Journal Pre-proof

Increasing the early strength of high-volume Hwangtoh–cement systems using

bassanite

Run-Sheng Lin, Ki-Bong Park, Xiao-Yong Wang, Gui-Yu Zhang

PII: S2352-7102(19)31027-7
DOI: https://doi.org/10.1016/j.jobe.2020.101317
Reference: JOBE 101317

To appear in: Journal of Building Engineering

Received Date: 24 June 2019

Revised Date: 25 February 2020
Accepted Date: 27 February 2020

Please cite this article as: R.-S. Lin, K.-B. Park, X.-Y. Wang, G.-Y. Zhang, Increasing the early strength
of high-volume Hwangtoh–cement systems using bassanite, Journal of Building Engineering (2020), doi:
https://doi.org/10.1016/j.jobe.2020.101317.

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Author statement

Run-Sheng Lin: Conceptualization, Methodology, Validation, Experiment, Writing-

Original draft preparation, Writing- Reviewing and Editing

Ki-Bong Park: Conceptualization, Writing- Original draft preparation

Xiao-Yong Wang: Conceptualization, Methodology, Validation, Writing- Reviewing

and Editing, Supervision

Gui-Yu Zhang: Conceptualization, Experiment

 1 Increasing the early strength of high-volume Hwangtoh–cement

2 systems using bassanite

3 Run-Sheng Lin, Ki-Bong Park, Xiao-Yong Wang,* and Gui-Yu Zhang

4 College of Engineering, Department of Architectural Engineering, Kangwon National

5 University, 200-701 Chuncheon-si, Republic of Korea

6 *Corresponding author: Xiao-Yong Wang

7 E-mail address: wxbrave@kangwon.ac.kr (Xiao-Yong Wang)

8 Abstract:

9 Calcined Hwangtoh (HT) clay is a potentially viable supplementary cementitious

10 material. However, using large amounts of HT significantly reduces the early strength

11 of concrete, and this problem has yet to be addressed. We explored the effectiveness

12 of improving the early strength of cement–HT systems by using bassanite (calcium

13 sulfate hemihydrate, CaSO4·0.5H2O) to activate HT. The effects of different contents

14 (0–4 wt.%) of bassanite on the mechanical properties, hydration reaction, and

15 microstructure of high-volume (45 wt.%) HT–cement systems were investigated. The

16 experimental results show that the addition of bassanite to HT–cement systems

17 facilitates the formation of ettringite crystals in the early stage, thereby increasing the

18 early strength. After one day, the compressive strength of the paste with a bassanite

19 addition of 3% increased by 82.3% compared with the paste without bassanite, and no

20 significant effect on the later strength was observed. However, for a bassanite addition

21 of >4%, excessive sulfate causes poor volume stability, leading to substantial

22 reductions in the compressive strength at later stages.

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23 Keywords: early compressive strength; calcined Hwangtoh; bassanite; sulfate;

24 concrete

25

26 1. Introduction

27 Presently, the usage of blended Portland cements is increasing rapidly in several

28 countries because of the clinker-saving and energy-saving potentials of these cements

29 [1]. The addition of traditional supplementary cementitious materials (SCMs), such as

30 fly ash, slag (ground granulated blast-furnace slag), and silica fume, to concrete can

31 increase its impermeability and strength [2][3][4]. However, in the long term, more

32 steel is being recycled as the demand for it dwindles, potentially limiting the supply of

33 slag. Meanwhile, because of environmental emission problems in thermal power

34 plants, the supply of fly ash is also in doubt. However, clay is a relatively abundant

35 material in most parts of the world and has a high pozzolanic activity after calcination

36 between 700 and 850 °C, making it a very promising SCM [5][6][7]. Numerous

37 recent studies have shown that calcined clay partially replacing ordinary Portland

38 cement (OPC) offers properties that are equivalent to or even better than those of

39 traditional SCMs for the improvement of cementitious materials [6][8]. At the same

40 time, the global warming potential (GWP) of calcined clay is between 0.33–0.43 CO2

41 kg/kg [9][10][11][12], which is much lower than the GWP of cement (0.83 CO2 kg/kg)

42 [13].

43 Hwangtoh (HT), as an eco-friendly material that is abundant in Korea, is

44 receiving increasing attention from researchers. HT is a clay produced by the

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45 weathering of rocks [14]. Because of its good disinfection, deodorization, and

46 purification capabilities, HT has been used in certain medical and cosmetic

47 applications in Korea [15]. Recently, with increasing interest in healthy housing, HT

48 has garnered considerable attention as a potential building material [16][17][18].

49 Previous studies [8][19][20] have shown that the addition of calcined HT in cement

50 can significantly increase the compressive strength at later stages, as a result of the

51 filler effect [21] and the pozzolanic reaction [22] of the HT powder. However, because

52 the pozzolanic reaction proceeds relatively slowly, the increase in strength only occurs

53 during the later stages of hydration. When the water-to-binder ratio (w/b) of the pastes

54 is 0.5, and the replacement quantity of HT is 10%, its three-day compressive strength

55 (24 MPa) is slightly higher than that of OPC paste (22 MPa). The compressive

56 strength of a sample with 20% HT replacement (19 MPa) is lower than that of OPC

57 [8].

58 Several techniques are used to increase the early strength of concrete containing

59 SCMs; these techniques include mechanical grinding [23][24], increasing the curing

60 temperature [25], and chemical activation [26][27][28][29]. Chemical activation

61 methods include alkali excitation and sulfate excitation. Alkali excitation is primarily

62 used to accelerate the decomposition of the glass phase through an alkali to increase

63 the early strength. Sulfate excitation involves the reaction of sulfates with the

64 aluminum phase to produce large amounts of ettringite (AFt) in the early reaction.

65 The formation of ettringite helps to increase the early strength [28].

66 The use of sulfate to increase early strength is more practical and economical

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67 than other activation methods, while also conforming to actual engineering needs.

68 Moreover, the content of sulfate in OPC may be generally sufficient, but it is not

69 sufficient in concrete with admixtures. A study by Poon et al. [30] showed that, in

70 mortar with 55% fly ash added, after adding 10% anhydrite, the three-day

71 compressive strength increased by ∼70%. Xu and Sarkar's study [31] showed that the

72 strength of pastes containing from 30% to 60% low-calcium fly ash increased

73 significantly after adding from 3% to 6% gypsum. Herrera-Mesen et al. [32] studied

74 the early performance of gypsum on a sprayed cementitious matrix, and the results

75 revealed that an appropriate addition of gypsum can improve the early strength of

76 sprayed cement. Although there has been considerable research on methods of

77 improving the early strength of concrete by using sulfate, there is still no research

78 examining the use of sulfate to improve the early strength of HT concrete, especially

79 regarding the optimal amount of sulfate to add.

80 In this study, the effects of different levels of bassanite (calcium sulfate

81 hemihydrate, CaSO4·0.5H2O) on a HT–OPC system were investigated. Calcined HT

82 was added at an amount of 45%, with w/b = 0.5, and the bassanite content was 0%–

83 4%. The mechanical properties and hydration reactions of the samples were analyzed

84 by a compressive strength test, X-ray diffraction (XRD), isothermal calorimetry,

85 attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR),

86 scanning electron microscopy (SEM), and mercury intrusion porosimetry (MIP).

87

88 2. Experimental details

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 89 2.1. Materials

90 The cement used in this study was Type I OPC produced by

91 Sung Shin Cement Company. The HT was prepared according to the method

92 previously described [7][8]; namely, it was calcined for one hour at 800 °C in a muffle

93 furnace for one hour, then rapidly cooled in air. The XRD pattern of calcined HT

94 (Figure 1) shows that the kaolinite–montmorillonite peak (2θ = 12.37°) essentially

95 disappears after calcination. This is consistent with the results of Go et al. [19]. EP

96 grade bassanite was used as an additive. The chemical compositions of the cement,

97 HT, and bassanite are listed in Table 1. Through particle size distribution (PSD)

98 analysis (Figure 2), the average particle sizes of cement, HT, and bassanite were

99 measured at 18.5, 12.2, and 15.8 µm, respectively. Their average particle sizes are

100 essentially identical.

101 2.2. Mix design information

102 All the pastes were prepared with w/b = 0.5. The experimental mix ratio program

103 is given in Table 2, illustrating that the replacement ratio of HT was 45% and the

104 bassanite content (0%–4%) was increased in increments of 1%.

105 2.3. Methods

106 The pastes were mixed by a mechanical stirrer and poured into molds with

107 dimensions of 40 × 40 × 160 mm. The molds were removed after one day and the

108 samples were wrapped with a film for sealed curing. Then, the samples were placed in

109 a 20 °C curing chamber, and the compressive strength of the samples was tested after

110 1, 3, 7, and 28 days, according to ASTM C349.

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111 The particle size distribution of the powders was measured using a Malvern

112 Mastersizer 3000 instrument, which uses low-angle laser-scattering technology to

113 measure particle size distributions from 0.1 to 1000 µm. The dispersant for all

114 samples was deionized water. The test time for each sample was 10–12 s; the tests

115 were performed three times, and the average value was used.

116 The chemical composition of the powders was analyzed with X-ray fluorescence

117 (XRF, ZSX Primus II). The XRF fused cast bead method (ISO 12677:2003) was used

118 in the sample preparation system (XRF-Scientific, Canada). Beads were prepared by

119 mixing ∼4 g each of lithium tetraborate and lithium metaborate with a test sample

120 (∼0.8 g). The resistance furnace was heated to a fixed temperature of (1025±25) °C.

121 The solvent exchange method was used for hydration stoppage of the hydrated

122 samples [33]. We ground the 5 g of hydrated samples into a powder. The powder was

123 then immersed in 150 ml of isopropanol (CP grade) for 15 min. The suspension was

124 vacuum filtered, rinsed once with isopropanol, and rinsed twice with ether (CP grade).

125 The filtered solids were dried in a drying oven at 40 ℃ for 8 min. Finally, the dried

126 powder was stored in a vacuum dryer. Testing of samples should be performed as

127 soon as possible, preferably within 2 days [33].

128 X-ray powder diffraction analysis was conducted on the raw materials and the

129 samples (after 1 day and 28 days of curing) after the hydration stoppage treatment.

130 PANalytical X'pert pro MPD diffractometers with Cu Kα radiation (λ = 1.5407 Å)

131 were used. The electric current and the working voltage were 30 mA and 40 kV,

132 respectively. The samples were scanned from 5° to 80° (2θ) in incremental steps of

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133 0.013°, with a cumulative time per step of 8.67 s.

134 The reaction heat of all samples was measured at 20 °C using a TAM Air

135 isothermal calorimeter. Prior to testing, the eight calorimeter cells of the TAM Air

136 instrument were calibrated simultaneously [34]. Glass (specific heat capacity = 0.8

137 J g−1 K−1) was used as the reference material for heat capacity [35]. To minimize

138 environmental thermal interference, the indoor temperature was maintained at ∼20 °C.

139 After mixing with a mechanical mixer, 5 g of paste was added to the ampoule using a

140 plastic dropper and the ampoule was then quickly placed into the calorimeter. It

141 should be noted that, when extracting the sample, the pastes are manually stirred at

142 the same time to ensure that the sample is evenly selected. The measurement time was

143 72 h.

144 The ATR-FTIR spectrum of the samples (after 1 day and 28 days of curing) after

145 hydration stoppage was measured using a Frontier spectrometer (PerkinElmer) with a

146 resolution of 0.4 cm−1. Background scanning of the ZnSe–diamond crystal was

147 performed before each measurement. The spectra were collected at room temperature

148 in the range of 4000–500 cm−1 and each sample was scanned 32 times. PerkinElmer

149 software was used to perform spectral normalization and baseline correction.

150 Microscopic observation of the sheet samples was performed using a

151 high-resolution field emission scanning electron microscope (S-4300, Hitachi) with an

152 acceleration voltage of 1.5 kV and an emission current of 7000 nA. The specimens

153 were broken, and the inner sheet was selected for testing. Prior to microscopic

154 observation, the surface of the samples was coated with platinum for 30 min using a

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155 Hitachi E-1010 ion sputterer.

156 MIP of the samples was performed using an Autopore IV series automatic

157 mercury porosimeter with a maximum pressure of 414 MPa. The samples were

158 smashed, and irregular particles with a diameter of ∼5 mm were selected. We soaked

159 the samples in isopropanol for 3 days and then placed them in a vacuum oven for 7

160 days to ensure that the samples were sufficiently dry. Then, the samples (∼4 g) were

161 placed into a dilatometer for testing. The test process consisted of two stages, one at

162 low pressure and the other at high pressure.

163

164 3. Results and discussion

165 3.1. Mechanical strength

166 When a high-volume mineral admixture is added to OPC, the sulfate content is

167 often insufficient; therefore, the system reacts in an undersulfated manner [36][37].

168 Several studies [36][38][39] have shown that aluminum lowers the formation rate of

169 the main hydration phase of tricalcium silicate. However, no consensus has been

170 reached regarding the kinetics of the reaction. The effect of aluminum on the

171 hydration of tricalcium silicate also depends on the simultaneous presence of sulfate,

172 which slows the aluminate reaction. There are two main assumptions in this case:

173 First, the reaction may be limited by the hydration product layer, which may be

174 ettringite or AFm [40][41]. However, it is possible that the adsorption of sulfate ions

175 and calcium ions on the active dissolution site of the aluminate slows the reaction

176 [42][43].

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177 Figure 3a shows the compressive strength values of the samples at 1, 3, 7, and 28

178 days. The relative compressive strengths compared with the HT45S0 reference are

179 shown in Figure 3b. Because the reactivity of HT is significantly lower than that of

180 OPC, the compressive strength of the OPC–HT systems analyzed in this study was

181 significantly lower than that of pure OPC pastes. At a curing age of 1 day, the addition

182 of bassanite significantly increased the compressive strength of the OPC–HT pastes;

183 when 3% bassanite was added, the compressive strength was maximized (5.34 MPa),

184 increasing by 82.3% compared with the HT45S0 reference (2.93 MPa). Proper

185 sulfation at an early stage may contribute to the formation of ettringite, which

186 increases the early strength of the paste [44]. Meanwhile, sulfate ions can accelerate

187 the C3S reaction, according to Minard’s study [42]. However, when the bassanite

188 addition reached 4%, the strength (3.41 MPa) only increased by 16.3%. The

189 compressive strength of HT45S3 exceeded that of the other samples at 1, 3, and 7

190 days, but the addition of ≤3% bassanite did not significantly increase the compressive

191 strength at 28 days of curing. In contrast, after adding 4% bassanite, the compressive

192 strength decreased. This may be because the addition of excess bassanite results in an

193 excess of sulfate in the system; this would cause the ettringite to continue growing in

194 the later stage, resulting in volume expansion of the paste and changes in the pore

195 structure [45].

196 3.2. Heat of hydration

197 Figure 4a shows the evolution rate of the hydration heat of the pastes within

198 three days. The exothermic curve of HT45S0 shows that a large amount of HT

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199 powder was added to the OPC; this resulted in a distinct aluminate exothermic peak at

200 ∼8 h, which overlapped with the C3S reaction peak. This may be due to the system

201 reacting in an undersulfated manner [36][37][46]. When bassanite was added to the

202 OPC–HT system, its exothermic curve was significantly affected by the bassanite

203 content. The dissolution of sulfate ions from bassanite into the liquid phase had a

204 delayed effect on the aluminate hydration. Because of the large amount of aluminum

205 phase in HT powder, proper sulfation in the OPC–HT system promotes reaction of the

206 aluminate with the sulfate to form ettringite, thus contributing to the improvement in

207 the early compression strength. Figure 4a shows that the aluminate peak was delayed,

208 and the intensity of the peak decreased with increasing sulfate content. This may be

209 limited by the hydration product layer [40][41] or by the adsorption of sulfate ions

210 and calcium ions on the active dissolution site of the aluminate [42][43]. A study by

211 Quennoz and Scrivener [47] showed that the mechanism of C3A dissolution rate

212 control is related to the absorption of sulfate ions and the available space on the

213 surface. Figure 4b clearly shows that, as the content of bassanite increases, the

214 occurrence of the aluminate peak is regularly delayed; this phenomenon is similar to

215 that observed by Quennoz and Scrivener [36]. Figure 4c shows the cumulative

216 hydration heat of the pastes. As the sulfate content in the system increases, the

217 cumulative hydration heat value also increases. Moreover, Figure 4d shows that there

218 is an clear linear relationship between the cumulative hydration heat and the

219 compressive strength at curing ages of 1 and 3 days.

220 3.3. X-ray diffraction

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221 The phase composition in the pastes at 1 and 28 days of hydration was studied,

222 and the XRD patterns are shown in Figure 5. When the pastes were hydrated for 1 day,

223 a large amount of portlandite crystals was produced (2θ = 18°). After 28 days of

224 hydration, the intensity of the portlandite peak of the OPC sample continued to

225 increase, while that of the portlandite peak of the cement–HT pastes decreased

226 significantly. This is because the pozzolanic reaction of HT consumes a large amount

227 of calcium hydroxide (CH) [8].

228 The characteristic peaks of ettringite (AFt) were observed at diffraction angles of

229 2θ = 9.1°, 15.8°, and 22.9°. It can be clearly seen that, although the amount of cement

230 clinker in the OPC–HT pastes is considerably less than that in the OPC sample, the

231 strength of the ettringite peak is similar at 1 day. This also explains why adding

232 bassanite to the cement facilitates early hydration. The aluminum phase in HT

233 promotes the growth of ettringite, thus increasing the early strength. After 28 days, as

234 shown in Figure 5b, the intensity of the ettringite peak increased with increasing

235 bassanite addition, and this was particularly obvious for HT45S4. Studies conducted

236 by Tian and Cohen [48] have shown that, in the later stage of hydration, excessive

237 sulfate leads to the formation of a large amount of poorly crystallized ettringite and

238 the recrystallization of gypsum in the pastes, resulting in poor volume stability and,

239 thus, expansion cracking. The mechanism of the expansion and cracking of cement

240 concrete remains unclear [48][49]. However, this is probably the reason why an

241 excessive addition of bassanite leads to a significant reduction in the later

242 compressive strength.

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243 At 1 day and 28 days, a small amount of monosulfoaluminate (Ms) was observed

244 at a position for which 2θ = 19.7°. In addition, a strätlingite (C2ASH8) phase (2θ =

245 7.1°) was observed in the cement–HT pastes at 28 days. Both Ms and strätlingite are

246 types of AFm phases [3][49][50][51]. The intensity of the strätlingite peak decreases

247 with the increase in bassanite content. It has been reported [52][53] that the formation

248 of strätlingite contributes to the development of strength in high-alumina cement.

249 Jackson et al. [54] found strätlingite in 1900-year-old Roman Empire mortar and

250 showed that strätlingite crystals can hinder the propagation of cracks, thereby

251 improving the durability of concrete.

252 3.4. ATR-FTIR spectra

253 The ATR-FTIR spectra of all samples at 1 day and 28 days are shown in Figure 6.

254 Table 3 lists the characteristic wavenumbers and related functional groups of the

255 materials. The absorption peak with a wavenumber of 3640 cm−1 is the O–H

256 stretching vibration of Ca(OH)2. For the OPC–HT pastes, after 28 days of curing, it

257 was found that the absorption peak of Ca(OH)2 almost disappeared, which is

258 consistent with the results observed by XRD (Section 3.3). The broad absorption peak

259 at 3390–3457 cm−1 is caused by the stretching vibration of H2O. After 1 day of

260 curing, it was found that the absorption peak of the pastes with added bassanite was

261 more obvious than that of the HT45S0 sample. The reason for this may be that the

262 addition of bassanite promotes hydration of the pastes, leading to an increase in bound

263 water; alternatively, the reason may be due to the vibration caused by the water in

264 sulfate. The absorption band of sulfate is usually in the range of 1100–1200 cm−1. As

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265 the amount of bassanite added increased, the sulfate peak became more pronounced.

266 Because many forms of sulfate absorption peaks are generated at this position, and the

267 asymmetrical stretching vibration of the Si042– group is also present at this position,

268 this results in a large amount of overlap [55][56]. Therefore, it is very difficult to

269 study the absorption peak of this region by FTIR. The wavenumbers 938–997 and

270 600–853 cm−1 are the Si–O–Si (Si–O–Al) asymmetrical stretching vibrations in

271 C(A)SH and the bending vibration of Al–O–H, respectively. As hydration progresses,

272 it can be seen that the intensity of the absorption peak of Si–O–Si (Si–O–Al) is more

273 obvious and covers the absorption peak of sulfate. Moreover, compared to the OPC

274 paste, the Si–O–Si (Si–O–Al) absorption peak of the OPC–HT pastes shifts to a

275 higher wavenumber, which may be due to the change in the Ca/Si ratio of C(A)SH

276 [8].

277 3.5. MIP

278 The pore distribution of the samples was measured at 28 days by MIP. As shown

279 in Figures 7a and 7b, when 1%–3% bassanite was added, there was less cumulative

280 intrusion volume compared to that of the OPC–HT paste without bassanite. Moreover,

281 it can be seen from the pore size distribution curve that a proper sulfation of OPC–HT

282 pastes can refine the pores, especially for samples HT45S2 and HT45S3. However,

283 when excessive bassanite was added, as in HT45S4, it was found that the cumulative

284 intrusion volume of the paste increased, and the size of the capillaries was not

285 improved. This may be due to excess sulfates leading to poor volume stability in the

286 system and changes in pore structure [45]. This may also be the reason why an

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287 excessive addition of sulfates will reduce the later compressive strength. Figure 7c

288 shows the linear relationship between the compressive strength of the pastes and the

289 cumulative intrusion volume at 28 days. However, it is clear that the compressive

290 strength and cumulative invasion volume have no linear relationship with the amount

291 of bassanite added, as the addition of 3% bassanite is the optimal amount.

292 3.6. Microscopic image

293 Figure 8 shows microscopic images of the samples observed by SEM at ae

294 curing age of 1 day. In the pure cement paste (Figure 8a), numerous hexagonal

295 flake-like portlandites can be observed, whereas in the OPC–HT pastes, no similar

296 hexagonal structure was observed. The portlandite may be covered by other hydration

297 products in the OPC–HT system. In the HT45S3 sample, numerous acicular

298 ettringites can be observed (Figure 8b). This is because the high ratio of sulfate and

299 aluminate leads to numerous ettringite crystals being precipitated, thus contributing to

300 early strength. However, in the pastes without bassanite, it was observed that the

301 ettringite crystals became short and the AFm phase was precipitated (Figure 8c). This

302 is due to a decrease in the ratio of sulfate to aluminate and an increase in the

303 concentration of aluminate in the solution, which makes ettringite unstable and

304 gradually transforms it into AFm. In Figure 8d, the transformation of ettringite into

305 AFm can be observed clearly.

306

307 4. Conclusions

308 The effectiveness of bassanite in improving the early strength of high-volume

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309 HT–cement systems was investigated in this study. The replacement amount of HT

310 was 45%, and w/b = 0.5. The compressive strength results demonstrate that the

311 addition of an appropriate amount of bassanite can increase the early strength of the

312 pastes, while having no notable effect on the later strength. The addition of 3%

313 bassanite increased the 1-day compressive strength of the pastes by 82.3%. However,

314 when >4% bassanite was added, the 28-day compressive strength was significantly

315 reduced.

316 Bassanite retards the hydration of aluminate in the pastes, and the cumulative

317 hydration heat increases with increasing sulfate content in the system. There is a clear

318 linear relationship between the early cumulative hydration heat and the early-age

319 compressive strength. The XRD diffraction pattern reveals that the HT–cement

320 system formed a large amount of ettringite in the early stage, thereby increasing the

321 early strength. The ettringite peak intensity increases with increasing bassanite

322 addition. During the later hydration, the formation of ettringite may be the reason for

323 the reduction in strength after excessive sulfation. Furthermore, the formation of

324 strätlingite crystals was discovered.

325 The addition of an appropriate amount of bassanite can refine the pores of the

326 28-day HT–cement pastes. However, excess sulfate causes an adverse effect on the

327 pore structure of the system. This may be because, in the later stage of hydration,

328 excess sulfate will cause a large amount of crystallized ettringite and recrystallization

329 of gypsum in the paste, resulting in poor volume stability. There is a linear

330 relationship between the compressive strength of the pastes and the cumulative

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331 intrusion volume at a curing age of 28 days.

332 Using sulfate is effective in increasing the early strength of high-volume HT–

333 cement systems. The amount of sulfate addition significantly affects the mechanical

334 properties, hydration process, and microstructure of the matrix.

335

336 Acknowledgments

337 This research was supported by the Basic Science Research Program through the

338 National Research Foundation of Korea (NRF), funded by the Ministry of Science,

339 ICT & Future Planning (No. 2015R1A5A1037548), and an NRF grant

340 (NRF-2020R1A2C4002093). It was also supported by the China Scholarship Council.

341

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547 List of Figures and Tables

548 Figures:

549 Figure 1. XRD pattern of (a) calcined HT and (b) bassanite.

550 Figure 2. Particle size distributions of Portland cement, HT, and bassanite.

551 Figure 3. (a) Compressive strength of pastes at 1, 3, 7, and 28 days. (b) Compressive strength of

552 pastes normalized to the strength of the HT45S0 reference.

553 Figure 4. (a) Normalized heat flows of pastes. (b) Effect of different bassanite dosages on the time

554 of the occurrence of the aluminate peak. (c) Cumulative hydration heat of pastes. (d) Relations

555 between compressive strength and cumulative hydration heat at curing ages of 1 and 3 days.

556 Figure 5. XRD patterns of pastes at (a) 1 day and (b) 28 days. (Ett. = ettringite; CH = portlandite;

557 Q = quartz; Ms = monosulfoaluminate; Strät. = strätlingite.)

558 Figure 6. ATR-FTIR spectra of pastes at (a) 1 day and (b) 28 days.

559 Figure 7. (a) Cumulative intrusion volume of pastes at a curing age of 28 days. (b) Differential

560 intruded volume. (c) Relations between compressive strength and cumulative intrusion volume at

561 28 days.

562 Figure 8. SEM images of (a) OPC specimens, (b) HT45S3 specimens, (c) HT45S0 specimens

563 with a magnification of 20,000, and (d) HT45S0 specimens with a magnification of 50,000.

564 Tables:

565 Table 1. Oxide chemical compositions measured with XRF spectroscopy in weight %.

566 Table 2. Mix design information in this study.

567 Table 3. Positions of infrared bands and functional groups in ATR-FTIR spectra.

568

26 / 37
 ♦ ・4
• - Bassanite, (CaSO 0.5H2O)
♦-Quartz
•
♣-Illite
•
♥-Feldspar

Intensity (a.u.)
Intensity (a.u.)

♦
•
♣ ♥
♣ ♣ ♥ ♦ ♦♦♦ ♦ ♦ •
♥ ♥ ♦ ♦ •
• ••

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
569 2-theta, degrees 2-theta, degrees

570 (a) (b)

571 Figure 1. XRD pattern of (a) calcined HT and (b) bassanite.

572
573

27 / 37
 10

9
Portland Cement
Hwangtoh Powder
8 Bassanite

Volume Density (%)

7

0
0.1 1 10 100 1000
Particle size (µm)
574

575 Figure 2. Particle size distributions of Portland cement, HT, and bassanite.
576

28 / 37
 1 day
3 day
50 7 day
28 day

Compressive strength (MPa)

40

30

20

10

0
577 OPC HT45S0 HT45S1 HT45S2 HT45S3 HT45S4

578 (a)

1 day
182.3
200
3 day
166.8

180 7 day
Compressive strength normalized

28 day
to the strength of HT45S0 (%)

144.5

160
141.5

133.9
132.5
124.6

140

119.7
114.5

116.3
106.9
106.1

103.9

120
101.8

99.6
100
100
100
100

100 88.4

80

60

40

20

0
HT45S0 HT45S1 HT45S2 HT45S3 HT45S4
579
580 (b)

581 Figure 3. (a) Compressive strength of pastes at 1, 3, 7, and 28 days. (b) Compressive strength of

582 pastes normalized to the strength of the HT45S0 reference.

583

29 / 37
 5.0
OPC
4.5 35

Time (h) of the occurrence of

Heat Flow (mW / g binder) HT45S0 HT45S0
HT45S1 HT45S1
4.0
HT45S2 30 HT45S2
HT45S3

aluminate peak
3.5 HT45S3
HT45S4 25 HT45S4
3.0
2.5
20
2.0
1.5 15

1.0
10
0.5
0.0 5
0 10 20 30 40 50 60 70 0 1 2 3 4
584 Time of hydration (hours) Bassanite content (%)

585 (a) (b)

250 30
225 OPC
HT45S0
Cumulative heat (J/g binder)

Compressive strength (MPa)

200 25
HT45S1
HT45S2
175
20 HT45S3
150 HT45S4
125 15
OPC y = 0.1413x-12.12
100 2
HT45S0 R = 0.968
75
10
HT45S1
50 HT45S2
HT45S3 5
25 HT45S4
0 0
0 10 20 30 40 50 60 70 0 50 100 150 200 250 300

586 Time of hydration (hours) Cumulative heat (J/g binder)

587 (c) (d)

588 Figure 4. (a) Normalized heat flows of pastes. (b) Effect of different bassanite dosages on the time

589 of the occurrence of the aluminate peak. (c) Cumulative hydration heat of pastes. (d) Relations

590 between compressive strength and cumulative hydration heat at curing ages of 1 and 3 days.

591

592

30 / 37
 Ett. C4AF Ett. CH Ett. Ms Q Ett.

HT45S4 1d

HT45S3 1d

HT45S2 1d

HT45S1 1d

HT45S0 1d

OPC 1d

5 10 15 20 25
Position [°2θ], CuKα
593

594 (a)

Strät. Ett. Ett. CH Ett. Ms Q Strät. Ett.

HT45S4 28d

HT45S3 28d

HT45S2 28d

HT45S1 28d

HT45S0 28d

OPC 28d

5 10 15 20 25
Position [°2θ], CuKα
595
596 (b)

597 Figure 5. XRD patterns of pastes at (a) 1 day and (b) 28 days. (Ett. = ettringite; CH = portlandite;

598 Q = quartz; Ms = monosulfoaluminate; Strät. = strätlingite.)

599

31 / 37
 1115.6 944.7
100 OPC 1d

HT45S0 1d

Transmittance (a.u.)
90
HT45S1 1d

80 HT45S2 1d

HT45S3 1d
70
HT45S4 1d

1645.8
3640.3

1418.2

786.0
60

3412.6
50

989.8
1098.5
40
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumbers (cm )
600
601 (a)

OPC 28d 1115.2 949.1

100
HT45S0 28d
Transmittance (a.u.)

90
HT45S1 28d

80 HT45S2 28d

HT45S3 28d
70
HT45S4 28d 785.6
3640.5

1646.2

60
1418.8
3411.9

50
973.4
1096.6

40
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumbers (cm )
602
603 (b)

604 Figure 6. ATR-FTIR spectra of pastes at (a) 1 day and (b) 28 days.

605

32 / 37
 0.24
0.22 OPC

Cumulative Intrusion (mL/g)

0.20 HT45S0
HT45S1
0.18 HT45S2
0.16 HT45S3
0.14 HT45S4
0.12
0.10
0.08
0.06
0.04
0.02
0.00
-2 -1 0 1
10 10 10 10

606 Pore Diameter (µm)

607 (a)

0.48
OPC
Log Differential Intrusion (mL/g)

0.44
HT45S0
0.40 HT45S1
0.36 HT45S2
0.32 HT45S3
HT45S4
0.28
0.24
0.20
0.16
0.12
0.08
0.04
0.00
-2 -1 0 1
10 10 10 10

608 Pore Diameter (µm)

609 (b)
60
y = -94.846x+63.069
Compressive strength (MPa)

55 2
R = 0.9055

50

45 OPC
HT45S0
HT45S1
40 HT45S2
HT45S3
HT45S4
35

30
0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22 0.24

610 Cumulative intrusion in 28 days (mL/g)

611 (c)

612 Figure 7. (a) Cumulative intrusion volume of pastes at a curing age of 28 days. (b) Differential

613 intruded volume. (c) Relations between compressive strength and cumulative intrusion volume at

614 28 days.

33 / 37
615

616 (a) (b)

617

618 (c) (d)

619 Figure 8. SEM images of (a) OPC specimens, (b) HT45S3 specimens, (c) HT45S0 specimens

620 with a magnification of 20,000, and (d) HT45S0 specimens with a magnification of 50,000.

34 / 37
621 Table 1. Oxide chemical compositions measured with XRF spectroscopy in weight %.
Sample SiO2 Al2O3 Fe2O3 CaO MgO Na2O TiO2 SO3 P2O5 K 2O LOI1
Cement 21.6 5.44 2.71 63.2 2.38 0.05 0.25 2.18 0.11 1.06 0.63
Hwangtoh 64.2 23.9 6.36 0.21 0.53 — 0.78 — 0.09 3.21 0.70
Bassanite 1.46 1.10 — 33.6 — — — 55.8 — — 7.69
622 1
Loss on ignition.
623

35 / 37
624 Table 2. Mix design information in this study.
Cement Hwangtoh Bassanite Water
Mix No. wt.% of wt.% of wt.% of
kg/m3 kg/m3 kg/m3 kg/m3
binder binder binder
OPC 100 1221.8 0 0 0 0 610.9
HT45S0 55 658.0 45 538.6 0 0 598.2
HT45S1 54 645.6 45 538.0 1 11.9 597.8
HT45S2 53 633.3 45 537.7 2 23.9 597.4
HT45S3 52 620.9 45 537.4 3 35.8 597.1
HT45S4 51 608.6 45 537.0 4 47.7 596.7

625

36 / 37
626 Table 3. Positions of infrared bands and functional groups in ATR-FTIR spectra.

Wavenumber (cm−1) Functional groups Reference

600–853 Al–O–H, δ [57][58]
938–997 Si–O–Si (Si–O–Al), υas [58][59][60]
1100–1200 SO42−, υas [60][55]
1400–1500 C–O (CO32−), υas [59][60][55][61]
1640–1650 H2O, δs [55][61]
3390–3457 H2O, υ [55][61]
3640–3644 Ca(OH)2, υ [60][55][61]
627

37 / 37
Highlights

The effect of sulfate content on the compressive strength of high-volume

Hwangtoh (HT)/cement systems was investigated.

Bassanite improves the early strength of high-volume HT/cement pastes.

The hydration progress and microstructure were analyzed by isothermal

calorimetry, XRD, ATR-FTIR, SEM and MIP.

The optimal content of bassanite was determined.

Conflict of interest:

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence

the work reported in this paper.