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Hydration, pore solution, and porosity of cementitious pastes made with

seawater

Article  in  Journal of Materials in Civil Engineering · May 2019

DOI: 10.1061/(ASCE)MT.1943-5533.0002818

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1 Hydration, pore solution, and porosity of cementitious pastes made with seawater

2 Luca Montanari1, Prannoy Suraneni, Ph.D.2, Marisol Tsui Chang3, Morteza Khatibmasjedi4,

3 Usama Ebead, Ph.D.5, Jason Weiss, Ph.D., M. ASCE6, Antonio Nanni, Ph.D., M. ASCE7

5 Abstract

6 Unreinforced concrete or concrete reinforced with non-corrosive reinforcement could

7 potentially be mixed with seawater in locations where potable water is scarce. A fundamental

8 understanding of the properties of concrete mixed with seawater is therefore essential. This

9 paper analyzes the hydration kinetics, hydrate phases, pore solution, and porosity of

10 cementitious pastes made with seawater and compares these results with the corresponding

11 ones from pastes made with deionized water. Pastes were prepared with cement and with a 20

12 % mass replacement of the cement with fly ash. Isothermal calorimetry (to study hydration

13 kinetics), thermogravimetric analysis (to study the hydrated phase assemblage), X-ray

14 fluorescence (to determine pore solution composition and electrical resistivity), and dynamic

15 vapor sorption (to determine the pore size distribution) were performed on the paste samples.

16 Seawater accelerates hydration kinetics at an early age; however, this effect is negligible at

17 later ages. Friedel‘s salt formation in systems with seawater at later ages is negligible (0.4 %

18 (by mass of paste) at 91 days). The primary difference between the hydrated phases of pastes

1
Concrete Materials Engineer, SES Group and Associates LLC at Turner-Fairbank Highway Research Center,
6300 Georgetown Pike, McLean, VA 22101, Email: montanal@oregonstate.edu
2
Assistant Professor, Department of Civil, Architectural and Environmental Engineering, University of
Miami, 1251 Memorial Dr, Coral Gables, FL 33146, Email: suranenip@miami.edu (corresponding author)
3
Project Engineer, Olson Engineering, Inc., 7529 Standish Place, Rockville, MD 20855, Email:
tsuicham@oregonstate.edu
4
Ph.D student, Department of Civil, Architectural and Environmental Engineering, University of Miami,
1251 Memorial Dr, Coral Gables, FL 33146, Email: mortezakhatib@umiami.edu
5
Professor, Department of Civil and Architectural Engineering, Qatar University, Doha, Qatar, PO Box 2713,
Email: uebead@qu.edu.qa
6
Head of School of Civil and Construction Engineering, Professor, Oregon State University, 101 Kearney
Hall, Corvallis, OR, 97331, Email: jason.weiss@oregonstate.edu
7
Head of Civil, Architectural and Environmental Engineering University of Miami, 1251 Memorial Dr, Coral
Gables, FL 33146, Email: nanni@miami.edu

1
19 made with seawater and with deionized water appears to be the absorption of chloride in the

20 calcium silicate hydrate. The pore solution in pastes made with seawater has higher sodium,

21 chloride, and hydroxide ion concentrations. The concentrations of sodium, potassium, and

22 hydroxide ions in the pore solutions are lower in pastes with fly ash compared to pastes

23 without fly ash. Pastes with seawater show a lower electrical resistivity than pastes with

24 deionized water due to the higher ionic concentrations. The paste with seawater has a slightly

25 finer pore structure compared to the paste with deionized water.

26

27 Keywords

28 Seawater concrete, fly ash, hydration, pore solution, pore size distribution

29

30 Introduction

31 The use of seawater to replace potable water for concrete mixing is an attractive

32 alternative in regions of the world where potable water is in short supply. While the idea of

33 making concrete with seawater is not new (Kaushik and Islam 1995; Mohammed at al. 2004;

34 Nishida et al. 2015; Shi et al. 2015), research on this topic is somewhat scarce. Further,

35 practical implementation has been extremely limited. The primary concern associated with

36 the use of seawater is related to the potential for corrosion of steel reinforcement in the

37 concrete due to the presence of chloride from the seawater. However, this concern need not

38 be a limitation for all concrete. First, not all concrete is reinforced, and, the use of seawater

39 for non-reinforced concrete applications should be given consideration. Second, fiber

40 reinforced polymer (FRP) may be used as reinforcement instead of steel. This suggests that

41 concrete made with seawater and reinforced with FRP maybe an alternative to conventional

42 steel reinforced concrete (Felicato et al. 2015; Khatibmasjedi et al. 2016; Xiao et al. 2017).

43 Such concretes could be used for underwater or marine applications such as seawalls or

2
44 artificial reefs. Seawater-mixed concrete generally shows superior performance to

45 conventional concrete when cured under seawater and in the tidal zone (Khatibmasjedi et al.

46 2018a). Studies in our lab have shown slightly lower strengths using seawater-mixed

47 concretes, depending on the curing conditions zone (Khatibmasjedi et al. 2018a; Younis et al.

48 2018). In order to evaluate whether other durability concerns exist in the development of

49 concrete with the use of seawater, a fundamental understanding of the material science and

50 their engineering properties of cementitious materials made with seawater is required.

51 Specifically, the use of seawater could increase the risk of alkali silica reaction due to the

52 greater alkali content in pore solution and the risk of sulfate attack due to the greater sulfate

53 contents in the system. Unfortunately, fundamental understanding of the material science nor

54 durability testing of alkali silica reaction and sulfate attack is not available in literature, and

55 the vast majority of studies that deal with seawater concrete (Kaushik and Islam 1995;

56 Mohammed at al. 2004; Nishida et al. 2015; Shi et al. 2015) discuss the compressive strength

57 of the concrete and the corrosion of the reinforcing steel (Mohammed at al. 2004; Nishida et

58 al. 2015; Shi et al. 2015). Other work in our lab has looked at strength, permeability, and

59 shrinkage in seawater-mixed mortar and concrete but fundamental properties of seawater-

60 mixed cementitious pastes have not been explored (Khatibmasjedi et al. 2018a;

61 Khatibmasjedi et al. 2018b; Younis et al. 2018). Therefore, this work reports the results of an

62 investigation on the early and later age properties of cementitious pastes made with seawater.

63 Specifically, the hydration (hydration kinetics and hydrate assemblage), the pore solution

64 (composition and electrical resistivity), and the pore size distribution of cementitious pastes

65 made with deionized water and seawater are studied. The results from this study show the

66 changes that seawater causes in the hydration, hydrates, pore solution, and porosity of

67 cementitious pastes and will be valuable in explaining the durability of seawater-mixed

68 concrete (which is currently ongoing in our laboratory).

3
69 Materials and mixing

70 A type II ordinary Portland cement (conforming to ASTM C150 – 17) and a Class F

71 fly ash (conforming to ASTM C618 – 17) were used in this study. Their oxide compositions

72 and the phase composition of the cement are listed in Table 1. The cement has a Blaine

73 fineness of 375 m2/kg. The ionic composition of the seawater (Key Biscayne Bay, FL) was

74 tested using X-ray fluorescence (XRF) and is presented in Table 2. The XRF is capable of

75 testing liquid samples and is specifically calibrated for the ions shown in Table 2 by testing a

76 wide range of ionic compositions. Further details of the XRF calibration and testing are

77 presented in the Experimental methods section below and discussed in literature (Chang et al.

78 2017). These results were compared with results from Inductively coupled plasma atomic

79 emission spectroscopy (ICP-AES) and for all ions, results from the two test methods had less

80 than a 10 % average absolute error.

81 Table 1. Composition of the cement and the fly ash (mass %).

Parameter Type II cement Fly ash

SiO2 20.50 46.80
Al2O3 4.90 19.30
Fe2O3 3.90 18.99
CaO 64.40 5.50
MgO 0.90 0.90
SO3 2.60 2.23
Na2Oeq. 0.25 0.88
Loss on ignition 2.10 3.10
C3S 60 -
C2S 14 -
C3A 7 -
C4AF 12 -
82 *According to cement chemistry notation, C is CaO, S is SiO2, A is Al2O3 and F is

83 Fe2O3.

4
84 Table 2. Seawater composition in ppm and mol/L.

Ionic species Concentration (ppm) Concentration (mol/L)*

Na+ 10735.7 0.479
K+ 380.0 0.010
Ca+2 424.0 0.011
Mg+2 1416.0 0.060
Cl- 19920.0 0.576
SO4-2 2697.0 0.029
85 *Compositions were measured in ppm and converted to mol/L using an assumed

86 seawater density of 1025 kg/m3 (Poisson et al. 1980).

87 Cementitious pastes were made with a water-to-cementitious material ratio (w/cm) of

88 0.40. The water used for mixing was either deionized water or seawater. In addition to

89 cement pastes, pastes were also made with fly ash. Fly ash was used to replace 20 % of the

90 cement by mass. The mixture proportions listed in Table 3 were chosen based on concrete

91 mixture proportions being used for durability testing (and for larger scale construction

92 projects) (Khatibmasjedi et al. 2016). Mixing was done using a vacuum mixer, which

93 minimizes the presence of entrapped air. Pastes were mixed for three minutes, with a break

94 after 90 seconds to scrape material from the blade and the sides of the mixer. The procedure

95 is described in detail elsewhere (Todd 2015). Isothermal calorimetry was done on pastes

96 immediately after mixing and is described in the Experimental methods section below. Paste

97 was cast in cylindrical molds of two sizes (35.8 mm diameter and 55.4 mm high and 50.8 mm

98 diameter and 101.6 mm high) and sealed with lids for hardened testing. The cylinders were

99 sealed cured at 23 ± 1 °C; one set of cylinders was cured at 23 ± 1 °C for 3 days and then at

100 50 ± 1 °C for 25 days to reach an equivalent age of 91 days (at 23 °C), based on maturity

101 calculations (Todd 2015).

102

103

5
104 Table 3. Mixture proportions* of the tested cement pastes (in g).

Water Air
Mixture Cement Fly ash Water w/cm Retarder
type entrainer**
Cement
430 0 172 0.40 Deionized 0.806 0.307
control
Cement
430 0 172 0.40 Seawater 0.806 0.307
seawater
Fly ash
344 86 172 0.40 Deionized 0.806 0.307
control
Fly ash
344 86 172 0.40 Seawater 0.806 0.307
seawater
105 *Mixture proportions are presented for one batch of the vacuum mixer. The fly ash

106 replacement is 20 % by mass, the w/cm is 0.40, the retarder and air entrainer are used at 0.19

107 % and 0.07 % of cementitious materials mass, respectively.

108 **Air entrainer is used here to ensure that compositions are similar to ones used in

109 other testing (Khatibmasjedi et al. 2016), however, it is not likely to entrain a significant

110 amount of air in vacuum mixed cementitious pastes.

111

112 Experimental methods

113 Isothermal calorimetry

114 After mixing, approximately 6 to 7 g of the paste was cast in a glass ampoule, which

115 was then gently tamped to ensure proper consolidation. The glass ampoule was then sealed

116 with a lid and placed in an isothermal calorimeter, which had been preconditioned at 23 ±

117 0.05 °C. The heat flow and the cumulative heat release were measured for a period of seven

118 days after mixing. The results were normalized to the mass of cementitious material. Further

119 details of isothermal calorimetry testing are provided elsewhere (Todd 2015; Todd et al.

6
120 2017). Two replicate samples of cement paste without fly ash or seawater showed differences

121 less than 3 % for cumulative heat release after one day.

122

123 Thermogravimetric analysis (TGA)

124 Testing was performed on each mixture after curing (23 ± 1 °C) at 12 hours, 1 day, 3

125 days, 7 days and 28 days. Testing was also performed on 91-day equivalent mixtures (cured

126 at 23 ± 1 °C for 3 days and then at 50 ± 1 °C for 25 days to reach an equivalent age of 91

127 days). The samples were first ground the sample to a fine powder using a lathe grinder. The

128 first few mm of material was removed due to edge effects and possible carbonation and the

129 remainder of the material was ground and passed through a 75 μm sieve to give a sample of

130 size approximately 5 g. TGA was performed on the different cementitious pastes to

131 determine the amount of Friedel‘s salt, the amount of Ca(OH)2, the bound water, and to

132 compare the phase assemblages for pastes with deionized water and seawater. To do this, the

133 test was performed by placing approximately 30 mg of ground material in a platinum pan,

134 which was heated to 1000 °C at a rate of 10 °C/min in an inert nitrogen atmosphere. The

135 Friedel‘s salt amount (g/100 g paste) was determined based on the mass loss between

136 approximately 230 °C and 380 °C (Shi et al. 2017), the Ca(OH)2 content (g/100 g paste) was

137 determined based on the mass loss between approximately 380 °C and 500 °C (Suraneni et al.

138 2017), and the bound water (g/100 g cement) was determined by using the entire mass loss

139 profile (Fagerlund 2009). Coefficient of variation for calcium hydroxide contents for cement

140 pastes using three replicates was approximately 1 %.

141

142 Pore solution extraction

143 Pore solutions were expressed from paste specimens using a highly pressurized

144 mechanical pore press device (Barneyback and Diamond 1981; Chang et al. 2018) at 12

7
145 hours, 3 days, and 28 days. Paste samples were demolded and crushed (to a fragment sizes

146 smaller than 9.5 mm diameter) in a plastic bag to minimize moisture loss. The crushed pieces

147 were then moved inside the pore press device, where the pore solution was expressed by

148 applying a mechanical load using a compression testing machine (with a maximum load of

149 890 kN, at a rate between 2.22 and 2.89 kN/s). The expressed pore solutions were collected

150 in 6 mL plastic vials and transferred into 6 mL syringes and stored inside an environmental

151 chamber at 5 ± 1 °C prior to testing. The storing in syringes allowed to minimize the contact

152 with air and reduce the potential for carbonation (Chang et al. 2018). Testing was completed

153 within one day of pore solution extraction. Further details about pore solution expression are

154 provided elsewhere (Barneyback and Diamond 1981; Chang et al. 2018).

155

156 X-ray fluorescence (XRF)

157 An energy dispersive XRF spectrometer was used to determine the chemical

158 composition and the calculated resistivity of the expressed pore solutions and the chemical

159 composition of the seawater. The pore solutions were analyzed using a pre-calibrated testing

160 application that detects the primary ions in the pore solutions: sodium (Na+), potassium (K+),

161 calcium (Ca2+), sulfide (S2-), and chloride (Cl-). It is assumed that the sulfide ions correspond

162 to the sulfate (SO42-) ions and stoichiometry is used to calculate sulfate concentrations. Charge

163 balance is then used to calculate hydroxide (OH-) concentrations. It should be noted that

164 magnesium (Mg+2) ions were not quantified in the tested pore solutions and this may lead to

165 slight errors in the calculated resistivity values (although their concentration in pore solutions

166 is not expected to be large). Calibration was performed with known standards (using varying

167 concentrations of >99% pure sodium chloride (NaCl), potassium chloride (KCl), calcium

168 chloride (CaCl2) and aluminum sulfate (Al2(SO4)3)). Further details about the XRF setup and

169 calibration are provided elsewhere (Chang et al. 2017; Chang et al. 2018).

8
170 The expressed pore solutions were measured directly in a plastic container with a 4 µm

171 thick polypropylene film base, chosen for its stability at high pH values typically encountered

172 in cementitious pore solutions. The containers were assembled and checked for leaks, and then

173 moved into the XRF and analyzed (Chang et al. 2017; Chang et al. 2018). Coefficient of

174 variation for Na+, K+, and OH- ions for three replicate measurements using the XRF was

175 approximately 5 % (Chang et al. 2018).

176 The electrical resistivity for expressed pore solutions was calculated using a model

177 (Snyder et al. 2003), which estimates the pore solution conductivity from the concentration of

178 the main ionic species in pore solution (Na+, K+, OH-, Ca2+, SO42, and Cl-), as shown in

179 Equations 1 and 2. This model has been used elsewhere and shown to be quite accurate (Snyder

180 et al. 2003; Chang et al. 2017; Chang et al. 2018).

181 𝜎"#$" = ∑( 𝑧( 𝑐( 𝜆( (1)

182

,∘-
183 𝜆( = 4/6 (2)
/ 0 1- 23

184 where:

185 σ89:8 = electrolyte conductivity of the ionic solution in S/m

186 λ< = equivalent conductivity of a single ionic species in cm2 S/mol

187 z< = valence concentration of a single ionic species

188 c< = molar concentration of a single ionic species in mol/L

189 λ∘< = equivalent conductivity of an ionic species at infinite dilution in cm2 S/mol

190 G< = empirical conductivity coefficient of a single ionic species in (mol/L)-1/2

191 IA = ionic strength (molar basis) in mol/L

192 i = a single ionic species

193

9
194 The electrical resistivity can be then directly calculated by taking the inverse of the

195 conductivity as shown in Equation 3.

/
196 𝜌"#$" = D (3)
EFGE

197 where:

198 σ89:8 = electrolyte conductivity of the ionic solution in S/m

199 ρ89:8 = resistivity of the ionic solution in cm2 S/mol

200

201 Dynamic vapor sorption (DVS)

202 Desorption isotherms of the pastes were measured using a dynamic vapor sorption

203 analyzer, in order to obtain information about pore size distribution (Montanari et al. 2018).

204 As the test is time consuming (approximately 14 days for each sample), the test was only

205 performed on the cement pastes without fly ash. Samples with an equivalent age of 91 days

206 were cut with a precision saw into small discs with a thickness of 0.8 ± 0.05 mm (Villani et

207 al. 2014). The samples were then vacuum saturated with a saturated calcium hydroxide

208 solution for a period of 24 hours. A sample of approximately 50 ± 5 mg was then obtained

209 from each disk, reduced to a surface dry condition, and moved to a tared quartz pan in the

210 DVS. The DVS measures the changes in the mass of the sample (degree of saturation) as a

211 function of relative humidity at constant temperature. Samples were introduced into the

212 device in a saturated surface dry state. The DVS was first stabilized at a relative humidity of

213 97.5 % for 24 hours. The relative humidity was then decreased stepwise, with a stepsize of 10

214 % from a maximum of 97.5 % to a minimum of 0 %, where it was stabilized for a period of

215 48 hours, to ensure total desorption. This final status was assumed to correspond to oven

216 dried conditions. Each relative humidity set value was maintained until the recorded change

217 of mass was less than 0.001 %/15 minutes or a period of time of 12 hours had passed (Villani

218 et al. 2014; Montanari et al. 2018). Desorption isotherms were obtained on the cement paste

10
219 systems. From this data, the pore size distribution was obtained using the Kelvin-Laplace

220 equation (Equation 4), which correlates the relative humidity step to the Kelvin pore radius

221 (Brunauer et al. 1968) assuming that the fluid leaving the pores is water.

2𝛾𝑉M
𝑟= (4)
𝑅𝑇𝑙𝑛(𝑅𝐻)

222 where:

223 γ = surface energy of water (0.072284 N/m)

224 Vm = the molar volume of water (1.8·105 mol/m3)

225 R = ideal gas constant (8.3145 N·m/mol·K)

226 T = temperature in K

227 RH = the relative humidity in decimal form

228

229 In principle, the above equation is true for water leaving the system and should be

230 adjusted for pore solution or for the effect of seawater. However, this is complex as the

231 composition of the desorbing fluid is unknown. The changes induced by pore solution or by

232 seawater are likely to be small, because ionic solutions generally tend to slightly increase

233 surface energy and slightly decrease molar volume. As an example, the use of seawater

234 increases the surface energy parameter (γ) by approximately 2 % (Nayar et al. 2014) and

235 decreases the molar volume by approximately 3 % (as the density decreases by 3 %) (Poisson

236 et al. 1980), therefore, the net effect is less than 1 % and is neglected.

237

238 Results and discussion

239 Isothermal calorimetry

240 Heat flow results for the tested cementitious pastes are shown in Fig. 1a and

241 cumulative heat release results are shown in Fig. 1b. Some selected parameters of the heat

242 flow and cumulative heat release curves for the tested cementitious pastes are shown in Table

11
243 4. From the heat flow results, it is evident that the seawater causes an acceleration in the

244 hydration reaction (kinetics) of the cementitious pastes, due to the presence of chloride in the

245 seawater. This acceleration is seen both as a larger silicate peak magnitude and as an earlier

246 time of peak occurrence. As an example, for the cement paste without fly ash, the peak is 35

247 % larger and occurs approximately 1.7 hours earlier. No difference is seen in the heat flow

248 (rate of reaction) at later ages due to the seawater. The use of fly ash results in a retardation

249 as compared to the pastes without fly ash – the peak is of lower magnitude (approximately 17

250 % smaller) and occurs later (3.2 hours later in the paste without seawater and 1.7 hours later

251 in the paste with seawater). The cumulative heat release results indicate that mixtures with

252 seawater have a higher cumulative heat at earlier ages, however, this effect decreases with

253 time. At seven days, cumulative heat in samples with and without seawater is almost identical

254 (approximately 1 % difference in cumulative heat in samples with and without seawater), or,

255 in other words, there is almost no effect of the seawater on the cumulative heat. Mixtures

256 with fly ash show a reduction in the cumulative heat release by approximately 10 %

257 compared to the paste samples without fly ash. For pastes with the same w/cm, the

258 cumulative heat release is correlated with compressive strength (Bentz et al. 2012), as both

259 are controlled by cement hydration. These results are consistent with the findings from

260 literature that show higher strengths for concrete made with seawater at earlier ages and

261 comparable strengths at later ages when compared to concrete made with potable water

262 (Kaushik and Islam 1995; Mohammed at al. 2004; Nishida et al. 2015; Shi et al. 2015;

263 Khatibmasjedi et al. 2018a). Similar isothermal results have been presented elsewhere

264 (Khatibmasjedi et al. 2018b; Younis et al. 2018). In one study focusing on properties of

265 seawater-mixed concrete, isothermal calorimetry of cement pastes (without fly ash) was used

266 to explain why seawater-mixed concrete shows higher early-age strength (Younis et al.

267 2018). In the second study, the main focus was on mortar shrinkage and the isothermal

12
268 calorimetry results (up to 60 hours) were used to explain trends observed in autogenous

269 shrinkage (Khatibmasjedi et al. 2018b).

270

271

272 Figure 1. Heat flow of the tested paste samples (a) and Cumulative heat release of the tested

273 paste samples (b). Replicate samples showed differences less than 3 % for cumulative heat

274 release.

275

276

277

13
278 Table 4. Selected parameters from heat flow and cumulative heat release curves.

Cumulative Cumulative Heat flow, Peak time,

Mixture heat, 3 day heat, 7 day silicate peak* silicate peak*
(J/g) (J/g) (mW/g) (hours)
Cement
260.1 300.7 4.0 8.2
control
Cement
280.3 302.7 5.4 6.5
seawater
Fly ash
231.7 270.8 3.3 11.4
control
Fly ash
247.8 273.5 4.5 8.0
seawater
279 * The silicate peak is the earlier of the peaks in the heat flow curve (Fig. 1a).

280

281 Thermogravimetric analysis (TGA)

282 Bound water contents for the tested cementitious pastes are shown in Fig. 2a and

283 calcium hydroxide contents are shown in Fig. 2b. A logarithmic X-Axis is used in order to

284 show early-age trends clearly. These results are consistent with the isothermal calorimetry

285 results: at early ages, there is an acceleration in the mixtures that contain seawater, reflected

286 in higher amounts of bound water and calcium hydroxide, however, at later ages, there is

287 very little effect of the seawater. As an example, calcium hydroxide amounts in cement

288 pastes with seawater are 2.85 % (by mass of cement) higher than in cement pastes with

289 deionized water at 12 hours; this difference is – 0.06 % (by mass of cement) at 91 days.

290 These results are consistent with literature (higher strengths for concrete made with seawater

291 at earlier ages and comparable strengths at later ages when compared to concrete made with

292 potable water (Kaushik and Islam 1995; Mohammed at al. 2004; Nishida et al. 2015; Shi et

293 al. 2015; Khatibmasjedi et al. 2018a)). At all ages, the bound water content is decreased due

294 to the fly ash, as expected. The use of fly ash leads to greater calcium hydroxide amounts at

14
295 early ages compared to pastes without fly ash; at later ages, this trend is reversed. In pastes

296 without fly ash, the amount of calcium hydroxide increases as the sample ages, whereas in

297 pastes with fly ashes, a decrease in the calcium hydroxide is seen due to the pozzolanic

298 reaction of the fly ash. Friedel‘s salt amounts in the pastes with seawater were also

299 determined (Shi et al. 2017; Qiao et al. 2018a) and are shown in Table 5. These amounts are

300 quite small, ranging from 0.37 – 2.27 % (by mass of paste). The reliability in the

301 quantification of these amounts is low and further testing of these amounts using X-ray

302 diffraction is ongoing. These amounts decrease with age, suggesting that the Friedel‘s salt is

303 not stable under the testing conditions. The Friedel‘s salt amount does not strongly depend on

304 the presence of fly ash. Since the amount of Friedel‘s salt is very small, it can be assumed

305 that most of the chloride binding in these samples is physical chloride binding in the C-S-H.

306 At later ages, pastes with and without seawater do not show any other obvious differences in

307 their TGA response, therefore, it can be concluded that the hydrate phase assemblage is

308 broadly similar.

309

15
310

311 Figure 2. Bound water of the tested paste samples (a) and Calcium hydroxide contents of the

312 tested paste samples (b). Coefficient of variation for calcium hydroxide contents for cement

313 pastes was approximately 1 %.

314

315 Table 5. Friedel‘s salts amounts in cementitious pastes made with seawater.

Friedel‘s salt (% by mass of paste)

Mixture
1 day 3 days 7 days 28 days 91 days
Cement seawater 0.85 2.27 1.02 0.47 0.37
Fly ash seawater 0.75 1.60 1.65 0.32 0.41
316

317 Ionic concentrations from X-ray fluorescence (XRF)

318 Ionic concentrations of Na+, K+, Ca+2, Cl-, and SO4-2 were measured using the XRF.

319 Concentrations of Ca+2 and SO4-2 are in general small (ranging between 0.002 and 0.035

320 mol/L). The values are shown in Table 6. Concentrations of Ca+2 and SO4-2 decrease over

321 time in pastes without seawater; however, trends in seawater are somewhat more complex.

322 The effect of seawater on Ca+2 is not obvious, but seawater increases SO4-2 concentrations by

16
323 up to a factor of eight. Further testing is required to understand the implications of such

324 differences in Ca+2 and SO4-2 concentrations on cement paste behavior.

325 Table 6. Concentrations of Ca+2 and SO4-2 in cementitious pastes made with seawater.

Mixture Ca+2 (mol/L) SO4-2 (mol/L)

0.5 day 3 days 28 days 0.5 day 3 days 28 days

Cement control 0.0052 0.0033 0.0023 0.0088 0.0036 0.0054

Cement seawater 0.0057 0.0026 0.0018 0.0241 0.0275 0.0362

Fly ash control 0.0113 0.0042 0.0022 0.0293 0.0027 0.0050

Fly ash seawater 0.0101 0.0039 0.0024 0.0315 0.0194 0.0235

326 Ionic compositions for the primary cations in the pore solution determined using XRF

327 are shown in Fig. 3. Compositions are converted to mol/L using an assumed pore solution

328 density of 1000 kg/m3 for the pastes made with deionized water and 1025 kg/m3 for the

329 pastes made with seawater (1025 kg/m3 is the seawater density (Poisson et al. 1980)). Fig. 3a

330 shows the evolution of Na+ and Fig. 3b shows the evolution of K+. From Fig. 3a, it is

331 apparent that pastes with seawater have a substantially higher Na+ concentration than samples

332 with deionized (DI) water. This is due to the high Na+ concentration in the seawater. The

333 concentrations of Na+ in the pore solution, which range between 0.70 and 0.80 mol/L for the

334 mixtures with seawater, are higher than the concentrations of Na+ in the seawater (0.48

335 mol/L). This is not a surprising result, as the pore solution concentrates as the water is

336 consumed due to hydration (or is lost due to drying). As the sample hydrates, the Na+

337 concentrations only slightly change, possibly due to the combined effect of alkali uptake and

338 water consumption due to hydration. Pore solutions in pastes without seawater show an

339 increasing Na+ concentration over time, as expected (Vollpracht et al. 2016; Chang et al.

340 2018). These values are approximately five to ten times smaller than in the pore solutions of

341 pastes with seawater. Fly ash does not have a clear or strong effect on Na+ concentrations.

17
342 Fig. 3b shows that seawater leads to an increase (approximately 20 %) in K+ concentrations

343 when compared to samples with deionized water. However, at later ages, the seawater does

344 not have a large effect on K+ concentrations (approximately 5 %). In general, the effect of

345 seawater on K+ concentrations is not as pronounced as it is on Na+ concentrations. This is due

346 to the lower K+ concentration in the seawater compared to the Na+ concentration. K+

347 concentrations increase over time in all pastes. The use of fly ash leads to a decrease in K+

348 concentrations at all ages, presumably due to dilution of the cement.

349

350

18
351 Figure 3. Na+ evolution of the tested pore solutions (a) and K+ evolution of the tested pore

352 solutions (b). Coefficient of variation for Na+ and K+ using the XRF was approximately 5 %

353 (Chang et al. 2018).

354

355 Ionic compositions for the primary anions are determined using XRF (Fig. 4). Fig. 4a

356 shows the evolution of Cl- and Fig. 4b shows the evolution of OH-. Pastes with seawater have

357 a much higher Cl- concentration in the pore solution than pastes with deionized water (100 –

358 200 times higher, as the latter has almost no Cl- in the pore solution) because of the high Cl-

359 concentration in the seawater. The concentrations of Cl- in the pore solution are initially

360 between 0.60 and 0.70 mol/L for the pastes with seawater. These values are somewhat higher

361 than the concentrations of Cl- in the seawater, which is 0.58 mol/L. This is because the pore

362 solution concentrates as the water is consumed due to hydration. The concentration of Cl- in

363 the pore solution is reduced over time, likely due to chloride binding. As mentioned earlier,

364 very little Friedel‘s salt forms in these systems and the amount of Friedel‘s salt reduces over

365 time. Therefore, the reduction in the Cl- concentrations is most likely due to the physical

366 absorption of Cl- in the C-S-H. If several assumptions (pore solution amount at 12 hours = 20

367 g; pore solution amount at 28 days = 10 g; and 60 g C-S-H forms for every 100 g of hydrated

368 cement paste at 28 days; all the Cl- reduction is due to absorption on the C-S-H), based on the

369 TGA data and cement chemistry, are made, the magnitude of the physical absorption can be

370 calculated to be approximately 5 mg Cl-/g C-S-H (for the cement paste with seawater at 28

371 days). This value compares favorably with values from literature of 3 – 18 g Cl-/mg C-S-H

372 for similar free chloride amounts (Hirao et al. 2005; Florea and Brouwers 2012; Qiao et al.

373 2018b). The effects of the absorption of Cl- on the C-S-H are unclear and further

374 investigation is required. Cl- concentrations in samples with fly ash are slightly

375 (approximately 5 %) higher than in samples without fly ash. Pastes with seawater have

19
376 similar OH- concentrations as compared to pastes with deionized water at early ages (less

377 than 5 % difference), although at later ages, pastes with seawater have higher OH-

378 concentrations (difference between 30 – 50 %). This is most likely attributed to the decrease

379 in the Cl- concentrations at later ages. Fly ash leads to an approximately 20 % reduction in

380 the OH- concentrations, likely due to dilution and possibly due to differences in Cl- binding.

381

382

383 Figure 4. Cl- evolution of the tested pore solutions (a) and OH- evolution of the tested pore

384 solutions (b). Coefficient of variation for OH- using the XRF was approximately 5 % (Chang

385 et al. 2018); values for Cl- were not tested.

20
386 Prediction of pore solution ionic concentrations

387 The Na+ concentrations in pastes with seawater may be predicted using the Na+

388 concentration in seawater (0.479 mol/L) and the free water in these pastes. At mixing, it is

389 assumed that all the water is free, and corresponds to w/cm 0.40. The free water at age may

390 be computed as the difference between the original free water and the bound water

391 (determined using TGA and shown in Fig. 2b). The contribution of the seawater to Na+

392 concentrations in pastes with seawater is calculated by multiplying the Na+ in seawater with

393 the ratio of the original free water to the free water at the given age. Na+ concentrations in the

394 pastes with seawater may be computed as the sum of the Na+ that is coming from the

395 seawater and the Na+ concentrations in pastes with deionized water. The results are shown in

396 Fig. 5a. At 12 hours, the agreement between the predicted and measured Na+ is excellent. As

397 the pastes hydrate, the difference between measured and predicted Na+ concentrations

398 increases. This discrepancy is likely due to the uptake of Na+ in C-S-H (Hong and Glasser

399 1999; Hong and Glasser 2002). The uptake is calculated to be between 0.02 – 0.05 mol/L at

400 12 hours and between 0.21 – 0.28 mol/L at 28 days for the pastes with seawater. If we

401 assume that 60 g C-S-H forms for every 100 g of hydrated cement paste at 28 days, then the

402 Na+ uptake is calculated to be approximately 2 mg Na+/g C-S-H (or 0.1 mM/g C-S-H), which

403 is lesser than the Cl- binding calculated in the previous section. Values from literature vary,

404 depending on Ca/Si values of C-S-H and Na+ solution concentration, but seem to range

405 between 0.1 – 0.3 mM/g C-S-H (Hong and Glasser 1999; Hong and Glasser 2002). Similar

406 calculations were performed for Cl- and the binding was found to be approximately 7 mg Cl-

407 /g C-S-H, which is higher than the amount determined in the previous section. Due the

408 various assumptions made, these numbers are likely to be approximate, and should be

409 considered with some caution. While the results shown here need to be validated for more

410 materials, these preliminary results suggest that a certain amount of Na+ and Cl- ions are

21
411 incorporated in C-S-H that is formed in seawater-mixed pastes, and this C-S-H is different

412 from C-S-H in pastes without seawater.

413 The reactivity of fly ash at ages below 28 days is generally low (Suraneni et al. 2016;

414 Durdzinski et al. 2017), therefore, the ionic concentrations in the fly ash pastes can be studied

415 assuming simple dilution, that is, the concentration of a particular ion in the fly ash pastes can

416 be estimated by multiplying the concentration of that ion in the cement pastes by the dilution

417 of the cement (one minus the mass fraction of the fly ash in the system) (Montanari et al.

418 2018). This is done for both pastes made with seawater and deionized water and the results

419 are shown in Fig. 5a and Fig. 5b for Na+, K+, Cl-, and OH-. Fig. 5 shows a strong correlation

420 between ionic concentrations measured by XRF and those calculated by dilution. For the fly

421 ashes pastes with deionized water, there is a 1:1 correlation, suggesting that dilution alone

422 explains the changes in concentration when cement is replaced with fly ash. These results are

423 consistent with those reported elsewhere (Montanari et al. 2018) and suggest that the

424 reactivity of fly ash is quite low at 28 days. Exploring the validity of this finding for other

425 cements and fly ashes is ongoing. For the fly ashes pastes with seawater, while the correlation

426 is strong, there is a deviation from the 1:1 line, suggesting that simple dilution does not fully

427 explain the changes in ionic concentrations when cement is replaced with fly ash. This could

428 be because of an acceleration in the fly ash reaction in pastes with seawater, or a synergistic

429 effect between fly ash and seawater (Khatibmasjedi et al. 2018a; Khatibmasjedi et al. 2018b),

430 however, isothermal calorimetry and TGA results in this work do not show an obvious

431 acceleration of the fly ash in seawater pastes.

22
432

433

434 Figure 5. Comparison of measured and predicted ionic concentrations for Na+ (a) and

435 Comparison of measured ionic concentrations and ionic concentrations predicted by dilution

436 for fly ash pastes (b).

437

438 Other pore solution properties

439 Two other properties of the pore solution that are of interest are the pore solution pH

440 and the pore solution ionic strength. The pH was calculated using the logarithm of the OH-

441 concentrations and is shown in Fig. 6a. As activity is not taken into account, these values may

23
442 overestimate the actual pH (Vollpracht et al. 2016). The pH may also directly be measured

443 using a pH meter, however, this is difficult for the small amounts for pore solution that were

444 extracted in this study. As the pH is calculated from the OH- concentrations, the trends in the

445 pH are the same as the trends in the OH- concentrations. At early ages, the seawater has only

446 a slight effect on the pH (< 0.05 units), however, at later ages, the pH is greater in pastes

447 mixed with seawater, with the difference in values for pastes with and without seawater being

448 between 0.14 – 0.18 units. Fly ash results in a reduction of the pH (between 0.06 – 0.1 units),

449 as expected (Thomas et al. 2011; Vollpracht et al. 2016). These results show that concrete

450 mixed with seawater would likely have higher OH- and alkali concentrations. The ionic

451 strength is calculated by summing the ionic strengths of the individual species in the pore

452 solution and is shown in Fig. 6b. The ionic strength increases with age, as the pore solution

453 concentrates. The use of seawater causes a large increase in the ionic strength – pastes made

454 with seawater have an ionic strength 3 – 4 times greater than pastes made with deionized

455 water. This is largely due to the increased amounts of Na+ and Cl- coming from the seawater.

456 Fly ash causes a slight (approximately 10 %) reduction in the ionic strength, presumably due

457 to dilution. The greater ionic strengths in pastes with seawater could lead to concerns

458 regarding leaching when such concretes are exposed to groundwater; however, and this needs

459 to be investigated further, however, the typical application for such concretes is likely to be in

460 marine regions or exposed to seawater.

24
461

462

463 Figure 6. pH evolution of the tested pore solutions (a) and Ionic strength evolution of the

464 tested pore solutions (b).

465

466 The evolution of the electrical resistivity of the tested pore solutions is shown in Fig.

467 7. The electrical resistivity of samples with seawater is approximately 40 – 50 % lower than

468 in samples with deionized water, as the pore solution is considerably more ionic due to the

469 seawater. Pastes with deionized water show a reduction (approximately 40 %) in the

470 electrical resistivity over time due to hydration, as expected (Chang et al. 2018). Pastes with

25
471 seawater show a smaller decrease in the resistivity over time (approximately 25 %), likely

472 because the resistivity is already lower due to the ions in the seawater and the decrease that

473 would occur due to hydration is reduced. Samples with fly ash have a higher resistivity

474 (approximately 20 %) than samples without fly ash, likely due to the dilution of the cement

475 by the fly ash. The pore solution resistivity was also directly measured using a resistivity

476 meter, using techniques outlined elsewhere (Chang et al. 2017; Chang et al. 2018), and the

477 values computed from XRF and the values measured using the resistivity meter were quite

478 similar (average absolute error of approximately 4 %).

479

480 Figure 7. Evolution of the resistivity of the tested pore solutions. Values computed from XRF

481 and values measured using the resistivity meter had average absolute error of approximately

482 4 %.

483

484 Dynamic vapor sorption (DVS)

485 The cumulative and differential pore size distributions of the cement paste samples

486 with seawater and deionized water (at 91 day equivalent age) are shown in Fig. 8a and Fig.

487 8b, respectively. It should be noted that this technique only provides information on pores

488 between 1 nm and 42 nm in size, so information about the largest pores is not obtained. The

26
489 tested pastes have a very similar total porosity (0.166 – 0.167 ml/g), likely because they have

490 the same w/cm and similar degree of hydration values (less than 5 % difference as calculated

491 from the calcium hydroxide and bound water contents). The paste with seawater has a

492 slightly finer pore structure compared to the paste with deionized water. The same conclusion

493 is obtained from the differential pore size distribution shown in Fig. 8b. While fly ash

494 samples were not studied, one may tentatively conclude that the use of seawater results in

495 slightly finer porosity, however, this topic needs to be further explored.

496

497

27
498 Figure 8. Cumulative pore size distribution (ml water/g sample) of the cement paste samples

499 (a) and Differential pore size distribution (ml water/g sample-nm) of the cement paste

500 samples (b).

501

502 The results from the testing of hydration, pore solution, and porosity suggest that

503 there are three major changes when cement pastes are made with seawater: a) an initial

504 acceleration in the hydration, which is reduced at later ages; b) an incorporation of Cl- in the

505 C-S-H (approximately 5 mg Cl-/g C-S-H); and c) increase in pore solution ionic strength,

506 specifically in sodium, chloride, and hydroxide concentrations. These results suggest that

507 unreinforced concrete or concrete reinforced with FRP could potentially prepared with

508 seawater. However, the durability of such concretes would have to be studied in detail.

509 Specifically, issues due to alkali silica reaction (due to greater alkalis in pore solution) and

510 sulfate attack (due to greater sulfate in the system) should be addressed. The findings

511 obtained here including the pore solution concentrations of alkali and sulfates could help with

512 better understanding the results from durability testing (which is currently ongoing).

513

514 Conclusions

515 The hydration, pore solution, and porosity of cementitious pastes made with seawater

516 were compared to the properties of pastes made with deionized water. These pastes were

517 made with cement and cement with a 20 % fly ash replacement. The results revealed that the

518 seawater has an accelerating effect on hydration kinetics at early ages (silicate peak is

519 accelerated 1.7 – 3.4 hours), but this effect is negligible after seven days of hydration. Fly ash

520 causes a slight retardation of the heat flow at early ages (silicate peak is retarded 1.5 – 3.2

521 hours) and an approximately 10 % reduction in cumulative heat release compared to pastes

522 with cement. Friedel‘s salt formation in pastes with seawater at later ages is minor (0.37 –

28
523 2.27 g/100 g paste) and the major difference in the hydrated phases between pastes with

524 seawater and deionized water is likely the incorporation of chloride in the C-S-H

525 (approximately 5 mg Cl-/g C-S-H). The pore solution in systems with seawater is more ionic

526 (approximately 3 – 4 times greater ionic strength), specifically in sodium, chloride, and

527 hydroxide, although trends with age can be complex. The concentrations of potassium and

528 hydroxide ions in the pore solutions are lower in pastes with fly ash when compared to pastes

529 without fly ash. Total porosity in cement pastes with and without seawater are rather similar

530 (values between 0.166 – 0.167 ml/g), however, the paste with seawater has a slightly finer

531 pore structure compared to the paste with deionized water.

532

533 Acknowledgements

534 The authors would like to express their gratitude to Infravation for funding under

535 project 31109806.005-SEACON, Qatar Foundation grant # NPRP9-110-2-052, and ACI

536 Foundation’s Concrete Research Council. The statements made herein are solely the

537 responsibility of the authors.

538

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