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Materials Science Forum Vol 689 (2011) pp 336-342 Online: 2011-06-10

(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.689.336

Evaluation of the Properties of Polyaspartic Polyurea Coated Concrete


Subjected to the Co-action of Freeze-Thaw Cycles and NaCl Solution
Immersion
HUANG Weibo, LIU Xudong*, LU Ping, ZHANG Jing
Research Institute of Functional Materials, Qingdao Technological University,
Qingdao, CHINA, 266033
*Corresponding author: POB No.111, 11 Fushun Road, Qingdao, CHINA
E-mail:spua@163.com, *liu.xu.dong-123@163.com, lvping-qd@163.com, jing861014@sohu.com

Keywords: Coated concrete; Polyaspartic polyurea; Co-action of freeze-thaw cycles-NaCl solution


immersion; Adhesion; Chloride ion diffusion.

Abstract.The deterioration of coated concrete subjected to co-action of freeze-thaw cycles-NaCl


solution immersion double factors exposure was investigated in this study. Adhesion, chloride
content and resistance of chloride ion diffusivity of two types of polyaspartic ester polyurea coated
concrete were analyzed. Test results showed that the adhesion of QF-1 (PAE-b-H12MDI prepolymer
H66) and QF-2 (PAE-b-H12MDI prepolymer H62) coated concrete reduced about 5% respectively
which kept excellent under the double factors exposure after 200, 300 days and 25, 50 times of
cycles. The degradation process of coated concrete simultaneously exposed to co-action exposure
was significantly accelerated. In co-action exposure tests, the average chloride ion content of coated
concrete increased about 33% and 87% after 25 and 50 times of cycles compared with single NaCl
solution immersion exposure; the chloride ion diffusion coefficient of concrete substrate increased
with the increase of exposure time and freeze-thaw cycles. Freeze-thaw cycles results showed a
severe influence on chloride ion diffusion and permeation of surface protection coating of concrete.
Research also showed that the chloride ion diffusion of coated concrete subjected to the co-action of
freeze-thaw cycles-NaCl solution was coincided with the Ficks second law.

Introduction
Most of concrete structures are subjected to the co-action of environmental corrosion. It has been
found that the deterioration of concrete could be accelerated when subjected to dual-damaging
processes, e.g., simultaneously subjected to both freezethaw cycling and salt immersion. New kind
of coating protection technique was considered as the most effective method for improving the
durability of concrete [1-2]. Thus, the co-action of environmental corrosion and protective surface
organic coatings have become the most striking study of durability of concrete structures [3].
One of the most common causes of concrete deterioration is the ingress of chloride ions through
the concrete pore network when the concrete is subjected in severe environments; The preparation
of new protective coating materials and investigations of high performance coating techniques are
significant since coating protection becomes the primarily and available method for the protection
of concrete [4]. Polyurea is a class of excellent performance protective coating. Adhesion is a
significant factor affecting performance of protective coating, which should tightly bond to the
concrete substrate to provide long-term protection against corrosive environments. This paper
thoroughly analyses the adhesion, chlorine ion content and chloride diffusion coefficient of two
kinds of polyaspartic ester (PAE) polyureas coated concrete, QF-1(PAE-b-H12MDI prepolymer
H66) coated concrete, QF-2 (PAE-f-H12MDI prepolymer H62) coated concrete, all of concrete
specimens are subjected to the NaCl immersion acceleration exposure and the co-action of freeze-
thaw cycles and NaCl solution immersion, this paper gives a comparative study on linear PAE
polyurea coated concrete performance influence law under the NaCl immersion exposure and the
co-action of load-NaCl solution immersion double factors exposure and provides a new method and
a new thinking for concrete protective coating research.

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Materials Science Forum Vol. 689 337

Experiment
Materials.Preparation and characterization of coating system.The surface protective coating
systems used in this study were polyarspatic polyurea, amine terminated polyether Jeffamine D2000
and HDI trimer were purchased from Huntsman, Bis(4-isocyanatocyclohexyl)methane (H12MDI)
was kindly provided by Du Pond. Prepolymer and chain exdenter were prepared in laboratory, the
input material composition and synthesized result of H prepolymer are given in Table 1, two kinds
of polyaspartic polyurea coatings are given in Table 2.

Table 1 Input material composition and synthesized result of H prepolymer


Sample H12MDI/g JeffamineD2000/g H12MDI /D2000/mol ratio NCO/%
H1 131 204 1:0.204 9.8
H2 131 65 1:0.065 20.2

Table 2 Input material composition of polyaspartic polyurea


Sample PAE-b/H prepolymer /D2000/mol ratio PAE-b/mol H.S/% NCO index
QF-1 1.00/1.58/0 1.00 66 1.05
Sample PAE-f /H prepolymer /mol ratio PAE-f/mol H.S/% NCO index
QF-2 1.00/1.58 1.00 62 1.05
prepolymer H2 is used, NCO%=20.2%

prepolymer H1 is used, NCO%=9.8%

H.S is hard segment content

Preparation and characterization of concrete mixesThe concrete cubes (100100100mm)


specimens were demoulded from a steel mould, the concrete mix was made according to
GB/T14902-2003[5].Mix proportions for the concretes are given in Table 3.The 28d average
compressive strength of QF-1 and QF-2 was 56 MPa and 45.3 MPa respectively.

Table 3 Mix proportioning of concrete in kg/m3


Mix proportioning(kg/m3)
Sample Coarse aggregate Fine aggregate
W/C Cement Water Superplasticizer
No.1 No.2 Sand Crushed sand
QF-1 0.45 405.4 182.4 536.2 591.6 516.3 184.2 3.04
QF-2 0.45 399.6 179.8 527.5 582.0 507.9 181.2 3.00

Preparation of coated concrete.Prior to apply surface coating, the surface of cured concrete
cubes should be polished cleanly and smoothly. The coating system application contented prime
brushing, putty scratching, polyurea spraying and topcoat spraying, all concrete should be cured for
7 days under standard condition after repaired by cement mortar, kept in naturally air-dried for 48
hours, and then spraying QF-1 and QF-2 polyaspartic polyurea coatings respectively. The thickness
was determined by ultrasonic thickness gauge after cured for 48 hours. The coated concretes were
prepared according to Ref. [6, 7].
Testing program.Exposure conditions.An accelerated freeze-thaw testing procedure was
developed whereby the specimens were simultaneously subjected to 10% NaCl content solution in a
specially designed environmental chamber. All specimens were immerged in NaCl solution for 4
hours prior to freeze-thaw cycles and the NaCl solution should be supplied at regular intervals to
keep the solution level consistent during the test process and stored for later analysis. The exposure
periods were 90d, 150days, 200days and 300days respectively. The freeze-thaw tests were based on
338 Materials Modeling, Simulation, and Characterization

the recommendation in GBJ82-85 for coated plain concrete and the freeze-thaw cycles were 25 and
50 times respectively, the exposure periods were 90days, 150days, 200days and 300days.
Chloride ion diffusion test.The chloride ion diffusivities of coated concrete specimens, which
were both exposed to F-T cycles and not, were investigated in accordance with ASTM C 1202
Standard Test Method for Electrical Indication of Concrete s Ability to Resist Chloride Ion
Penetration testing procedure [8]. In this research the quantitative measurement technique on
chloride ion diffusivity developed by Luping et al. [9] was used. They have successfully suggested
effective diffusion coefficient of chloride ions in concrete is given by:
C 2C
= Dc 2 (1)
t x
where x is the distance from the concrete surface (mm), Dc is the coefficient of chloride diffusivity
(m2/s) and c is the surface chloride ions concentration when the penetration depth is x(%), and t is
exposure time (h).
Where initial condition and boundary condition are C ( x = 0 , t ) = Cs, 0 < t < ; C (x , t = 0) =
C0, 0 < x < , the equation are as follows:
x
C ( x , t ) = C s (C s C i ) erf (2)
2 D t
c
where C (x, t) is the surface chloride ions concentration when the penetration depth is x (%), Cs is
the surface chloride ions concentration (%), Ci is the initial chloride ions concentration of concrete
(%) (In this test, if no chloride additives, Ci is 0), and t is exposure time (h).
In order to measure penetration depth of chloride ions, specimens after test were split-tensioned
and 0.1 N AgNO3 and 0.1% sodium fluorescein solutions were sprayed on fractured surface of the
specimen. The 0.1% sodium fluorescein solution was used to clarify the differences between color
of concrete and color of AgCl. At the chloride penetrated area, silver ions reacts with chloride ions
and changes into whitish color. The equation chloride ions content in concrete is shown as follows:
C ( AgNO3 ) (V1 V2 ) 0.03545
WCl = 100 (3)
m s 50.00 / 250.0
where WCl is chloride ions mass percentage in concrete(%), C (AgNO3)-AgNO3 standard solution
substance concentration(mol/l),V1 is the amount of AgNO3 standard solution substance (ml),V2 is
the amount of AgNO3 standard solution substance in blank test (ml), 0.03545 is chloride ions milli
mole mass (g/mmol), ms is the quality of concrete samples (g).
Adhesion test.The pull-off tests [10] were used to determine the bonding strength of coatings to
concrete according to ASTM D4541-02.
Thickness of dry film test.Thickness of dry film was tested by non-breakage law according to
ASTM D 6132 [11].

Results and discussions


Adhesion results.The adhesive tests results of QF-1 and QF-2 coated concretes subjected to 10%
NaCl solution immersion and the co-action of freeze-thaw cycles-10% NaCl solution immersion
double factors exposure (25, 50 cycles respectively) for blank test, 200d and 300d were shown in
Fig.1.
It is observed that the adhesion of QF-1 and QF-2 were about 2.4 MPa and 2.0 MPa respectively
before exposure, the adhesion of QF-1 reduced approximately 3.3 % and 7.1 % after 25 freeze-thaw
cycles and 200d exposure, and it was further decreased by 2.9 % and 4.9 % after 50 freeze-thaw
cycles and 300d exposure. As for QF-2 coating, it showed a lower decreased rate and kept a good
adhesion after the co-action of two double factors exposure. After each test, the failure surface was
examined to identify the failure plane. Observations of the separated coating indicated that failure
occurred within the thin interface region close to the concrete surface where the primer impregnates
the concrete.
Materials Science Forum Vol. 689 339

The coated concrete was not only suffered to the corrosive substance invasion but also the
freeze-thaw cycles and it played a significant difference compared with single immersion exposure
only, the damage extent is increased and the damage rate accelerated, also. The protective
performance of coating decreases due to developing internal micro cracks caused by freeze-thaw
attack as concrete specimen is exposed to freeze-thaw cycles. The coated concrete interface
produced tensile after freeze-thaw cycles which damaged the adhesion of the coating and the
damage degree was related to the coating flexibility. QF-2 coating extended by PAE-f soft chain
extender showed high elasticity, so the adhesion damage was lower than QF-1 coating.

Fig. 1 Adhesion of QF-1 and QF-2 coated concrete before and


after the co-action freeze-thaw cycles-NaCl exposure

Influences to the Content of Chloride.Fig. 2 showed the chloride ion content of QF-2 coated
concrete at a penetration depth of 5mm to concrete surface. The thickness of polyaspartic polyurea
coating is 402m in Fig. 2a, in Fig. 2b, the thickness is 302 m.
Analysis of the results directly revealed the chloride content influenced by the co-action of
freeze-thaw cycles-NaCl exposure compared with single NaCl solution exposure. In Fig.2, QF-2-N,
QF-2-NF25 and QF-2-NF50 denoted separately before freeze-thaw cycles, 25 freeze-thaw cycles
and 50 freeze-thaw cycles, the immersion time is 90d, 150d, 200d and 300d respectively. The
average content of chloride was increased by 4.3% and 10% after 25 and 50 freeze-thaw cycles
when subjected to the co-action of freeze-thaw cycles-NaCl solution immersion compared with
single NaCl solution immersion exposure.

0.05 0.05
90d 90d
Chloride Content /%

150d 150d
Chloride Content /%

0.04 0.04
200d 200d
300d 300d
0.03 0.03

0.02 0.02

0.01 0.01

0.00 0.00
QF2-N QF2-NF25 QF2-NF50 QF2-N QF2-NF25 QF2-NF50

(a) coating thickness is 402m (b) coating thickness is 302m


Fig.2 Chloride concentration of QF-2 coated concrete subjected to the co-action freeze-thaw cycles-
NaCl exposure at a penetration depth of 5mm to concrete surface
340 Materials Modeling, Simulation, and Characterization

The thickness of protective coating to concrete can also influence the chloride permeation
content, Fig.2b presents correspondence freeze-thaw cycles-NaCl exposure test while coating
thickness is 302m. The average content of chloride was increased by 33% and 87% after 25 and
50 freeze-thaw cycles when subjected to the co-action of freeze-thaw cycles-NaCl solution
immersion compared with single NaCl solution immersion exposure. It should be noted that the
chloride content increased with the decreasing of coating thickness.
Fig.3 showed the distributive rules of chlorine ion of QF-2 coating at different depth in coated
concrete when subjected to the co-action of freeze-thaw cycles-NaCl solution exposure. In Fig.3,
QF-2-N, QF-2-NF25 and QF-2-NF50 denoted separately before freeze-thaw cycles, 25 freeze-thaw
cycles and 50 freeze-thaw cycles, the immersion time is 90d and 300d respectively. The thickness
of polyaspartic polyurea coating is 402m.

0.50 QF2-N-90 0.50 QF2-N-300


Chloride Content /%

Chloride Content /%
QF2-FT25-90 QF2-FT25-300
QF2-FT50-90 QF2-FT50-300

0.25 0.25

0.00 0.00
0.004 0.006 0.008 0.010 0.012 0.004 0.006 0.008 0.010 0.012

Depth/mm Depth/mm

(a) test period is 90 days (b) test period is 300 days


Fig.3 Chloride concentration profile with depth for QF-2 coated concrete subjected to the co-action
of freeze-thaw cycles-NaCl solution exposure

It is obviously obtained that the average content of chloride was increased under the co-action of
freeze-thaw cycles-NaCl solution immersion compared with NaCl solution exposure from Fig.3.
Fig.3a showed that the decrease trend of average chloride content varied with the depth of
penetration from the concrete surface, and there existed a turning point in the decrease curve of the
chloride ion content at the same time, the turning-point appeared when the penetration depth of
concrete was approximately 0.005mm; when the depth was less than 0.005, the average chloride
content was decreased rapidly then exhibited a slight decline. The results also indicate a consistent
decrease in freeze-thaw cycles with an increase in the number of freeze-thaw cycles. Comparing
absolute magnitudes can be misleading as is evident from the specimens used for 50 freeze-thaw
cycles. Similar behavior was obtained from all specimens tested. A study of similar experimental
phenomena was appeared in Fig.3b. In addition, the content of chloride increased greatly with the
increasing of exposure time, which was consistent to the result studied in reference [12-13].
Furthermore, at the same penetration depth in concrete, the average chloride content of 50
freeze-thaw cycles was significantly higher than that of 25 freeze-thaw cycles. Even thought all
coated concrete specimens showed an excellent chlorine anion penetration resistance, it might be
due to high elasticity and compaction densities of polyaspartic polyurea coating in micro-structural
development between concretes incorporating surface protective coating. From Fig.3b, for instance,
at the same penetration depth of 0.003, the average chloride content of coated concrete were
0.4497%, 0.4795% and 0.5815% at 0, 25 and 50 freeze-thaw cycles respectively. This phenomenon
was observed irrespective of both conditions before and after freeze-thaw cycles. The particle
packing effect (micro filling effect) and a development of additional barrier for particles effect
caused by surface coating system would be also responsible for reducing the diffusion coefficient to
block the path for chloride ion.
The increase of the content of chloride was due to the co-actions of acceleration chloride ion
diffusion and permeation velocity in concrete subjected simultaneous to the action of freeze-thaw
cycles and concrete damage generated by increasing micro-crack in tensile area.
Materials Science Forum Vol. 689 341

Coefficient of chloride ion diffusivity.The exposed samples were tested after 30, 90, 150, 200
and 300days of exposure to chloride, the coating thickness is 402m. Table 1 shows the corrected
chloride concentration percentage and the chloride diffusion coefficient Dc (in terms of cement
mass) for 30, 90, 150, 200 and 300days of exposure respectively. It is observed that the chloride
concentration of concrete substrates is consistently higher than that of QF-1 and QF-2 coated
concrete. The diffusion coefficients (Dc) for both concrete types at different ages of exposure were
determined in accordance with the Eq.[1~3].
It can be seen from Table 1 that the chloride diffusion coefficient Dc of all samples decreased
with the aging time extended and the decreasing tendency was towards stability after 150d.
Therefore, the inference of the resistance of the coated system on concrete to chloride permeability
could be analyzed by investigating Dc of every group samples after 300d exposures. The Dc of
concrete substrate was 4.36710-12 m2/s after 300d exposure, but it decreased to 4.61310-14 m2/s
and 5.22710-14 m2/s respectively after 25 and 50 freeze-thaw cycles with an decrease of about
one~two order of magnitude over previously experiments. The coatings displayed a good shielding
effect to chloride diffusion. When Buenfeld N and Zhong Shiyun studied the coated concrete such
as SBR, they found that Dc of SBR, PVC and CPE coated concrete was 1.5910-11m2/s ~ 1.810-13
m2/s [14] after they had been immersed for one year in approximately 3.5% NaCl solution, which
was obviously higher than in PAE polyurea coated concrete, in other words, the chloride
penetration resistance of PAE polyurea coated concrete was superior to SBR, PVC, CPE etc. coated
concrete mentioned above.
The generation of the tension in the cross sections of coated concrete can increase the micro-
crack and result in the coating defect or fatigue ageing subjected to the co-actions of freezethaw
cycling and solution immersion double factors exposure compared with chloride immersion
exposure independent effect, so the adhesion of coating decreases and the chloride diffusion
coefficient increases.
In addition, the Dc correlation coefficient of Table 1was higher, and it proved that the Dc was
anastomosed well with the corresponding formula, and the chloride diffusion in the linear PAE
polyurea coated concrete was coincided with the Ficks second law.

Table1 Chloride diffusion coefficient of QF-1, QF-2 coated concretes and concrete substrates
subjected to the co-action of freeze-thaw cycles-NaCl solution exposure
Surface Diffusion
correlation coefficient
Specimen concentration coefficient Characteristics
R2
[Cs/%] Dc10-12/[m2/s]
C0-N-30 1.015 10.19 0.9969
C0-N-90 0.957 7.833 0.9982
concrete
C0-N-150 1.025 6.618 0.9892
substrate
C0-N-200 1.074 5.727 0.9988
C0-N-300 1.220 4.367 0.9957
QF-1-NF25-90 6.1472 0.15931 0.9999
QF-1-NF25-150 5.6013 0.10115 0.9999 QF-1
coated
QF-1-NF25-200 6.3791 7.65910-2 0.9998 concrete
-2
QF-1-NF25-300 6.9177 4.61310 0.9997
QF-2-NF50-90 5.8970 0.16244 0.9999
QF-2-NF50-150 5.4770 0.10229 0.9998 QF-2
-2
QF-2-NF50-200 6.1668 7.78910 0.9998 coated
QF-2-NF50-300 6.6162 5.22710-2 0.9997 concrete
342 Materials Modeling, Simulation, and Characterization

Conclusions
(1) The results of the experiment of 10% NaCl solution immersion indicate that the linear PAE
polyureas QF-1, QF-2 coated concrete still have excellent wet adhesion and capability of resistance
to chloride diffusion when tested by immersion-aging after 90~300days, and the coated concrete
has excellent immersion-corrosion resistant properties.
(2) The results of the concrete samples subjected to the co-action of freezethaw cycles-NaCl
solution immersion double factors acceleration exposure indicate that QF-1 and QF-2 coatings
decrease the chloride diffusion in concrete, and the chloride diffusion coefficient keeps at
10-13~10-14m2/s in the coated concrete.
(3) The chloride diffusion in the linear PAE polyurea coated concrete is coincided with the Ficks
second law. The chloride diffusion coefficient declines with the extension of accelerated aging time.
References
[1] Mehta PK, Gerwick BC. Concrete in the service of modern world. In: Proceedings of
International Conference on Concrete in the Service of Mankind, University of Dundee,
Scotland. 1996.
[2] S.Srinvasan, N.S.Rengaswamy. Concrete corrosion and monitoring. Chemical Weekly, 1998,
43 (39):163-166.
[3] Ru Mu, Changwen Miao, Xin Luo, Wei Sun. Interaction between loading, freezethaw cycles,
and chloride salt attack of concrete with and without steel fiber reinforcement, Cement and
Concrete Research, 2002, 32(1):1061-1066.
[4] LU Ping, HUANG Wei-bo, GAO Song, CHEN Guo-hua. Study on the Properties of
Polyaspartic Polyurea Coated Concrete under Salt Fog Exposure. 3rd international conference
on concrete,2008.10,yantai, China.
[5] National Standards of CHINA GB/T 14902-2003. Ready-Mixed concrete. Beijing, 2003.12.
[6] LU Ping, CHEN Guo-hua, HUANG Wei-bo. Aliphatic Polyurea Coating Based on Novel
Polyaspartic Ester. Polymer Materials and Engineering..2007, 23(3):55-58.
[7] Lu Ping, Chen Guohua, Huang Weibo. Study on dynamic mechanical behavior of polyaspartic
polyurea. Journals in Wuhan University of Technology, 2007, 29(4): 61-63.
[8] ASTM C 1202 Standard Test Method for Electrical Indication of Concrete s Ability to Resist
Chloride Ion Penetration.
[9] LU Ping, CHEN Guohua, HUANG Weibo. Research on the morphology and properties of
polyaspartic ester polyurea with different hard segment contents. Modern Chemical
Industr,2006,26(9):28-31.
[10] ASTM Designation D4541-02, Standard Test Method for Pull-off Strength of Coatings Using
Portable Adhesion Testers, 2002.
[11] ASTM Designation D4541-02, Standard Test Method for Pull-off Strength of Coatings Using
Portable Adhesion Testers, 2002.
[12] Yu Hong-Fa, Sun wei,Ma Haiyan. Prediction model for service life of reinforced concrete
structures in salt lakes and its applications. Journal of Southeast University (Natural Science
Edition), 2002, 32(4):638-642.
[13] Buenfeld N R, Zhang J. Chloride diffusion through surface treated mortar specimens [J].
Cement and Concrete Research,1998,28(5):665-674.
[14] ZHON G Shi-yun,CHEN Zhi-yuan. Chloride Diffusing through Polymer Coated Mortar
Specimen. JOURNAL OF BUILDING MATERIALS, 2002,1(5):225-229.
Materials Modeling, Simulation, and Characterization
10.4028/www.scientific.net/MSF.689

Evaluation of the Properties of Polyaspartic Polyurea Coated Concrete Subjected to the Co-Action of
Freeze-Thaw Cycles and NaCl Solution Immersion
10.4028/www.scientific.net/MSF.689.336

DOI References
[3] Ru Mu, Changwen Miao, Xin Luo, Wei Sun. Interaction between loading, freezethaw cycles, and
chloride salt attack of concrete with and without steel fiber reinforcement, Cement and Concrete Research,
2002, 32(1): 1061-1066.
doi:10.1016/S0008-8846(02)00746-9
[13] Buenfeld N R, Zhang J. Chloride diffusion through surface treated mortar specimens [J]. Cement and
Concrete Research, 1998, 28(5): 665-674.
doi:10.1016/S0008-8846(98)00031-3