Accepted Manuscript

Effects of inorganic surface treatment on water permeability of cement-based

materials

Lufeng Jia, Caijun Shi, Xiaoying Pan, Jiake Zhang, Linmei Wu

PII: S0958-9465(16)30001-4
DOI: 10.1016/j.cemconcomp.2016.01.002
Reference: CECO 2591

To appear in: Cement and Concrete Composites

Received Date: 31 January 2015

Revised Date: 22 November 2015
Accepted Date: 1 January 2016

Please cite this article as: L. Jia, C. Shi, X. Pan, J. Zhang, L. Wu, Effects of inorganic surface treatment
on water permeability of cement-based materials, Cement and Concrete Composites (2016), doi:
10.1016/j.cemconcomp.2016.01.002.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT
1 Effects of inorganic surface treatment on water permeability of cement-
2 based materials
3

4 Lufeng Jia1, Caijun Shi1∗, Xiaoying Pan1, Jiake Zhang1, Linmei Wu1
5
1
6 College of Civil Engineering, Hunan University, Changsha, Hunan, 410082, China

PT
7
8 Abstract: The permeability of the cement-based materials can be used as an important

RI
9 indicator of their durability. Surface treatment is a simple way to reduce permeability and
10 improve durability of cement-based materials. This paper studied the effects of fluosilicate

SC
11 and sodium silicate surface treatments on the permeability of cement-based materials using
12 the Autoclam water permeability and water absorption testing method. The experimental

U
13 results showed that both fluosilicate and sodium silicate surface treatments could effectively
14 reduce the permeability of cement-based materials. However, fluosilicate worked within the
AN
15 first 28days after treatment, while sodium silicate showed more obvious effect at later ages.
16 Autoclam water permeability index exhibited an exponential relationship with the water
M

17 absorption of the cement-based materials. In addition, mercury intrusion porosimetry result

18 suggested that these inorganic surface treatment agents could reduce the porosity of surface
D

19 layer of cement-based materials.

20
TE

21
22 Keywords: Surface treatment; Magnesium fluosilicate; Sodium silicate; Sodium fluosilicate;
EP

23 Water absorption; Permeability

24
C

25
AC

∗Corresponding author. Tel./fax: +86 731 8882 3937.

E-mail address: cshi@hnu.edu.cn (C. Shi)

1
 ACCEPTED MANUSCRIPT
26 1. Introduction

27 The permeability of concrete affects the transport of gases, liquids, and ions through it
28 under gradient of pressure, chemical potential, or electric potential [1, 2]. Since many
29 aggressive substances can transport by water, water permeability is a key property of concrete
30 governing its long-term durability [3-8].

PT
31 Many methods, such as reducing water to binder ratio and adding mineral admixtures
32 etc., are often used for decreasing the permeability of concrete by reducing its porosity [9].
33 However, these methods often cannot be used for existing concrete structures. Compared with

RI
34 reducing water to binder ratio and adding mineral admixtures, protective surface treatment
35 wins favor in that it does not interrupt construction work, and is hence cost-effective [10, 11].

SC
36 Surface treatment has been proven to be effective in limiting water penetration [12, 13]. In
37 very aggressive environments, they also can dramatically reduce the material degradation and

U
38 steel corrosion which affect strength and stability of concrete structures [14, 15]. In addition,
AN
39 some surface treatment agents can also extended service life of cracked concrete, while
40 admixtures cannot prevent ingress of aggressive substances in cracked concrete [10, 14].
41 Concrete surface treatment shares at least one of two objectives: to make the concrete cover
M

42 zone less permeable to aggressive substances or to reduce its moisture content and thereby to
43 increase the concrete resistivity with appropriate barrier characteristics. Both effects can
D

44 increase the service life of the structures [17].

TE

45 Surface treatment agents can be classified into inorganic and organic categories. The
46 organic treatments do not react with the concrete substrate, but create a physical barrier
EP

47 against the ingress of aggressive substances. The service life of organic treatment agents
48 depend largely on their adhesive ability with the concrete substrate and resistance of
49 weathering. There were many encouraging results demonstrated their good performance, but
C

50 they still showed some drawbacks. Acrylic coatings could significantly reduce the
AC

51 permeability of concrete [18]. However, its poor resistance to chloride ion penetration limits
52 its application in the marine structures [19, 20]. The resistance of organic sealers to aging is
53 so poor that they cannot be used in long-life structures such as dams and bridges. Though the
54 silane performs well in reducing the permeability of concrete, it is difficult to ensure its
55 longevity. Some organic treatment agents have poor fire resistance, possibly leading to
56 cracking and detachment, limited service life and hard to remove after losing effectiveness
57 [21, 22].

2
 ACCEPTED MANUSCRIPT
58 The inorganic surface treatment agents are mainly aqueous solutions of sodium silicate,
59 also known as “waterglass”, and, to a much lower extent, potassium silicates and fluosilicates
60 [23]. These silicates are one of pore-blocking treatments which react with cement paste
61 forming calcium silicate hydrate (C–S–H) gel, and increase hardness and impermeability of
62 concrete surface layer [23]. However, the published results on the effect of sodium silicate
63 surface treatment are very limited [10]. Some results [10] show that sodium silicate hardly

PT
64 penetrates into concrete substrate and is quite ineffective in preventing water absorption and
65 chloride penetration. Furthermore, waterglass may increase the risk of alkali-silica reaction

RI
66 due to the increase of alkali content. Others reported that it performed well in preventing
67 water adsorption and resisting of carbonation [24]. Kagi showed that its performance could be

SC
68 significantly improved by post-treatment with cationic surfactants (alkylquaternary
69 ammonium salts) [25].
70 This paper investigated the effects of fluosilicate and silicate surface treatments on water

U
71 permeability of concrete using Autoclam method and water absorption. Mercury intrusion
AN
72 porosimetry (MIP) was also used to investigate the porosity of concrete surface layer after
73 surface treatments. The purpose was to examine the effectiveness of those inorganic surface
M

74 treatment agents, and the interactions between those surface treatment agents and concrete.

75 2. Raw materials and testing methods

D

76 2.1. Materials
TE

77 P• 52.5 Portland cement with a specific surface area of 336 m2/kg, and an ignition loss
78 of 2.49% was used. It gave compressive strength of 26.6MPa at 3 days and 57.3MPa at 28
EP

79 days. Its chemical composition is shown in Table 1. Medium size sand and gravel from Xiang
80 River, Hunan, China, after sieving with 40mm sieve were used as fine and coarse aggregates.
C

81 An industrial grade waterglass with modulus (n) of 3 was used. NaOH was added to the
AC

82 waterglass to obtain a solution with modulus of 2. Their physical and chemical properties are
83 shown in Table 2. Waterglass N2 and N3 and water were mixed in a mass ratio of 1:4 to
84 obtain waterglass solutions for surface treatment.
85 Because sodium fluosilicate is often used as an accelerator of waterglass, three sodium
86 fluosilicate solutions with concentrations of 1%, 2% and 3% were used for pretreatment to
87 enhance the efficiency of waterglass treatment. Magnesium fluorosilicate solutions with
88 concentrations of 10%, 20%, and 30% were prepared and used as surface treatment agents.

3
 ACCEPTED MANUSCRIPT
89 2.2. Mixture proportions and preparation of specimens
90 The mixture proportion of the concrete is given in Table 3. The concrete mixture was
91 prepared in the laboratory using a 60L mixer. Cylinders of Φ110mm×100mm were cast for
92 water absorption testing (three cylinders/group), slabs of 300×230×75mm were cast for water
93 permeability testing (one slab/group). Mortar with the same mixing ratio of cement, sand and
94 water was casted in Φ110mm×100mm PVC pipes for porosity measurement. All the molds

PT
95 with specimens were compacted using a vibration table, then covered with plastic films and
96 placed in a lab room at T=20±1 for 24 h. Then concrete specimens were demolded and

RI
97 cured in a moist curing room at T=20±1 and RH≥98%, while the mortar specimens were
98 cured with the mold in same environment. The mortar samples could not be demolded until

SC
99 surface treatment, because the molds could prevent treatment agent from penetrating into
100 lateral faces during treatment.

U
101 2.3. Surface treatments
AN
102 After 6 days of curing in the curing room, cylinder specimens were cut into 50mm length
103 from the middle. Then all the concrete specimens were placed in an environment of
104 T=20±2°C, RH = 55 ± 5% for 24h before surface treatment to ensure that moisture condition
M

105 of the specimen surface was dry as recommended in the publication [25]. The treatment
106 methods are summarized in Table 4. The top side of concrete slabs, all faces of concrete
D

107 cylinders would be treated, while the treatment agents was only applied on top face of mortar
TE

108 cylinders. From groups 1-2 to 1-6, the treated faces were brushed with surface treatment
109 agents using a nylon brush every two hours for four times according to Table 4. In term of
EP

110 groups 1-7 to 1-12, the treated faces were brushed with sodium fluosilicate every two hours
111 for four times. After 24 hours, the waterglass treatment agents were applied on the treated
112 surface for 4 times. After treatment, they were put back into the curing room T=20±1 and
C

113 RH≥98% until testing ages.

AC

114 2.4. Testing methods

115 2.4.1. Water permeability

116 Concrete slabs were placed in laboratory at T = 20 ± 2 ° C and RH = 55 ± 5% for 24
117 hours before Autoclam permeability measurement which is quite sensitive to moisture
118 condition [26]. The water permeability indexes were measured 14d, 28d and 56d after surface
119 treatment. It took about 5 minutes for the concrete samples to achieve saturation and for the

4
 ACCEPTED MANUSCRIPT
120 instrument to reach a steady state [27]. Thus only data between 5th and 15th minutes were
121 recorded. Criteria of water permeability are shown in Table 5 [28].

122 2.4.2. Water absorption test

123 The water absorption were measured at 0d, 14d, 28d and 56d after surface treatment. The
124 0 day measurements were tested immediately after surface treatment. Concrete specimens of
125 Φ110mm×50mm were first vacuumed for 4 hours, and then immersed in saturated calcium

PT
126 hydroxide solution for 24 hours. After wiping the surface water, the mass (m1) of specimens
127 were measured under surface-dry condition, then the samples were dried in an oven at 105

RI
128 until constant mass (m2). The water absorption of the specimen can be calculated as following
129 equation. The means of three specimens were presented in the results.

SC
130

131 2.4.3. Pore structure

U
AN
132 The mortar specimens were cut into thin-disc about 5mm of thickness below the treated
133 surface 56d after treatment. The discs were crushed into fragments about 0.5 cm size by a
M

134 plier. The small fragments were immersed in anhydrous ethanol at least 7d to stop further
135 hydration, then dried in an oven at 60 for 24h. Pore structure of the dried mortar samples
D

136 were measured by means of mercury intrusion porosimetry (MIP). The contact angle was
137 assumed as 140º, and surface tension 106.7 psi-µm.
TE

138 3. Result and discussion

EP

139 3.1. Water permeability index of concrete from Autoclam method

140 The regression analysis results showed that there was a linear relationship between the
C

141 quantity of water entering the untreated concrete and the square root of time, as shown in Fig.
AC

142 1. The slope of line was defined as water permeability index of concrete [29]. The
143 permeability indexes decreased with sample age, because of the continuous hydration of
144 cement and generation of C-S-H gel which could fill the pore space [30]. Because setting and
145 hardening of cement occurs mainly at early ages, the reduction in permeability coefficient was
146 more obvious before 28d.

5
 ACCEPTED MANUSCRIPT
147 3.1.1. Effect of magnesium fluosilicate treatment on water permeability index
148 The permeability index of concrete treated with magnesium fluosilicate is plotted in Fig.
149 2. It could be seen that permeability indexes were reduced after magnesium fluosilicate
150 surface treatment. Compared with untreated concrete, the permeability indexes were reduced
151 by 32, 44, and 53% after treatment with 10, 20, and 30% magnesium fluorosilicate solutions
152 at 56d. Magnesium fluorosilicate could penetrate into concrete after brushing, react with

PT
153 calcium hydroxide, and form insoluble silica gel which acted as a micro-filler and resulted in
154 a less porous and permeable micro-structure [9]. The lowest permeability index (188
µL/min1/2) showed in the concrete treated with 30% Mg2SiF6 solution. It indicated that high

RI
155
156 concentration of Mg2SiF6 solution was more effective in protecting concrete structures.

SC
157 Furthermore, permeability indexes of concretes treated with 10, 20, and 30% magnesium
158 fluorosilicate solutions decreased about 22%, 23%, and 33% from 14d to 28d. However, the
159 reductions of permeability indexes were 25%, 27%, and 19% from 28d to 56d after treatment

U
160 with 10, 20, and 30% magnesium fluorosilicate solutions. The results indicated that the effect
AN
161 of magnesium fluosilicate was more significant within the first 28 days.

162 3.1.2. Effect of sodium silicate treatment on permeability index

M

163 The water permeability indexes of concretes treated with N2 and N3 waterglass are
164 shown in Fig. 3. Compared with the untreated concrete, the permeability indexes of the
D

165 concretes treated with N2 and N3 decreased by 29% and 23% at 14d, 37% and 40% at 28d,
166 and 52% and 53% at 56d, respectively. It could be seen that waterglass was very effective in
TE

167 reducing permeability of concrete. The result was consistent with previous researches [23].
168 Since the watergalss treatment led to a decrease in the contact angle, its protective effect
EP

169 probably due to the reaction with calcium hydroxide to produce C-S-H gel, which blocked the
170 capillary pores [10, 31]. The result also suggested that N2 waterglass was more effective than
C

171 N3 waterglass at early ages, while this superiority diminished at later ages. The reason was
172 that osmotic pressure for penetration would increase with viscosity of the waterglass solution
AC

173 which increased with its modulus [32]. Therefore, N3 waterglass could not penetrate as
174 deeply as N2 waterglass into the concrete at early ages. However, when N3 waterglass
175 gradually penetrated into the concrete with time, it could finally block more pores probably
176 due to its higher silica content. In silicate surface treatment agents, SO32- plays a key role
177 because the higher the silica content is, the greater the amount of the gel produced by the
178 reaction is [33].

6
 ACCEPTED MANUSCRIPT
179 3.1.3. Effect of composite treatment of sodium silicates and sodium fluosilicate on water
180 permeability index of concrete
181 Fig. 4(a) shows the water permeability indexes of concretes after sodium fluosilicate
182 pretreatment and N2 waterglass treatment. It could be seen that the permeability indexes of
183 the concretes treated with N2 waterglass alone were higher than those treated with sodium
184 fluosilicate pretreatment before N2 waterglass treatment. Especially at the 14d, permeability

PT
185 indexes of concretes pretreated with 1%, 2% and 3% sodium fluosilicate solutions dropped by
186 24%, 35% and 32% compared with the concretes treated with N2 watergalss alone. However,

RI
187 the effect of sodium fluosilicate pretreatment became less obvious at later ages. The
188 permeability indexes of concretes pretreated with 2% sodium fluosilicate solutions dropped

SC
189 by 35%, 31% and 25% compared with the concretes treated with N2 watergalss alone at the
190 14d, 28d and 56d respectively. Because sodium fluosilicate is an accelerator for setting of
191 waterglass, it enhanced the impermeability more significantly at early age [34]. However, it

U
192 also can found that this improvement did not disappear in later ages, which indicated that the
AN
193 sodium fluosilicate was not only an accelerator of waterglass setting, but also reacted with
194 cement paste. In the reaction, insoluble products were formed, which blocked the capillary
M

195 channel and thereby further reduced the water permeability index of concrete [9].
196 Similar trend was observed for the samples treated with N3 sodium silicate, as show in
D

197 Fig. 4 (b). Compared with the concrete treated with N3 waterglass, water permeability
198 indexes were reduced by 25%, 30% and 23% after sodium fluosilicate pretreatment at 14d.
TE

199 Among the concrete specimens pretreated with sodium fluosilicate, 2% sodium fluosilicate
200 solution performed best. In fact, overdose sodium fluosilicate would generate redundant
EP

201 sodium fluoride which could dissolute the silica gel and result in higher porosity [34].
202 Therefore, the recommended amount of sodium fluosilicate was 10 -15% of total mass of
203 waterglass.
C

204 3.1.4. Comparison of the three treatment methods

AC

205 Based on the permeability of concretes treated with magnesium fluosilicate, sodium
206 silicate and pretreated with sodium fluosilicate, it could be found that magnesium fluosilicate
207 and N2 waterglass worked mainly before 28d, while N3 waterglass worked mainly after 28d.
208 The pretreatment of sodium fluosilicate could greatly improve the performance of waterglass
209 treatment, especially at early age. Permeability grades of concretes before and after treatments
210 based on Autoclam test are given in Table 6. The concrete with surface treatment belonged to
211 Grade A at 28d, while the untreated concrete belonged to Grade B at 56d. Obviously, the
7
 ACCEPTED MANUSCRIPT
212 inorganic treatment agents used in this paper were helpful in reducing the permeability of
213 concrete.

214 3.2. Effect of surface treatment on water absorption

215 3.2.1. Effect of magnesium fluosilicate on water absorption

216 The water absorption of concrete treated with magnesium fluosilicate is shown in Fig. 5.

PT
217 It could be seen that the rate of reduction in water absorption is highest during the first 28
218 days after magnesium fluosilicate treatment, which agreed with the water permeability index
219 results. Compared with the untreated concrete, water absorptions were reduced by 3, 12, 12

RI
220 and 11% at 0, 14, 28 and 56d after 30% magnesium fluosilicate treatment. Water absorption
221 can reflect the porosity of concrete to some extent. Thus, it could indicate that the magnesium

SC
222 fluosilicate improves the permeability performance by reducing porosity of concrete. Most
223 surface coating and hydrophobic impregnation are organic polymers. It was reported that

U
224 these organic surface treatment agents were very helpful in extending service life of concrete.
AN
225 Almusallam et al. [16] studied the effects of organic surface treatment agents on water
226 absorption, and reported that water absorption of concrete was 28% lower than the untreated
227 concrete. Though organic surface treatment agents can greatly reduce water absorption, they
M

228 still have shortcomings. Medeiros et al. [35, 36] reported that silane and siloxane also could
229 not prevent water ingress under pressure. In addition, all the organic surface treatment agents
D

230 may lose their protective effect under high temperature and weathering [37]. In term of
TE

231 inorganic surface treatments, they are not only effective in protecting concrete structure, but
232 also can resist weathering.
EP

233 3.2.2. Effect of waterglass and sodium fluosilicate on water absorption of concrete
234 The absorption results of concretes with waterglass treatment and composite treatment
C

235 are plotted in Fig. 6. The sodium fluosilicate pretreatment could reduce water absorption at
236 early age. Though this effect was gradually diminished, 2% sodium fluosilicate solution could
AC

237 slightly reduce the water absorption at 56d. This was another evidence for the assumption that
238 the sodium fluosilicate also participated in the reaction with cement paste. From the water
239 absorption results of all three surface treatment methods, it was interesting to notice that the
240 magnesium fluosilicate was more effective before 28d, while the waterglass worked mainly
241 after 28d, and the pretreatment of sodium fluosilicate enhanced the effect of waterglass at
242 early ages. The findings were consistent with the water permeability index results.

8
 ACCEPTED MANUSCRIPT
243 3.2.3. Relationship between Autoclam water permeability index and water absorption
244 Fig. 7 shows the relationship between water absorption and water permeability index of
245 concrete at 56d after treatment with magnesium fluosilicate. It could be seen that there was a
246 good exponential relationship between Autoclam water permeability index and water
247 absorption.

248 3.3. Pore structure

PT
249 According to previous experimental results, the penetration depth of the three treatment
250 agents was about 5mm [31]. Thus, surface layers with thickness of 5mm were used for pore

RI
251 structure measurement. Fig. 8 shows the pore size distribution of the control sample and
252 surface-treated mortars. According to the figure, the porosity of concrete decreased by surface

SC
253 treatment. Magnesium fluosilicate could slightly reduce the critical pore diameter while the
254 waterglass and sodium fluosilicate pretreatment could greatly decrease the critical pore

U
255 diameter. The porosity of mortar treated with waterglass was significantly lower than that of
256 the mortar treated with magnesium fluosilicate. It also could be seen that the higher the
AN
257 modulus of the waterglass was, the lower the porosity is. The pore size distribution indicated
258 that the three inorganic surface treatment agents could reduce the porosity of surface layer.
M

259 The MIP results were consistent with our previous results in that inorganic surface treatment
260 almost eliminated the pores larger than 100nm [31]. These inorganic surface-treatment agents
D

261 could densify the surface layer of the mortar due to the filling of capillary pores by new
TE

262 products, such as C-S-H gel, silica gel and calcium carbonate [31, 38]. Garboczi et al. [39]
263 found that permeability was related to critical pore diameter and capillary porosity form MIP
264 measurement, which can explain the reduction in permeability after surface treatment.
EP

265 The porosity of mortars after surface treatment is shown in Table 7. The pores in cement
266 paste could be divided into four types [40, 41]: gel pores (<10nm), transition pores (10-
C

267 100nm), capillary pores (100-1000nm) and macro-pores (>1000nm). The transport properties
AC

268 of cement-based materials are greatly dependent on the porosity, size and connectivity of
269 capillary pores [42]. Mehta et al. [43] thought that the pores larger than 100nm were related to
270 the permeability of concrete. Thus the amount of capillary and macro-pores is important to
271 the resistance of concrete to water penetration [44]. After magnesium fluoride treatment, the
272 proportion of macro-pores and capillary were decreased by 31% and 15% respectively, which
273 indicated that magnesium fluoride refined the pore structure of mortar. The proportion of
274 macro-pores of mortar after treated with N2 and N3 waterglass decreased by 26%. The
275 proportions of their capillary pores were reduced by 47% and 53%, respectively. Thus,
9
 ACCEPTED MANUSCRIPT
276 magnesium fluoride could block more macro-pores than waterglass, while waterglass was
277 more effective in blocking capillary pores. It could also be seen that the volumes of capillary
278 and macro-pores were reduced with the increase of waterglass modulus, which could explain
279 the effect of N2 and N3 waterglass on water permeability. After the sodium fluosilicate
280 pretreatment, the proportions of macro-pores of specimens were reduced by 29% and 34%,
281 and capillary pores were reduced by 65% and 71%, with respect to mortar treated with N2

PT
282 and N3 waterglass treatment alone. Thus it could conclude that the porosity and pore size of
283 cement mortar were decreased further by sodium fluosilicate pretreatment. Sodium

RI
284 fluosilicate can also react with concrete substrate to generate new products [38]. The volume
285 of pore smaller than 100nm increased after surface treatment, which indicated that these

SC
286 surface treatment agents were effective in filling capillary pores coarser than 100 nm.

287 4. Conclusion

288
U
Effects of fluosilicate and sodium silicate surface treatment on water permeability, water
AN
289 absorption were studied. Their effects on pore structures of superficial cement mortar and
290 their pore refinement were examined. The following conclusions can be drawn based on the
M

291 above experimental results and analyses:

292 (1) The three inorganic surface treatment agents could improve the concrete resistance to
D

293 water penetration, especially at early ages. The use of 30% magnesium fluosilicate solution
294 performed the best and reduced water permeability by 52% at 56d. Waterglass treatment also
TE

295 could reduce the water permeability by about 50%, and sodium fluosilicate could improve the
296 performance of waterglass treatment at early ages by about 35%.
EP

297 (2) Water absorption of concrete reduced by about 10% after inorganic surface treatment.
298 In addition, there was a good exponential relationship between Autoclam water permeability
C

299 index and water absorption of concrete. The inorganic surface treatment decreased the water
AC

300 transport properties of hardened concrete mainly due to blockage of pores larger than 100nm.
301 (3) The magnesium fluosilicate worked mainly at early ages, while the effects of
302 waterglass lasted longer, especially N3 waterglass. Sodium fluosilicate pretreatment could not
303 only react with waterglass, but also with concrete substances.
304 (4) These three inorganic surface treatment agents could reduce the macro and the
305 capillary pores, but slightly increased the volume of pores smaller than 100nm. The
306 magnesium fluoride could block more macro-pores while waterglass was more effective in
307 blocking capillary pores. In addition, sodium fluosilicate could react with concrete substrate
10
 ACCEPTED MANUSCRIPT
308 and waterglass, showing further decrease in porosity. The pores on concrete surface were
309 blocked by insoluble calcium silicate hydrate and silica gel which were generated by reactions
310 between inorganic surface treatment agent and Ca(OH)2 in concrete.
311

312 Reference:

313 [1].Khatri RP, Sirivivatnanon V. Effect of curing on water permeability of concretes prepared

PT
314 with normal Portland cement and with slag and silica fume. Magazine of Concrete Research

RI
315 1997; 49(180): 167-172.

316 [2].Zhao T, Permeability of concrete. Science Press; 2005. (in Chinese)

SC
317 [3].Banthia N, Mindess S. Water permeability of cement paste. Cem and Concr Res 1989,

318 19(5): 727-736.

319
U
[4]. Ahmad S. Reinforcement corrosion in concrete structures, its monitoring and service life
AN
320 prediction––a review. Cem Concr Compos 2003, 25(4): 459-471.
M

321 [5]. Hilsdorf H, Kropp J. Performance criteria for concrete durability. CRC Press 2004.

322 [6]. Basheer PAM, Chidiact SE, Long AE. Predictive models for deterioration of concrete
D

323 structures. Construct Build Mater 1996, 10(1): 27-37.

TE

324 [7]. Basheer L, Kropp J, Cleland DJ. Assessment of the durability of concrete from its

325 permeation properties: a review. Construct Build Mater 2001, 15(2): 93-103.
EP

326 [8].Hoseini M, Bindiganavile V, Banthia N. The effect of mechanical stress on permeability

327 of concrete: a review. Cem Concr Compos 2009, 31(4): 213-220.

C

328 [9].Bertolini, L, Elsener B, Pedeferri P, Redaelli E, Polder RB. Corrosion of steel in concrete:
AC

329 prevention, diagnosis, repair. John Wiley & Sons; 2013.

330 [10].Dai JG, Akira Y, Wittmann FH, Yokota H, Zhang P. Water repellent surface

331 impregnation for extension of service life of reinforced concrete structures in marine

332 environments: the role of cracks. Cem Concr Compos 2010; 32(2):101-109.

333 [11].Diamanti MV, Brenna A, Bolzoni F, Berra M, Pastore T, Ormellese M. Effect of

11
 ACCEPTED MANUSCRIPT

334 polymer modified cementitious coatings on water and chloride permeability in concrete.

335 Construct Build Mater 2013; 49:720-728.

336 [12].Hoseini M, Bindiganavile V, Banthia N. The effect of mechanical stress on permeability

337 of concrete: A review. Cem Concr Compos 2009; 31(4):213-220.

338 [13].Neville A. Good reinforced concrete in the Arabian Gulf. Mater Struct 2000; 33(10):

PT
339 655-664.

RI
340 [14].Swamy RN, Tanikawa S. Surface coating for sustainable protection and rehabilitation of

341 concrete structures. Kohbunsha Publishing Co., Ltd., Japan, 2012, 257 pp.

SC
342 [15].Swamy RN. Design for durable service life/linchpin for sustainability in concrete

343 construction. ACI Special Publication 1999; 186.

344
U
[16].Tittarelli F, Moriconi G. The effect of silane-based hydrophobic admixture on corrosion
AN
345 of reinforcing steel in concrete. Cem Concr Res 2008; 38(11):1354-1357.
M

346 [17].Moradllo MK, Shekarchi M, Hoseini M. Time-dependent performance of concrete

347 surface coatings in tidal zone of marine environment. Construct Build Mater 2012; 30:198-
D

348 205.
TE

349 [18].Almusallam AA, Khan FM, Dulaijan SU, Al-Amoudi OSB. Effectiveness of surface

350 coatings in improving concrete durability. Cem Concr Compos 2003; 25(4):473-481.
EP

351 [19].Ibrahim M, Al-Gahtani AS, Maslehuddin M, Dakhil FH. Use of surface treatment

352 materials to improve concrete durability. J Mater Civ Eng 1999; 11(1):36-40.
C

353 [20].Buenfeld NR, Zhang J. Chloride diffusion through surface-treated mortar specimens.
AC

354 Cem Concr Res 1998; 28(5):665-674.

355 [21].Hansson CM, Mammoliti L, Hope BB. Corrosion inhibitors in concrete—part I: the

356 principles. Cem Concr Res 1998; 28(12):1775-1781.

357 [22].Delucchi M, Barbucci A, Cerisola G. Study of the physico-chemical properties of

358 organic coatings for concrete degradation control. Construct Build Mater 1997; 11(7):365-371.

12
 ACCEPTED MANUSCRIPT

359 [23].Thompson JL, Silsbee MR, Gill PM, Scheetz BE. Characterization of silicate sealers on

360 concrete. Cem Concr Res 1997; 27(10):1561-1567.

361 [24].Franzoni E, Pigino B, Pistolesi C. Ethyl silicate for surface protection of concrete:

362 Performance in comparison with other inorganic surface treatments. Cem Concr Compos

363 2013; 44:69-76.[23].Dai J, Akira Y, Kato E, Yokota H. Investigation of chloride ingress in

PT
364 cracked concrete treated with water repellent agents. In 5th International Conference on Water

RI
365 Repellent Treatment of Building Materials. Aedificatio Publishers Freiburg; 2008. p. 299-310.

366 [26].Yang K, Basheer PAM, Magee B. Investigation of moisture condition and Autoclam

SC
367 sensitivity on air permeability measurements for both normal concrete and high performance

368 concrete. Construct Build Mater 2013. 48: 306-314.

369
U
[27].Basheer PAM. # Clam' permeability tests for assessing the durability of concrete.
AN
370 Queen's University of Belfast, 1991.
M

371 [28].Basheer PAM. The ‘Autoclam’ for measuring the permeation properties of hardened

372 concrete near the surface. Operations manual, 1991.

D

373 [29].Hall C. Water sorptivity of mortars and concretes. Mag. Concr. Res 1989; 41(147): 51-61.
TE

374 [30].Taylor HF. Cement chemistry. Thomas Telford, 1997.

375 [31].Pan X, Shi C, Jia L, Zhang J, Wu L. Effect of Inorganic Surface Treatment on Air
EP

376 Permeability of Cement-Based Materials. Journal of Materials in Civil Engineering,

377 04015145.
C

378 [32].Zhou H. Engineering fluid mechanics. Metallurgical Industry Press, 1988. (in Chinese)
AC

379 [33].Moon HY, Shin D G, Choi D S. Evaluation of the durability of mortar and concrete

380 applied with inorganic coating material and surface treatment system. Construct Build Mater

381 2007; 21(2):362-369.

382 [34].Hu W, Research and engineering application of heat-resistant sodium water glass

383 adhesive. South China University of Technology, 2011.

13
 ACCEPTED MANUSCRIPT

384 [35].Medeiros M, Helene P. Efficacy of surface hydrophobic agents in reducing water and

385 chloride ion penetration in concrete. Materials and Structures 2008. 41(1):59-71.

386 [36].Medeiros MH, Helene P. Surface treatment of reinforced concrete in marine environment:

387 Influence on chloride diffusion coefficient and capillary water absorption. Construct Build

388 Mater 2009; 23(3):1476-1484.

PT
389 [37].Levi M, Ferro C, Regazzoli D, Dotelli G. Comparative evaluation method of polymer

RI
390 surface treatments applied on high performance concrete. Journal of Materials Science 2002;

391 37(22):4881-4888.

SC
392 [38].Pan X, Shi C, Zhang J, Wu L. Interactions between inorganic surface treatment agents

393 and matrix of cement-based materials. The 14th International Congress on the Chemistry of

394 Cement. Beijing, China, 13-16 October, 2015

U
AN
395 [39].Garboczi EJ, Bentz DP. Digitised simulation of mercury intrusion porosimetry. Ceram.
M

396 Trans 1990; 16:365-380.

397 [40].Lian H, Tong L, Chen E. Foundation of research on building material. Tsinghua

D

398 University Press, 1996. (in Chinese)

TE

399 [41].Shen A, Zhang D. Cement and concrete. China Communications Press, 2000. (in Chinese)

400 [42].Jennings HM, Bullard JW, Thomas JJ, Andrade JE, Chen JJ, Scherer GW.
EP

401 Characterization and modeling of pores and surfaces in cement paste: correlations to

402 processing and properties. Journal of Advanced Concrete Technology 2008, 6(1): 5-29.
C

403 [43].Manmohan D, Mehta PK. Influence of pozzolanic, slag and chemical admixtures on pore
AC

404 size distribution and permeability of hardened cement pastes. Cement, Concrete, and

405 Aggregates 1981; 3(1):63-6

406 [44].Dubinin MM, Kataeva LI, Ulin VI. Capillary effects and information concerning the pore

407 structure of adsorbents. Bulletin of the Academy of Sciences of the USSR, Division of

408 chemical science 1977; 26(3): 459-463.

409
14
 ACCEPTED MANUSCRIPT
410 LIST OF TABLES
411

412 Table 1. Chemical composition of cement

413 Table 2. Chemical composition and parameters of waterglass

414 Table 3. Mix proportion of concrete specimens

PT
415 Table 4. Methods of concrete surface treatment

416 Table 5. Criteria of concrete water permeability

RI
417 Table 6. Permeability index and grade of concrete before and after different surface

418 treatments

SC
419 Table 7. Pore structure of surface layer of mortar
420
421
U
AN
422
423
424
M

425
426
D

427
428
TE

429
430
EP

431
432
433
C

434
AC

435
436
437
438
439
440
441
442
443

15
 ACCEPTED MANUSCRIPT
444
445
446
447

448 Table 1 Chemical composition of cement (%)

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3

PT
21.91 5.30 3.67 65.10 1.51 0.62 0.19 2.03

449
450

RI
451

U SC
AN
M
D
TE
EP
C
AC

16
 ACCEPTED MANUSCRIPT
452
453
454
455

456 Table 2 Chemical composition and parameters of waterglass

Code Modulus Na2O (%) SiO2 (%) Baume degree Density (kg/m3)

PT
N3 3 9.05 26.5 38.4 1369
N2 2 12.9 25.0 44.1 1440

RI
457
458

U SC
AN
M
D
TE
C EP
AC

17
 ACCEPTED MANUSCRIPT
459
460
461
462

463 Table 3 Mix proportion of concrete specimens

Compressive
Cement Water Coarse aggregate Fine aggregate

PT
w/c strength at 28d
(kg/m3) (kg/m3) (kg/m3) (kg/m3)
(MPa)
0.45 400 181 1299 520 49.5

RI
464

SC
465

U
AN
M
D
TE
C EP
AC

18
 ACCEPTED MANUSCRIPT
466
467
468
469
470 Table 4 Methods of concrete surface treatment
Treatment method
Specimen
MgSiF6 (%) Na2SiO3 (M) Na2SiF6solution (%)

PT
1-1 0 0 0
1-2 10 0 0

RI
1-3 20 0 0
1-4 30 0 0

SC
1-5 0 2 0
1-6 0 3 0

U
1-7 0 2 1
AN
1-8 0 2 2
1-9 0 2 3
1-10 0 3 1
M

1-11 0 3 2
1-12 0 3 3
D

471
TE

472
473
C EP
AC

19
 ACCEPTED MANUSCRIPT
474
475
476
477

478 Table 5 Criteria of concrete water permeability

Grade

PT
Project Very good Good Poor Very poor
A B C D

RI
Water permeability index
≤370 370-940 940-1380 >1380
(µL /min1/2)

SC
479
480
481
482

U
AN
483
M
D
TE
C EP
AC

20
 ACCEPTED MANUSCRIPT
484
485
486
487

488 Table 6 Permeability index and grade of concrete before and after different surface treatments
Permeability index (µL/min1/2) and grade
NO.

PT
14d 28d 56d
1-1 529 B 432 B 400 B
1-2 468 B 362 A 273 A

RI
1-3 405 B 310 A 225 A
1-4 350 A 233 A 188 A

SC
1-5 374 B 272 A 192 A
1-6 406 B 260 A 186 A

U
1-7 284 A 240 A 158 A
AN
1-8 243 A 215 A 133 A
1-9 256 A 230 A 145 A
1-10 304 A 210 A 167 A
M

1-11 284 A 198 A 129 A

1-12 313 A 215 A 140 A
D

489
TE

490
C EP
AC

21
 ACCEPTED MANUSCRIPT
491
492
493
494

495 Table 7 Pore structure of surface layer of mortar

Proportion (%) Porosity
NO.
(cm3/g, ×10-2)

PT
<10nm 10-100nm 100-1000nm >1000nm
1-1 3.58 60.94 24.59 10.89 12.97

RI
1-4 3.81 67.83 20.83 7.53 12.60
1-5 4.86 74.00 13.05 8.09 10.59

SC
1-6 5.39 75.09 11.51 8.01 10.51
1-8 4.63 79.09 8.58 7.7 10.52
1-11 4.31 81.39 7.07 7.23 10.07

496
U
AN
497
M
D
TE
C EP
AC

22
 ACCEPTED MANUSCRIPT
498 LIST OF FIGURES
499

500 Fig. 1. Relationship between the quantity of water entering the untreated concrete and the

501 square root of time

502 Fig. 2. Effect of magnesium fluosilicate surface treatment on water permeability index of

PT
503 concrete

504 Fig. 3. Effect of waterglass treatment on water permeability index of concrete

RI
505 Fig. 4. Effect of sodium fluosilicate pretreatment and waterglass treatment on water

506 permeability of concrete

SC
507 Fig. 5. Water absorption of concrete treated with magnesium fluorsilicate

U
508 Fig. 6. Effect of sodium fluosilicate pretreatment and waterglass treatment on water
AN
509 absorption

510 Fig. 7. Relationship between water permeability index and water absorption of concrete after
M

511 magnesium fluosilicate treatment

512 Fig. 8. Pore size distribution of mortars without and with different surface treatments
D

513
TE

514
C EP
AC

23
 ACCEPTED MANUSCRIPT
515
516
517
518
2200

14d
2000 28d
56d

PT
1800 y1=529x+25
y2=432x+19
Inflow water (mL)

2
R =0.99 2
1600 R =0.99

RI
1400

1200 y3=400x+29.6

SC
2
R =0.99
1000

800

U
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
1/2
519 Time (min )
AN
520 Fig. 1. Relationship between the quantity of water entering the untreated concrete and the
521 square root of time
522
M

523
D
TE
C EP
AC

24
 ACCEPTED MANUSCRIPT
524
525
526
527
600

1-1
1-2
500

PT
Permeability index (mL/min1/2)

1-3
1-4

400

RI
300

SC
200

U
100
14 28 42 56
AN
528 Age (d)

529 Fig. 2. Effect of magnesium fluosilicate surface treatment on water permeability index of
530 concrete
M

531
532
D
TE
C EP
AC

25
 ACCEPTED MANUSCRIPT
533
534
535
536
600
1-1
1-5
500 1-6
Permeability index (mL/min )

PT
1/2

400

RI
300

SC
200

U
100
14 28 42 56
Age (d)
AN
537
538 Fig. 3. Effect of waterglass treatment on water permeability index of concrete
539
M

540
D
TE
C EP
AC

26
 ACCEPTED MANUSCRIPT
541
542
543
544

600
1-1
1-5

PT
500 1-7
Permeability index (mL/min )
1/2

1-8
1-9
400

RI
300

SC
200

U
100
14 28 42 56
AN
Age (d)
545
546 (a) N2 waterglass treatment
547
M

600
1-1
D

1-6
500 1-10
Permeability index (mL/min )
1/2

1-11
TE

1-12
400
EP

300

200
C
AC

100
14 28 42 56
Age (d)
548
549 (b) N3 waterglass treatment
550 Fig. 4. Effect of sodium fluosilicate pretreatment and waterglass treatment on water
551 permeability of concrete
552
553

27
 ACCEPTED MANUSCRIPT
554
555
556
557

5.8 1-1
1-2
1-3

PT
5.6
1-4

5.4
Absorption (%)

RI
5.2

5.0

SC
4.8

4.6

0 14

U
28 42 56
AN
558 Age (d)
559 Fig. 5. Water absorption of concrete treated with magnesium fluorsilicate
560
M

561
D
TE
C EP
AC

28
 ACCEPTED MANUSCRIPT
562
563
564

5.8 1-1
1-5
5.6 1-7
1-8
5.4 1-9

PT
Absorption (%)

5.2

5.0

RI
4.8

4.6

SC
4.4

0 14 28 42 56

U
565 Age (d)
566 (a) N2 waterglass
AN
567
M

5.8 1-1
1-6
5.6 1-10
1-11
D

5.4 1-12
Absorption (%)

5.2
TE

5.0

4.8
EP

4.6

4.4
C

0 14 28 42 56

568 Age (d)

AC

569 (b) N3 waterglass

570 Fig. 6. Effect of sodium fluosilicate pretreatment and waterglass treatment on water
571 absorption
572
573
574
575
576

29
 ACCEPTED MANUSCRIPT
577
578
579
580

450

PT
400
Permeability index (mL/min )
1/2

y=-2.34exp(-x/0.1+50.7)+437
2
R =0.93
350

RI
300

SC
250

U
200
4.6 4.7 4.8 4.9 5.0 5.1 5.2 5.3 5.4
AN
581 Absorption (%)

582 Fig. 7. Relationship between water permeability index and water absorption of concrete after
583 magnesium fluosilicate treatment
M

584
585
D
TE
C EP
AC

30
 ACCEPTED MANUSCRIPT
14

Cumulative pore volume(cm3/g, × 10-2)

1-1
12
1-4

10

PT
2

RI
10 100 1000 10000 100000
Pore diameter (nm)
586
587 (a) Without and with magnesium fluosilicate treatment

SC
14
1-1
Cumulative pore volume (cm /g, × 10 )
-2

12 1-5
1-8

U
3

10
AN
8

4
M

2
D

0
10 100 1000 10000 100000
Pore diameter (nm)
588
TE

589 (b) Without and with N2 waterglass treatment

14
1-1
Cumulative pore volume (cm3/g, × 10-2)

EP

12 1-6
1-11

10
C

8
AC

0
10 100 1000 10000 100000
Pore diameter (nm)
590
591 (c) Without and with N3 waterglass treatment
592 Fig. 8. Pore size distribution of mortars without and with different surface treatments
593

31