed to the liq- (12 weeks) in DI water. During this period, the
uid phase and vapor phase. (This method is intended weight increased for dry and wet concrete by 0.91%
for use as a relatively rapid test to evaluate the and 0.35%, respectively. The dry and wet concrete
acidic resistance of coated specimens under antici- specimens in 3% sulfuric acid had a weight loss over
pated service conditions.) Dry and wet (water satu- 2% in seven days.
rated) cement concrete specimens were coated on When coated concrete specimens are immersed in
all sides and tested. For the test, two radial holes D.I. water and sulfuric acid solution, liquid will pen-
were drilled into the coated specimen approxi- etrate through the coating film, pinholes, and inter-
mately 15 mm deep (considering the sizes of aggre- face (exposed at the pinholes) into concrete. The
gates used in the concrete specimens). In this test, mass increase for the coated concrete in the solu-
the changes in (1) weight of the specimen, and (2) tions may vary according to different coatings. The
appearance of the specimen were monitored at reg- typical mass increase in coated concrete for some
ular intervals. The two test reagents selected for this coatings are shown in Figs. 21.9 through 21.11.
study were (1) deionized (DI) water (pH = 5 to 6), When sulfuric acid solution penetrates into concrete,

TABLE 21.2 Failure Types in CIGMAT CT-2 Test and CIGMAT CT-3 Test

Failure Type Description (Modified ASTM D4541 Test) (ASTM C321 Test)

Type B1 Substrate Failure

Type B2 Coating Failure

Type B3 Bonding Failure

Type B4 Bonding and Substrate Failure

Type B5 Bonding and Coating Failure

acid will react with the Ca(OH)2 and other com- • Criterion 3: Multiple blistering, multiple cracking
plexes in the cement. Based on the pH and sulfate on the coating surface which is not included in
concentration in the specimen, gypsum and/or et- Criteria 1 and 2
tringite are formed. Ettringite expands and causes • Criterion 4: Weight gain is more than 2%
coating cracking and blistering. Failure types ob-
served when sulfuric acid attacked the coated con-
21.3.5 Coating Concrete Failure Types
crete specimens included blistering at the pinhole,
cracking of coating starting from the pinhole, or on The coating failure types observed during the testing
the surface of the specimens. included cracking across the pinhole (mainly along
the length of the cylindrical specimens), spalling,
21.3.4 Failure Criteria and blistering around the pinhole. The configura-
tions of the failure types are shown in Figure 21.12.
In order to evaluate the performance of various coat-
ings, the failure criteria for coated concrete are de- Type C1 Failure
fined as follows:
Major cracking across pinhole (Figure 21.12(a)).
• Criterion 1: When the diameter of the blister on For coated specimens with pinholes, the concrete is
the coating becomes larger than 25 mm (1 in.) directly in contact with sulfuric acid through the pin-
• Criterion 2: When the length of the crack on the holes. Calcium hydroxide and other calcium com-
coating is longer than 25 mm (1 in.) plexes react with acid and forms gypsum and ettrig-

(a) (b) (c)



FIGURE 21.4 Bonding test failure types confiugred in Table 21.1: (a) Type B1 failure; (b) Type B2 failure; (c) Type
B3 failure; (d) Type B4 failure; (e) Type B5 failure.



FIGURE 21.5 Test results from CIGMAT CT-2 (modified ASTM D 4541) tests. (a) For dry coated concrete. (b) For
wet coated concrete.

ite at different pH levels. Expansion can be observed men. Generally, coated concrete specimens that
in the region, subjecting the coating to hoop tensile have larger pinholes cracked first.
stresses and strains. Initially, small blisters are
formed around the pinholes. The blisters continue to
grow with the immersion time. Hence, the coating Type C2 Failure
tends to confine the expansion of concrete, resulting Random cracking of coating (Figure 21.12(b)).
in tensile stresses and strains in the coating. Pinholes When sulfuric acid penetrates through the coating
further magnify the stresses in the coating. When film and reacts with the concrete on the interface of
tensile stress caused by concrete expansion exceeds the coating, and the concrete substrate reacts with
the tensile strength of the coating, cracks occur in the primer of the coating, random cracking may
the direction of the length of the cylindrical speci- occur on the coating film. If the tensile strength of

FIGURE 21.6 Test results from CIGMAT CT-3 (modified ASTM C 321) test. (a) For dry coated concrete. (b) For wet
coated concrete.

the coating is low or the coating film is very thin cracking, and blisters mainly occur around the pin-
(less than 1.5 mm), the coating film will crack at holes. This type of failure was observed in epoxy-
weak points due to concrete expansion. Cracks fur- and polyurethane-coated concrete specimens with
ther develop and cause the coating film to peel off of pinholes in 3% sulfuric acid.
the concrete substrate. In such cases, coatings fail
faster than other failure types. Type C4 Failure
Blistering on the coating surface (Figure 21.12(d)). Type C3 Failure
In some cases, blisters are also observed on the coat-
Blistering around pinholes (Figure 21.12 (c)). ing film. Hard blisters on coating surface are caused
When concrete expands, coatings deform without by expansion of corroded concrete (or primer), while

FIGURE 21.7 Chemical tests on coating materials for concrete (CIGMAT CT-1, modified ASTM G-20).

soft blisters on the coating surface are caused by os- t50 = time for coated concrete 50% pass
motic pressure. in acid.
t0 = time when uncoated concrete fails
21.3.6 Time-to-failure Factor in acid.
D, W = dry and wet conditions, respec-
For uncoated specimens in 3% sulfuric acid, failure
was defined by 2% weight loss, and all specimens
failed in seven days (t0). In order to quantify the per- By comparing the time-to-failure factors for differ-
formance of coated concrete, the time-to-failure fac- ent coatings, the acid resistance of the coatings can
tor (K) is defined as the ratio of the failure time of clearly be classified. The higher the time-to-failure
the coated specimens to the failure time of the un- factors, the better the acid resistance of the coating.
coated specimens in 3% sulfuric acid. (t) as follows:
K (21.1)
As shown in Figure 21.13(a) and (b), the time-to-
failure factors for Epoxy-1 are as follows. In order to better quantify the factors influencing the
For 100% passing: performance of coated concrete, models were devel-
oped based on a mass transfer concept.
tD100 200
Dry condition K100    29,
t0 7
21.4.1 (a) Physical Model
100 500 When coated concrete came into contact with liquid,
Wet condition K100    71.
t0 7 liquid penetrated through the coating film into the
concrete. Physical models for coated concrete when
For 50% pass:
immersed in liquid can be divided into the following
tD50 300 two categories, based on the reactivity of the liquids
Dry condition K50    43, with the concrete substrate and coatings.
t0 7
50 1100 Category 1:
Wet condition K50    157.
t0 7 No Chemical Reaction
Where t100 = time for coated concrete 100% If the liquid did not chemically damage either the
pass in acid. coating film or the concrete, such as D. I. water in

FIGURE 21.8 Weight change in uncoated concrete: (a) D.I. water; (b) 3% sulfuric acid.

the present study, the physical model of liquid pene- Category 2:
trating into the coated concrete specimens can be
With Chemical Reaction
represented as shown in Figure 21.14(a).
In this case, the liquid saturated the contact sur- If the liquid, such as sulfuric acid solutions, reacts
face of the coating film. Due to the gradient of the with the concrete substrate and damages the concrete
degree of saturation in the coating film, the liquid matrix, the concrete will be attacked layer by layer,
penetrated through the coating film into the concrete starting from the interface of the coating film and the
substrate. It was assumed that there was no physical concrete substrate. The physical model for this case
damage to either the coating film or the concrete. can be represented as shown in Figure 21.14(b)

FIGURE 21.9 Weight change of coated concrete in D.I. water: (a) Dry concrete; (b) Wet concrete.

where there is a region of reacted concrete and the de- the models. According to the observed mechanisms,
gree of saturation of the liquid in this concrete sub- the assumptions for modeling the liquid uptake by
strate is only in the reacted and affected zone. coated concrete cylinders are as follows:

1. Degree of saturation of liquid (S) for coating and Assumptions in Developing concrete is defined as follows:
the Models
To simplify the process of liquid transport in coated Mass of Liquid Absorbed
concrete, some assumptions are made in developing Solid Volume

FIGURE 21.10 Pinhole effect on weight change of Epoxy-2 coated concrete in D.I. water: (a) Dry concrete; (b) Wet

2. The process can be modeled by second-order dif- 4. Coating surface in contact with the liquid is as-
ferential equation (Crank, 1975) sumed to be saturated
5. Coating film and concrete surface are in good
 Da 2  2  2 b;
0S 0 2S 0 2S 0 2S contact, so there is no accumulation of liquid at
0t 0x 0y 0z the interface
6. Coating film does not react with liquid
where S is the degree of saturation of the coating
or concrete
3. The mass transfer coefficient is a constant in the 21.4.2 (b) Film Model (Model 1)
coating film (DCT), un-reacted concrete cylinder The coating thickness on the concrete cylinder was
(DCO), or reacted concrete region (DrCO) in the range of 1.5–2.0 mm for the two epoxy coat-

FIGURE 21.11 Weight change in coated concrete in 3% sulfuric acid: (a) Dry concrete; (b) Wet concrete.

ings; hence, it can be treated as a thin plane sheet. T = time, sec
The degrees of saturation of the coating surface on x = dimension in the coating thickness di-
the liquid side and the interface are SCT CT
0 and Si , re- rection, cm
spectively (Figure 21.14(a)). DCT = mass transfer coefficient, cm2 /sec
The mass transport process in one dimension
under non-steady state, if the transport parameter is For a coating film on a porous substrate, the de-
DCT, is given by (Crank, 1975) gree of saturation on the interface of the coating film
and the substrate vary with time. If a small time in-
0S 0 2S terval t to (t + dt) is considered, the process can be
 DCT 2 , (21.3) assumed to be a pseudo steady state. In this case, Eq.
0t 0x
(21.3) in one dimension reduces to
where S = degree of saturation, g liquid/cm3 d2S
 0. (21.4)
solid dx2

FIGURE 21.12 Failure types of coated concrete specimens.

Integrating Eq. (21.4) and applying the conditions at where βCT is a coating material parameter related to
0 and x = , S = Si , we have
x = 0, S = SCT CT
the rate of the coating film saturation. The lower the
value of βCT, the lower is the rate of saturation in the
0 x coating film. In selecting coatings for rehabilitation,
CT  . (21.5) low value of βCT will be preferred.
Si  S0

Eq. (21.6) can be written as:
The rate of mass transfer F (g liquid/ cm2 solid)
through a plane sheet under steady state is given DCT CT bCTt
F1t2  S0 e , (21.8)
(Crank, 1975) /

F  DCT a b,
dS The amount of the substance transported through the
(21.6) coating film (in the present case around the cylindri-
cal coated specimen) from time t to (t + dt) is:
Assuming that the degree of saturation on the inter-
face (coating-concrete) varies with time t and can be dWt  2pRhF1t2dt (21.9)
represented by the following exponential function:
The accumulated amount of the substance trans-
i  S0 11  e 2,
b t CT
(21.7) ported through the coating film from time 0 to t is:

FIGURE 21.13 Percentage passing versus immersion time for dry and wet coated concrete in 3% sulfuric acid: (a) Dry
coated concrete; (b) Wet coated concrete.

Wt  2pRh F1t2dt, 0
(21.10) Wt 
11  eb t 2 . (21.12)

where R = radius of concrete specimen, cm Eq. (21.12) (Model 1) is the film model to predict
h = height of specimen, cm the mass transfer through coating film on cylindrical
concrete specimen which results in the measured
That is mass change in the specimens.
The ultimate degree of saturation, S0, was ob-

DCT CT bCTt tained from the experiments on pure coating bulk
Wt  2pRh S e dt, (21.11)
/ 0 materials. Relating Eq. (21.12) to the mass change-
time relationship of coated concrete, the mass trans-
Finally, by integrating Eq. (21.11), the following re- fer coefficient and parameter βCT for the two coat-
lation is obtained: ings can be obtained.



FIGURE 21.14 Physical models of coated concrete in solution: (a) Film model; (b) Concrete model.

arDCO b,
21.4.3 (c) Bulk Model (Based on Concrete) 0S 1 0 0S
 (21.13) Non-reactive Solution (Model 2) 0t r 0r 0r
For mass transport in cylindrical specimens, if the
degree of saturation is a function of radius and time where DCO is the mass transfer coefficient of the
only, the second-order differential equation is: substrate.

For liquid transport in a coated concrete cylinder 4 q exp1DCOa2nt2
without chemical reaction, the degree of saturation  a a2 5a2>1b>D 2  16 . (21.15)
R2 n1 n n CO
on the concrete surface changes with time. If the de-
gree of saturation at the concrete surface is φ (t), the
solution of the second-order differential Eq. (21.13) Figure 21.15 shows the liquid uptake curves for
is given (Crank, 1975) by different values of parameter bR2/DCO(λ) (Crank
1975). /
2DCO q anJ0 1ran 2 From Figure 21.15, the solution uptake is deter-
S a J1 1Ran 2
exp1DCOa2nt2 mined by the parameter bR2/DCO, which represents
R n1 the effects of the coating material properties, and the
t parameter (DCOt/R2)1/2 (x-axis), which represents
COant2f1t2dt, (21.14) the time effect.

where J0 1Ran 2 is the Bessel function of the first order lCO  bR2>DCO.
zero, J1 1Ran 2 is the Bessel function of the first order,
and s are the roots of J0 1Ran 2 .
Assuming f1t2  SCO 0 51  exp1bt26 , repre-
Approximating Eq. (21.14) and considering an ex-
senting the degree of saturation at concrete surface ponential function of the form
(coating-concrete interface) which approaches a
limiting value SCO WCO
e c a b d f , (21.16)
0 , the sorption-time curve is given t DCOt n
by Crank (1975):  1  exp lCO
0 R2
where n is a constant.
0 The Eq. (21.16) is best fitted to the standard
curves in Figure 21.16 for different λCO values by
2J1 51br2>DCO 2 1>2 6exp1bt2 using the least-square method. The parameter λCO
1bR2>DCO 2 1>2J0 51bR2>DCO 2 1>2 6 and n with coefficient of correlation are summarized

FIGURE 21.15 Calculated sorption curves for a surface degree of saturation given by S0CO{1–exp(–bR t)} (Numbers
on curves are values of b2 / DCO) [Source: Crank, 1975]

FIGURE 21.16 Comparing exact (solid line) solution to the approximate solutions for a surface degree of saturation
given by: S0CO{1–exp(–b t)} (Numbers on Curves Are Values of bR2 / DCO (λ))

 e ar bf,
TABLE 21.3 Values of Parameter n from Curve Fitting 0S 1 0 DCO 0S
λCO n Coefficient of Correlation 0t r 0r k  1 0r

0.01 1.006 0.99
0.1 1.009 0.99
where k is coefficient of chemical reaction. Eq.
0.5 1.042 0.99 (21.17) can be solved analytically as Eq. (21.13).
1 1.001 0.99 The mass transfer coefficient DCO is replaced by DrCO
5 1.346 0.99 where

DrCO  .
in Table 21.3. The value of n varied from 0.98 to 1.26
when the value ofλ was in the range of 0.01 to 5. So the solution for liquid transport in coated reactive
The approximate solution for Eq. (21.16) is in cylinder substrate is as follows:
good agreement with the solution suggested by
Wrt DrCOt n
e c a b d f , (21.18)
Crank (1975) (Figure 21.16). The solid curves are
the standard curves (Eq. (21.15)) as given by Crank  1  exp lr
pR2hSro R2
(1975) while the dotted lines are the approximate so-
lution from Eq. (21.16). The agreement of the fit in- where Wrt is the mass change, is the ultimate degree
dicates that the approximate solution can predict the of saturation in the reacted area, lrCO is the mass
mass increase in the specimens as the exact solution transfer coefficient in reacted area, and is defined as
does Eq. (21.15) for the assumed degree of satura- before for the reacted region.
tion (φ(t)) at the concrete interface. Effect of Holiday Sizes Reactive Solution (Model 3) It is difficult to apply coatings on a concrete surface
For liquid transport in concrete cylinders with chem- uniformly without any defects. Holidays (pinholes)
ical reaction, Eq. (21.13) can be modified as follows and other defects will develop during the coating
(Crank, 1975): process (Redner et al., 1994). Under service condi-

tions, the liquid will penetrate through the holidays Introducing Eq. (21.19) to Eqs. (21.12), (21.16) and
on the coating surface into the concrete substrate (21.18), the equations become
and the interface. The holiday effect on liquid uptake
can be clearly seen in Figure 21.17; hence, it is Model 1
important to account for the holiday effect in the
11  eb t 2,
Wt  j
modeling. CT (21.12a)
The effect of holiday sizes on the liquid uptake of b /
the coated substrate can be taken into account by in-
troducing a parameter ξ which is a function of holi-
day sizes, to Eqs. (21.12), (21.16) and (21.18). Para- Model 2
 j e 1 exp clCOa 2 b d f , (21.16a)
meter ξ will be equal to 1 and assumed to reach the t DCOt n
limiting value when the holiday size is large; hence pR2hSCO
0 R
parameter ξ is defined as

dh and
j1 ; (21.19)
k1  k2dh
Model 3
Wrt DrCOt n
where dh = holiday diameter, cm  j e1 exp clr
COa b d f. (21.18a)
k1, k2 = parameters related to the coating pR2hSro R2

FIGURE 21.17 Comparison of the experimental data with Model 1 predictions in D.I. water and 3% sulfuric acid.

21.4.4 (d) Verifications of Models transfer coefficients (DCT) (Table 21.5) are very
close in D.I. water and 3% sulfuric acid. The result Film Model (Model 1)
indicated that solutions did not affect the perfor-
Using Eq. (21.12a), the mass change in the test spec- mance of coating films, but the mass transfer coeffi-
imens were predicted and compared to the experi- cient of the Epoxy 2 coating film had substantially
mental data in Figure 21.17. The ultimate degree of higher value in 3% sulfuric acid than that in D.I.
saturation of the coating (SCT 0 ) was also determined water. Comparing the mass transfer coefficient
from pure coating test data (Table 21.3). Based on (DCT) from model 1 (Table 21.5) with the mass
the model predictions, the values of βCT and DCT for transfer coefficient (D) [from Mebarkia (1995)]
the two epoxy coatings in D.I. water and 3% sulfu- (Table 21.3), the results indicate that the film mass
ric acid are summarized in Table 21.4 and Table transfer coefficients (DCT) (Model 1) were lower
21.5. than the bulk mass transfer coefficients (D) (Me-
The material parameter (βCT) determines the rate barkia 1995), except for Epoxy 2 in 3% sulfuric acid.
of saturation on the coating-concrete interface, and The comparison of model 1 and experiment data
parameters S0CT, βCT and DCT influence the total up- for Epoxy 1 is shown in Figure 21.17.
take of liquid. The material parameters (βCT) for
epoxy coatings varied from 0.0020–0.0035. The pa-
rameter βCT for Epoxy 1 coating was not much af- Bulk Models
fected by the liquid type and the conditions of con-
(Model 2 and Model 3)
crete (dry or wet). This was not the case with Epoxy
2, where βCT changed with liquid type and condition The mass transfer coefficients of concrete in D.I.
of concrete. The parameter (CT almost tripled from water (DCO) and 3% sulfuric acid (DrCO) can be ob-
dry concrete in D.I. water to wet condition in acid. tained by fitting the cylindrical model (Mebarkia,
The mass transfer coefficient (DCT) is propor- 1995)] to experimental data of uncoated concrete
tional to the flux of the liquid. For Epoxy 1, the mass specimens. The values of mass transfer coefficients
were 2.55 1010 m2/s and 3.08 1010 m2/s in D.I.
water and 3% sulfuric acid, respectively.
Using Eq. (21.16), Eq. (21.18), and experimental
data, the parameters n, λ, and b can be obtained for
TABLE 21.4 Values βCT for Different Coatings (Model 1) different coatings. The values of n, λ, and for dif-
(No Pinhole) ferent coating systems are shown in Table 21.4. The
Material Parameter βCT comparisons of model prediction (Eq. (21.16),
Model 2 and Eq. (21.18), Model 3) to experiment
D. I. water 3% Sulfuric acid data are shown in Figure 21.18.
Material Dry Wet Dry Wet
The parameter b represents the saturation rate of
the concrete surface. It can reflect the conditions of
Epoxy-1 0.0023 0.0020 0.0020 0.0017 the interface between the coating and the concrete.
Epoxy-2 0.0026 0.0035 0.0064 0.0070 Higher b value means that the coating may not form
a good barrier on the concrete surface against solu-
tion penetration. From Table 21.6, the parameter b
varied from 0.86  10–8 to 1.46  10–8 in D.I. Water,
TABLE 21.5 Values of Mass Transfer Coefficient (DCT) for and from 2.20  10–8 to 4.71  10–8 in 3% sulfuric
Different Coatings acid, respectively. The parameter n varied from
0.521 to 0.579 in D.I. Water, and from 0.493 to 0.761
Mass Transfer Coefficient DCT from Model 1 in 3% sulfuric acid. The values of the parameter n
10–13  m2/sec (10–12  ft2/sec)
for coated concrete are much less than the value of
D.I. water 3% Sulfuric acid the parameter n from standard curves. This indicates
Coating that the process of liquid penetrating into coated
Material Dry Wet Dry Wet concrete is not a pure diffusion process.
Epoxy-1 4.51 (4.86) 3.94 (4.24) 2.43 (2.62) 1.97 (2.11) Relating Eqs. (21.16a) and (21.18a) to the exper-
Epoxy-2 4.86 (5.23) 10.3 (11.1) 27.8 (29.9) 28.9 (31.1) imental data under different holiday sizes, parame-
ters k1 and k2 can be obtained. The values of k1 and

FIGURE 21.18 Comparison of the experimental data with Model 2 and Model 3 prediction in 3% sulfuric acid.

TABLE 21.6 Values of n and λ for Different Coating Coated Concrete

n λ β̄  10–8 s1

Coating Application 3% Sulfuric 3% Sulfuric 3% Sulfuric
Material Condition D.I. water Acid D.I. water Acid D.I. water Acid

Epoxy-1 dry 0.556 0.741 0.059 0.107 1.04 2.27
wet 0.521 0.761 0.060 0.104 1.05 2.20
Epoxy-2 dry 0.579 0.493 0.049 0.222 0.86 4.71
wet 0.535 0.574 0.083 0.164 1.46 3.48

k2 for different coatings in different solutions are cates the effect of holiday sizes on the liquid uptake
summarized in Table 21.7. of coated substrates. The smaller the value of k2, the
The value of k1 indicates the effect of holidays on more the effect of holiday sizes on the liquid uptake
liquid uptake of coated substrates. The smaller the of coated substrates. The prediction of holiday size
value of k1, the more the effect of holidays on the liq- effect on mass change of Epoxy 1 coated concrete is
uid uptake of coated substrates. The value of k2 indi- shown in Figs. 21.17 and 21.18.

TABLE 21.7 Values of k1 and k2 for Different Coatings the performance of coated substrate in long-term
immersion conditions.
D. I Water 3% Sulfuric Acid
Coating Coating 5. Bulk parameters obtained by testing coating ma-
Code Condition k1 k2 k1 k2 terials alone may not represent the performance
of coatings on concrete substrates.
Epoxy-1 Dry 0.84 0.32 0.75 0.51
Wet 1.79 0.20 0.85 1.58 6. Holidays can substantially increase the mass
Epoxy-2 Dry 0.21 0.32 0.35 0.78 change in coated concrete. The test results and
Wet 0.30 0.50 0.55 1.07 analyses showed that there is a limiting value for
holiday size, beyond which the effect is minimal
(depending on coatings and solutions).


A series of full-scale and laboratory tests were de- This project was supported by the Center for In-
veloped to evaluate the performance of coating ma- novative Grouting Materials and Technology
terials for protecting dry and wet concrete substrates (CIGMAT), under grants from the City of Houston,
exposed to sulfuric acid environments. Commer- National Science Foundation (CMS-9526094,
cially available polymer- and cement-based coatings CMS-9634685), and various industries.
were studied for a period of over five years. Analyt-
ical models were developed to predict mass change
and holiday size effect on coated concrete. The per- 21.7 REFERENCES
formance of epoxy coated concrete in D.I. water and
3% sulfuric acid was investigated over three years. 1. Coti, H., Fernandez-Prini, R. and Gomez, D. 1982. Protec-
Based on the experimental results and analyses, the tive Organic Coatings: Membrane Properties and Perfor-
following observations are advanced: mance. Progress in Organic Coatings. Vol. 10(1), 5–33.
2. Crank, J. The Mathematics of Diffusion, 2nd Ed. New York:
Oxford University Press, 1975.
1. The full-scale hydrostatic test was used to effec- 3. Ehrich, S., Helard, L., Letourneux, R., Willocq, J. and Bock,
tively evaluate the applicability of coatings onto E. 1999. Biogenic and Chemical Sulfuric Acid Corrosion of
concrete under hydrostatic back pressure up to Mortars. Journal of Materials in Civil Engineering, Vol.
105 kPa (15 psi) with a moisture emission of 536 11(4), 340–344.
µg/(m2.sec) (9.49 lb/(1,000 ft2.24 h)). Over 90% 4. Fattuhi, N. I. and Hughes, B. P. 1988. The Performance of
of the coatings tested passed this test. Cement Paste and Concrete Subjected to Sulfuric Acid At-
2. Two bonding tests were modified, based on the tack. Cement and Concrete Research, Vol. 18(4), 545–553.
ASTM standards. Based on the test results, five 5. Gospodinove, P. N., Kazandjiev, R. F., Partalin, T. A. and
modes of failure have been identified. Bonding Mironova, M. K. 1999. Diffusion of Sulfate Ions into Ce-
strength of the coatings varied from 0.25 MPa (36 ment Stone Regarding Simulaneous Chemical Reactions
psi) to 2.50 MPa (360 psi). and Resulting Effects. Cement and Concrete Research, Vol.
29(10), 1,591-1,596.
3. Chemical resistance tests can effectively evaluate
6. Hinsenveld, M. 1995. The Shrinking Core Model as a Rep-
the acid resistance of coated concrete. Test results
resentation of Leaching Processes in Cement Stabilized
showed that coatings substantially reduce solu- Waste. Contaminated Soil (Netherlands), 1,251–1,252.
tion penetration into coated concrete. The service
7. Islander, R. L., Devinny, J. S., Mansfeld, F., Postyn, A. and
life of coated concrete can be prolonged 14 to 114 Shih, H. 1991. Microbial Ecology of Crown Corrosion in
times more than uncoated concrete in acid solu- Sewers. Journal of Environmental Engineering, Vol. 117(6),
tions. 751–770.
4. The film model and concrete model developed in 8. Liu, J. and Vipulanandan, C. 1999. Testing Epoxy Coatings
this study can be used to predict mass increase of for Dry and Wet Concrete Wastewater Facilities. Journal of
coated concrete in reactive and non-reactive solu- Protective Coatings and Linings, Vol. 16(12), 26–37.
tions. The model parameters were sensitive to the 9. Liu, J. and Vipulanandan, C. 2003. Modeling Water and Sul-
changes in coatings, solutions, and holiday sizes. furic Acid Transport through Coated Cement Concrete.
Results showed that the models can better predict Journal of Engineering Mechanics, Vol. 129(4), 426–437.

10. Mainguy, M. Tognazzi, C., Torrenti, J-M. and Adenot, F. 15. Sand, W., Dumas, T., Marcdargent, S., Pugliese, A. and
2000. Modeling of Leaching in Pure Cement Paste and Cabiron, J. 1994. Tests for Biogenic Sulfuric Acid Corro-
Mortar. Cement and Concrete Research, Vol. 30(1), 83–90. sion in a Simulation Chamber Confirms the On Site Perfor-
11. Martys, N. S. and Ferraris, C. F. 1997. Capillary Transport mance of Calcium Aluminate-Based Concrete in Sewage
in Mortars and Concrete. Cement and Concrete Research, Application. ASCE Material Engineering Conference, San
Vol. 27(5), 747–760. Diego, CA, November 14–6,1994.
12. Mebarkia, S. and Vipulanandan, C. 1995. Mechanical Prop- 16. Soebbing, J. B., Skabo, R. R. and Michel, H. E. 1996. Re-
erties and Water Diffusion in Polyester Polymer Concrete. habilitating Water and Wastewater Treatment Plants. Jour-
Journal of Engineering Mechanics, Vol. 121(12), 1,359– nal of Protective Coatings and Linings, Vol. 13(5), 54–64.
1,365. 17. Tang, L. and Nilsson, L. 1992. A Study of The Quantitative
13. Nguyen, T., Bentz, D. and Byrd, E. 1995. Method for Mea- Relationship between Permeability and Pore Size Distribu-
suring Water diffusion in a Coating Applied to a Substrate. tion of Hardened Cement Pastes. Cement and Concrete Re-
Journal of Coatings Technology, Vol. 67(844), 37–46. search, Vol. 22(4), 541–550
14. Redner, J. A., Hsi, R. P. and Esfandi, E. J. 1994. Evaluating 18. Thomas, N. L. 1991. The Barrier Properties of Paint Coat-
Coatings for Concrete in Wastewater Facilities: An Update. ings. Progress in Organic Coatings, Vol. 19(2), 101–121.
Journal of Protective Coatings and Linings, Vol. 11(12),