Cement and Concrete Research 31 (2001) 1539 – 1547

Characteristics of acrylic latex-modified and partially

epoxy-impregnated gypsum
Adnan C˛olak
Department of Civil Engineering, Faculty of Engineering, İstanbul University, 34850, Avcılar, İstanbul, Turkey

Received 6 February 2001; accepted 12 June 2001

Abstract

The properties of unmodified, acrylic latex-modified and partially epoxy-impregnated gypsum composites are investigated. A
hyperbolic function of the form ax/(1 + bx)n is derived empirically to describe the water/gypsum ratio dependence of the mechanical
properties of gypsum. This function shows good agreement with the test results. The water/gypsum ratios, which give the maximum
mechanical properties, are dependent on the material parameters n and b in proposed function, the values of which lie between 17.8%
and 18.14%. The setting times of acrylic latex (methacrylic acid esters and styrene)-modified gypsum composites increase with an
increase in latex content in the mix. These composites show a clear improvement in flexural strength. However, their compressive
strengths remain almost in the same range of the unmodified gypsum. Epoxy impregnation does not lead to a significant increase in
splitting tensile strength. The durability of the composites is examined by determining their behaviour in water after different periods.
Seven days of immersion in 20
C water causes a reduction of about 70% in the mechanical strengths of latex-modified gypsum,
whereas epoxy (diglycidyl ether of bisphenol A epoxy resin cured with an alkylenediamine curing agent)-impregnated gypsum
composites with a surface coating of epoxy retain 100% of their original strengths even after 7 days exposure to water. D 2001 Elsevier
Science Ltd. All rights reserved.

Keywords: Gypsum; Acrylic latex; Epoxy; Physical; Mechanical and durability

1. Introduction treatment prevents the ingress of water in liquid form, it

also stops the transport of water-soluble salts into the
Water-related deterioration is the principal source of gypsum. Various types of polymers are used for this
difficulty with calcium sulfate-based materials as it is with purpose. In an application, the weatherability of gypsum
most building materials. The protection of gypsum is considerably improved by using a surface coating based
requires prevention against penetration of moisture to on chlorosulfonated polyethylene [1]. In the second
avoid progress of damage. A variety of methods that are method, the ingress and migration of moisture in liquid
capable of preventing and controlling the degradation of and vapour can be prevented or retarded to varying
gypsum have been used. The techniques used in the first degrees by the incorporation of a waterproofing admixture
method include protection of gypsum by waterproofing in gypsum mix. A waterproofing admixture is a powder,
materials. The method depends on the formation of a good liquid or suspension, which, when mixed with fresh
bond between the gypsum and the protective polymer and gypsum, imparts a water repelling or hydrophobic property
is therefore prone to adhesion failure because of the to the hardened gypsum. The most widely used water-
critical surface preparation requirements. Waterproofing proofing admixtures for gypsum are metal stearates,
materials are applied on gypsum surface to form imper- siliconates, acrylics and methacrylates. In a study [2],
vious coatings that prevent the passage of water in liquid high-strength gypsum products resistant to moisture are
form and may also retard vapour transmission in varying obtained by pressing the hemihydrate at low pressure in
degrees, depending on the type of coating. Since the the presence of 0.2 – 2% Al stearate. A development [3]
in which a water-soluble alkyl siliconate is added to the
gypsum (at the rate of 0.1% on the weight of the
E-mail address: adnan@istanbul.edu.tr (A. C˛olak). calcium sulfate hemihydrate) produces casts with reduced

0008-8846/01/$ – see front matter D 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 8 - 8 8 4 6 ( 0 1 ) 0 0 5 7 5 - 0
1540 A. C˛olak / Cement and Concrete Research 31 (2001) 1539–1547

Table 1 tested after different periods of immersion in water at

Properties of acrylic latex
20
C. The effect of immersion in water on the water
Type of latex Methacrylic acid esters and styrene absorption and the mechanical strengths of the composites
Appearance Milky white aqueous dispersion
was investigated.
Solid content (%) 30 ± 2
pH 9.5 – 10
Specific gravity at 20
C (g/cm3) 1
Viscosity at 25
(mPa s) 11 2. Experimental materials and methods

The specimens were prepared with the hydration of

water absorbency. The amount of additive could be calcium sulfate hemihydrate, (b-hemihydrate). For the
raised to 1% or 2% for improvement in the performance. latex-modified gypsum, acrylic latex was used. The
Bijen and Van Der Plas [4] form a moisture-resistant properties of the latex are given in Table 1. The latex/
gypsum composite that contains a thermosetting acrylic gypsum ratio was varied from 5% to 15% by weight of
polymer in dispersion state and high level of glass fiber gypsum. The quantity of water was adjusted to achieve a
(13% by weight). Even at high moisture contents up to 32 ± 2 mm constant indentation of the Vicat probe. In a
9%, the composite is still quite strong, with flexural second series of experiments, water was kept constant to
strengths of approximately 35 MPa. However, one of eliminate the effect of the water/gypsum ratio on the
the serious drawbacks in the use of water-soluble poly- results. The setting times of the acrylic latex-modified
mers is that these types of admixtures are effective in gypsum specimens were determined by Vicat needle.
maintaining water repellency only if present in suffi- After the castings were made, they were cured in
ciently high concentrations. Another effective means of laboratory conditions at 20
C and 65% relative humidity
protecting gypsum from moisture is to use water-insolu- (R.H.) for 7 days followed by drying in an oven at 40
C
ble or hardly soluble vinyl-type monomers such as Me- for 24 h. Porosities were measured by using water
methacrylate [5]. The strength and durability of the displacement method. Density was calculated from the
hardened gypsum are improved considerably by this type mass and volume of the sample. Flexural strength was
of polymer. Some proprietary admixtures combine mate- determined by using 4
4
16 cm specimens tested
rials from two or more groups and may be regarded as under three-point loading on a span on 10 cm. To
multifunctional. The object of such composite mixtures is determine compressive strength, 4
4
4 cm specimens
to impart waterproofing without strength loss. The studies were tested. For the epoxy-impregnated gypsum, two
indicate that gypsum products with good waterproofness kinds of epoxy formulations were used. The properties
are made by blending organic products with each other of epoxy formulations are given in Table 2. The speci-
[6] or with organic resins such as urea –formaldehyde mens used in this process were 20 mm diameter
40 mm
and lignin [7]. The latter formulation is design to deal long gypsum cylinders. The water/gypsum ratio was
with the problem of water penetration without affecting varied between 50% and 100%. As soon as the gypsum
the strength. specimens were set, they were stored in laboratory
Inorganic products are also used for waterproofing pur- conditions for 24 h. Then, they were dried to constant
poses. In this treatment, hardened gypsum products are weight at 40
C followed by cooling to room temperature
immersed in an aqueous sodium carbonate [8] or barium in a desiccator. The specimens were impregnated with
sulfate [9] solution to form waterproof layers on the surface the EP1 and EP2 epoxy formulations for 30 and 60 min
of gypsum. and then were polymerised at 20
C for 7 days. After
In this study, two methods were applied to improve the polymerisation, the epoxy-impregnated gypsum specimens
resistance of gypsum to water. In the first method, the were not cleaned and had a surface coating of epoxy
plaster was modified with acrylic latex. The latex/gypsum with a thickness ranging from approximately 0.5 mm up
ratio was chosen as the quantitative parameter for inves- to 1 mm. Splitting tensile test was applied to the speci-
tigating the improvement of resistance of gypsum to water mens. The depth of impregnation from surface was
by acrylic latex. In the second method, epoxy-impregnated determined by visual examination of the cut sections
gypsum specimens with a surface coating of epoxy were of samples.

Table 2
Properties of epoxy formulations
Epoxy system Resin Reactive diluent Hardener Viscosity at 30
C (mPa s)
EP1 Diglycidyl ether of bisphenol A Diglycidyl ether Trimethylhexamethylenediamine 70
EP2 Diglycidyl ether of bisphenol A Diglycidyl ether Triethylenetetramine 130
 A. C˛olak / Cement and Concrete Research 31 (2001) 1539–1547 1541

Table 3
Physical and mechanical properties of gypsum
Water/gypsum (%) Density (g/cm3) Setting time (min) Theoretical flexural strength (MPa) Theoretical compressive strength (MPa)
50 1.34 6 7.33 17.26
60 1.20 10 5.77 13.41
70 1.10 13 4.54 10.37
80 1.00 15 3.57 8.03
90 0.94 16 2.83 6.23
100 0.88 18 2.26 4.86

The durability of latex-modified and epoxy-impregnated decrease as the water/gypsum ratio is increased. The
gypsum composites was examined by determining its beha- mechanical behaviour in the descending part can be
viour in water. The mechanical strengths and water absorp- described by a mathematical function in the form of hyper-
tion values of the composites immersed in water were bola [10]. The mechanical strengths of the gypsum speci-
determined at different time periods. mens were calculated and presented in Fig. 1. The
applicability of the test data obtained for the gypsum to
the proposed function was investigated. The proposed
equation is
3. Results and discussion
y ¼ ax=ð1 þ bxÞn ð1Þ
3.1. The properties of gypsum
where a, b and n are the material parameters to be
The test results of the unmodified specimens for which determined and y and x are the mechanical properties of
the water/gypsum ratio is varied between 50% and 100% are the gypsum and water/gypsum ratio, respectively.
presented in Table 3. It is seen that the density and Using Eq. (1), it is possible to predict both compressive
mechanical strengths of the gypsum decrease and the setting and flexural strengths of the gypsum. However, several
times increase as the water/gypsum ratio is increased. The additional conditions have to be satisfied by Eq. (1) to
change of mechanical strengths as a function of water/ predict an acceptable mechanical behaviour –water/gypsum
gypsum ratio consists of two parts, i.e., ascending and ratio curve. These conditions are as follows:
descending part. In the fist part, the mechanical properties
of the gypsum increase up to water/gypsum ratio required At x = 0, y = 0
for its complete hydration. In the second part, which begins ( y; represents mechanical properties of gypsum).
from this ratio, the mechanical properties of the gypsum At x = 1, y = 0.

Fig. 1. Theoretical and experimental mechanical strengths of gypsum.

1542 A. C˛olak / Cement and Concrete Research 31 (2001) 1539–1547

Table 4
Material constant, correlation coefficients and xm values for gypsum

Mechanical Material constant Correlation

properties a b n coefficient (r2) xm (%)
Flexural strength 213.396 1.067 6.263 .98 17.8
Compressive strength 489.782 0.84 7.564 .98 18.14

The proposed equation satisfies these boundary conditions.

dy=dx ¼ 0; x ¼ xm
Fig. 3. Relation between water/gypsum ratio and latex/gypsum ratio at
where xm is the water/gypsum ratio, which gives the constant indentation (32 ± 2 mm).
maximum mechanical properties. By solving the latter
condition, the following result is obtained for the value considerably. The convenience of the mechanical properties
of xm. determined in this case with the values calculated according
xm ¼ 1=bðn1Þ ð2Þ to the proposed equation should be investigated.

As seen in the Eq. (2), xm is dependent on the material 3.2. Properties of acrylic latex-modified gypsum
parameters n and b in the proposed equation. The
nonlinear least-square method was used to calculate the The influence of the latex/gypsum ratio on the setting
material parameters in the proposed equation. The material time of latex-modified gypsum specimens with a constant
parameters, correlation coefficients and xm values found water/gypsum ratio of 50% is shown in Fig. 2. As can be
for gypsum are given in Table 4. The proposed equation seen in Fig. 2, the setting times of the composites change
proves satisfactory for defining the mechanical strengths of depending on the latex/gypsum ratio. In general, the latex
gypsum. As seen in Table 4, the correlation coefficients interferes with the hydration of gypsum and causes pro-
calculated by this equation approach one. longed setting times. This effect is more pronounced when
The water/gypsum ratios that give maximum mechanical the latex/gypsum ratio is increased. It can be seen that the
strengths according to the Eq. (2) lie between 17.8% and addition of about 15% latex increases the setting time from
18.14%. The maximum flexural strength for the gypsum approximately 6 to 54 min. Such a high extension of the
corresponds to the 17.8% water/gypsum ratio and the setting time might be due to the interaction that occurs
maximum compressive strength for the gypsum corresponds between the two systems.
to the 18.14% water/gypsum ratio. These values are very Fig. 3 shows the water/gypsum ratio required to obtain
close to the theoretical water value (18.3%) required for latex-modified plaster with similar consistency as a function
complete hydration of the calcium sulfate hemihydrate. The of the latex/gypsum ratio. For latex/gypsum ratio of 15%, a
gypsum obtains its highest mechanical properties at a reduction of about 36% in water requirement is observed.
calculated value, which is very close to the theoretical water The possibility of a significant reduction of the water/
percentage necessary for its chemical reaction. The mechan- gypsum ratio by using acrylic latex appears to offer a
ical properties corresponding to the 18.3% water/gypsum potential for producing better gypsum plaster. The main
ratio could not be determined since it is not possible to advantage of the system is its good workability and ease of
obtain a gypsum of pourable consistency using theoretical application when compared to other similar systems. How-
water quantity. However, it might be possible to produce a ever, these characteristic features of acrylic latex-modified
gypsum near to the theoretical water/gypsum ratio quantity gypsum paste are very much dependent on the admixture
dosage rate. Small amounts of polymer in gypsum paste has
little effect on workability. The addition of the polymer

Table 5
Test results for the latex-modified gypsum
Water/ Latex/ Density Porosity Flexural Compressive
gypsum (%) gypsum (%) (g/cm3) (%) strength (MPa) strength (MPa)
50 0 1.35 31.3 8.8 16.9
50 5 1.27 30.6 9.0 16.2
40 0 1.53 25.9 10.8 24.4
40 5 1.41 24.9 10.7 25.0
40 10 1.36 22.0 11.7 20.3
Fig. 2. The setting times of latex-modified gypsum with a constant water/
35 10 1.41 19.4 12.6 24.6
gypsum ratio of 50%.
 A. C˛olak / Cement and Concrete Research 31 (2001) 1539–1547 1543

Fig. 4. Effect of water immersion on the water absorption of composites.

begins to have a significant effect when its content exceeds of the fresh mix, but also it is capable of exerting a
approximately 5%. Additions of the polymer between 5% substantial influence on the flexural strength of the har-
and 10% by weight of gypsum dramatically reduce the dened composite.
water demand when compared to gypsum without acrylic The relationships between mechanical strengths and
latex. The decrease of water requirement may arise from latex content at different water/gypsum ratios are given
the decrease in the quantity of gypsum and also from the in Table 5. The flexural strength of latex-modified gyp-
lubricating effect of polymer particles in the latex. Higher sum specimens with a water/gypsum ratio of 40% shows
proportions of the polymer usually between 10% and 15% a minimum at 5% latex content. It subsequently increases
by weight of gypsum modify further the properties of the with further increase in latex content to 10%. The water/
mix. The results show that not only does the increase in gypsum ratio is kept constant for these specimens. There-
the quantity of polymer strongly improve the workability fore, this parameter can not be regarded as the reason for

Fig. 5. Effect of water immersion on the flexural strength of composites.

1544 A. C˛olak / Cement and Concrete Research 31 (2001) 1539–1547

Fig. 6. Effect of water immersion on the compressive strength of composites.

strength improvement in the latex-modified gypsum [11]. The effect of latex addition on the compressive strength
The volume fraction porosities measured for the unmodi- becomes remarkable at high latex/gypsum ratio. In consid-
fied and modified gypsum specimens with a water/gyp- ering the results obtained at constant water/gypsum ratios, it
sum ratio of 40% are approximately constant with is found that latex-modified gypsum specimens with latex
0.22  p  0.26 where p is the volume fraction of poros- content of 5% have compressive values strength very close
ity. As a result, the increase in the flexural strength may to unmodified ones. Latex addition of 10% causes a reduc-
be ascribed to the presence of latex in these samples and tion of about 17% in compressive strength when compared
not to a reduction in porosities. However, it can be seen with unmodified gypsum with a water/gypsum ratio of 40%.
from Table 5 that the flexural strength of the composites The decrease in strength is due to the high content of the
increases with decreasing water/gypsum ratio and reaches soft polymeric material in the stiff gypsum matrix [13].
a maximum value at 35% water/gypsum ratio. These However, decreasing the water/gypsum ratio from 40% to
findings clearly indicate that two mechanisms, i.e., the 35% positively influences the compressive behaviour of
reduction in water content and the strengthening effect of latex-modified gypsum. The compressive strength of these
the latex, will be responsible for the improvement of the specimens is quite close to that of unmodified gypsum with
strength of latex-modified gypsum [12]. a water/gypsum ratio of 40%. Table 5 gives also the

Fig. 7. Effect of gypsum quantity and viscosity of epoxy on penetration depth.

 A. C˛olak / Cement and Concrete Research 31 (2001) 1539–1547 1545

Table 6
Properties of epoxy-impregnated gypsum with a surface coating of epoxy
Splitting tensile Splitting tensile
Epoxy Water/ Thickness of Penetration depth strength of impregnated strength of unimpregnated
system gypsum (%) surface coating (mm) from surface (mm) gypsum (MPa) gypsum (MPa)
EP1 50 0.5 1.0 4.68 4.63
EP1 70 1.0 2.2 3.00 2.93
EP1 100 0.7 3.5 2.11 1.68
EP2 50 0.6 0.6 4.65
EP2 70 0.8 1.3 2.97
EP2 100 1.0 2.0 1.72

relationships between the density and the latex content. The to rapid loss of flexural and compressive strength at all latex
decrease is due to air entrainment caused by the surfactant in contents. This is due to potentially adverse effects of water
the latex [14]. on the polymer phase in latex-modified gypsum composite.

3.3. Effect of water on the properties of 3.4. Properties of epoxy-impregnated gypsum

latex-modified gypsum
Fig. 7 shows the change of epoxy impregnation depth and
The effect of immersion in water on the water absorption rate with time. The curves are similar in shape, with the rate
and mechanical strengths of the latex-modified gypsum declining with increased penetration. The decrease in the rate
composites is shown in Figs. 4 –6. The results obtained at of epoxy penetration into hardened gypsum may be the result
constant water/gypsum ratios indicate that the water absorp- of the viscosity of the impregnant to increase with time due to
tion values of the latex-modified gypsum composites are polymerisation [15]. It can be seen that the penetration depth
about the same as those of unmodified ones (see Fig. 4). It and rate depend on the viscosity of epoxy and the gypsum
can be seen from Figs. 5 and 6 that the flexural and quantity. The depth of epoxy penetration into hardened
compressive strength of latex-modified gypsum are much gypsum varies between 0.6 and 3.5 mm. Since the impreg-
lower than that of unmodified gypsum composite. The nated zone is only a small proportion of the cross-section of
results show that after 7 days immersion in water, the the sample, the tensile-splitting strengths of the epoxy-
unmodified gypsum with a water/gypsum ratio of 40% impregnated gypsum do not significantly increase compared
retains 50% of the original strength, whereas the latex- to the unimpregnated gypsum specimens [16]. The experi-
modified gypsum composites retains only 30% of the mental results in Table 6 show only a 25% increase in tensile-
original strength. In general, immersion in 20
C water leads splitting strength at about 3.5 mm epoxy penetration depth.

Fig. 8. Effect of water immersion on the water absorption of composites with epoxy impregnation.
1546 A. C˛olak / Cement and Concrete Research 31 (2001) 1539–1547

Fig. 9. Effect of water immersion on the splitting tensile strength of composites with epoxy impregnation.

3.5. Effect of water on the properties of 2. The addition of acrylic latex to gypsum allows a
epoxy-impregnated gypsum remarkable reduction in the water/gypsum ratio.
3. The water absorption values of the latex-modified
Figs. 8 and 9 show the results of water absorptions gypsum composites are about the same as those of unmo-
and splitting tensile strength of unimpregnated and epoxy- dified ones. However, the water absorption of the compo-
impregnated gypsum after different periods of immersion sites is decreased with a reduction in water/gypsum ratio.
in 20
C water. EP1 epoxy-impregnated gypsum compo- 4. About 5% latex addition does not lead to increase in
sites show water absorption values approximately equal to flexural strength compared to unmodified gypsum. How-
zero. No change in splitting tensile strength of the ever, increase in polymer content from 5% to 10% causes a
composite with time could be detected. The results show significant improvements in flexural behaviour. Decreasing
that after 7 days of immersion in water, the composites the water content from 40% to 35% positively influences the
retain 100% of their original strengths. These findings mechanical behaviour of latex-modified gypsum and leads
clearly indicate that EP1 epoxy formualtion forms on the to 43% increase in flexural strength compared to unmodi-
gypsum a continuous and resistant protective layer, which, fied gypsum with a water/gypsum ratio of 50%.
at least for 7 days, prevents the penetration of water. The 5. The depths of penetration of EP1 and EP2 systems
increase in epoxy coating thickness from 0.5 to 1 mm epoxy resins into the gypsum are found to vary between
does not influence the shielding function of EP1 epoxy 0.6 and 3.5 mm. The increase in viscosity of epoxy resin
formulation against the diffusion of water. EP2 epoxy during the first 30 min does not support a good penetra-
formulation seems to act in a different manner; it is tion behaviour.
effective in reducing the speed of water entry but does 6. Epoxy impregnation does not lead to a significant
not provide a water-tight barrier. Mechanical damage increase in tensile-splitting strength.
occurs with the ingress of water into gypsum. 7. EP1 epoxy-impregnated gypsum composites show
The unimpregnated gypsum shows water absorption water absorption values approximately equal to zero at the
values higher than 67%. After 7 days of immersion in end of 7 days of water immersion, whereas the water
water, their tensile-splitting strengths decrease, with absorption of the EP2 epoxy-impregnated gypsum compo-
approximately 15% original strength being retained at all sites tends to increase in time because of the slow ingress of
water/gypsum ratios. water into gypsum.
8. Immersion in 20
C water does not influence the
durability performance of the EP1 epoxy-impregnated gyp-
4. Conclusions sum with a surface coating of epoxy. After 7 days of
immersion in water, the composites retain 100% of the
The following conclusions can be drawn from this original strength. The protection offered by EP1 epoxy
experimental investigation: system may be lost after a long-term period of water immer-
1. The acrylic latex in the form of a water-based sion. A potential solution to this problem is the evaluation of
suspension at high dosages tends to retard the hydration the product for a long-term period under natural aging
process. The effects show mainly as increased setting times. conditions. However, the length of testing time may not be
 A. C˛olak / Cement and Concrete Research 31 (2001) 1539–1547 1547

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