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Abstract
The influence of styrenebutadiene rubber (SBR) latex on cement hydrates Ca(OH)2, ettringite, C4AH13 and CSH gel and the degree of
cement hydration is studied by means of several measure methods. The results of DSC and XRD show that the Ca(OH)2 content in wet-cured
SBR-modified cement pastes increases with polymercement ratio (P/C) and reaches a maximum when P/C is 5%, 10% and 10% for the pastes
hydrated for 3 d, 7 d and 28 d, respectively. With wet cure, appropriate addition of SBR promotes the hydration of cement, while the effect of SBR
on the content of Ca(OH)2 and the degree of cement hydration is not remarkable in mixed-cured SBR-modified cement pastes. XRD results
illustrate that SBR accelerates the reaction of calcium aluminate with gypsum, and thus enhances the formation and stability of the ettringite and
inhibits the formation of C4AH13. The structure of aluminum-oxide and silicon-oxide polyhedron is characterized by 27Al and 29Si solid state
NMR spectrum method, which shows that tetrahedron and octahedron are the main forms of aluminum-oxide polyhedrons in SBR-modified
cement pastes. There are only [SiO4]4 tetrahedron monomer and dimer in the modified pastes hydrated for 3 d, but there appears three-
tetrahedron polymer in the modified pastes hydrated for 28 d. The effect of low SBR dosage on the structure of aluminum-oxide and silicon-oxide
polyhedron is slight. However, the combination of Al3+ with [SiO4]4 is restrained when P/C is above 15%, and the structure of Al3+ is changed
obviously. Meantime, the polymerization of the [SiO4]4 tetrahedron in CSH gel is controlled.
2006 Elsevier Ltd. All rights reserved.
1. Introduction penetrability [13,14] and frost resistance [15]. A late report ex-
hibited that SBR could be used to make self-leveling materials
Polymer-modified mortar and concrete are good repair [16]. Our earlier work indicated that SBR could reduce water
materials for construction in most conditions for their excellent requirement, effectively enhance both flexural strength and
physical and mechanical properties and durability [13]. It was tensile bond strength, substantially decrease the ratio of com-
reported that the property improvement of mortar and concrete by pressive strength to flexural strength, and improve the ratio of
polymer modification was related to the influence of polymer on flexural strength to elastic modulus. The prepared SBR-modified
the material structures, cement hydration, porosity and unit water mortar is suitable for bridge repair [17,18]. With same water
content, and also to the chemical and physical interactions cement ratio (W/C), the compressive and flexural strengths of
between the polymers and cement hydrates [410]. However, the SBR-modified mortars are directly proportional to its apparent
polymer modification mechanism is unclear, which confines bulk density at polymercement ratio (P/C) below 10% [19].
further development of polymer modified cementitious materials. Inter-penetrating structures of polymer and cement hydrates
Styrenebutadiene rubber (SBR) latex has been widely used to formed in SBR-modified mortars, and the interface structures and
significantly modify mortar. Previous results showed that SBR- anti-cracking property of the cement mortar are improved by SBR
modified mortar had good mechanical properties [11,12], anti- modification [20].
It was reported that SBR retarded the early hydration
Corresponding author. Tel.: +86 21 6598 0526; fax: +86 21 6598 5385. reaction of cement in SBR-modified cement pastes but had
E-mail addresses: wr_irene@163.com, ruwang@mail.tongji.edu.cn no effect on the degree of cement hydration at long curing
(R. Wang). age by hydration heat, chemical combined water content and
0008-8846/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cemconres.2006.05.020
R. Wang et al. / Cement and Concrete Research 36 (2006) 17441751 1745
2. Experimental
2.1. Materials
Table 1
The integrated results of XRD diffraction peak of (100) crystal plane of ettringite
P/C d-value FWHM Max. Integ. Integ:int:1 P=C
() () int. int. Integ:intP=C0
Wet-cured, 0 9.719 0.223 96 32.09 1.00
3d 0.05 9.611 0.273 162 50.96 1.67
Fig. 3. XRD curves of SBR-modified cement pastes at 2 range of 813.
0.10 9.670 0.239 156 49.65 1.70
0.20 9.659 0.235 285 86.60 3.24
Wet-cured, 0 9.583 0.293 36 14.32 1.00
7d 0.05 9.665 0.239 89 28.80 2.11
frequency of 27Al and 29Si is 104.26 and 79.49 MHz, rotation
0.10 9.645 0.284 174 58.88 4.52
speed of the sample is 9 and 5 kHz, pulse time is 0.75 and 4.5 s, 0.20 9.659 0.220 370 104.8 8.78
retard time is 0.5 and 1.5 s for 27Al and 29Si, respectively, and the Wet-cured, 0 9.641 0.135 31 11.24 1.00
pulse energy is 2 dB. 28 d 0.01 9.673 0.175 35 11.40 1.02
0.05 9.711 0.284 85 28.17 2.63
0.08 9.709 0.275 111 37.62 3.61
3. Results and discussion
0.10 9.659 0.261 161 53.43 5.23
0.12 9.680 0.262 167 56.71 5.65
3.1. DSC analysis 0.15 9.669 0.255 168 56.42 5.77
0.20 9.659 0.261 220 71.09 7.59
Ca(OH)2 is one of the important cement hydrates. Its Mixed- 0 9.654 0.155 46 17.65 1.00
cured, 28 d 0.01 9.679 0.183 82 23.76 1.36
content differs and can be up to 25% according to chemical
0.05 9.669 0.205 95 26.50 1.58
compositions of the cement, hydration time and condition. 0.08 9.657 0.286 109 37.93 2.32
Previous researches proved that the degree of cement hydra- 0.10 9.687 0.271 127 45.64 2.84
tion calculated based on the content of Ca(OH)2 measured 0.12 9.679 0.239 162 50.00 3.17
with DSC is credible [21,22]. Fig. 1 shows the DSC curves of 0.15 9.691 0.256 213 64.63 4.21
0.20 9.686 0.248 300 90.95 6.18
SBR-modified cement pastes hydrated for different ages at
R. Wang et al. / Cement and Concrete Research 36 (2006) 17441751 1747
Table 2
The integrated results of XRD diffraction peak of C4AH13
P/C d-value FWHM Max. Integ. Integ:int:1 P=C
() () int. int. Integ:intP=C0
Wet-cured, 7 d 0 7.573 0.367 78 32.14 1.00
0.05 7.553 0.339 110 48.03 1.57
0.10 7.600 0.377 61 27.42 0.94
0.20 0 0
Wet-cured, 28 d 0 7.553 0.332 511 174.49 1.00
0.01 7.550 0.243 589 195.78 1.13
0.05 7.587 0.240 523 176.59 1.06
0.08 7.579 0.246 423 155.93 0.97
0.10 7.568 0.261 355 131.78 0.83
0.12 7.578 0.262 277 108.36 0.70
0.15 7.568 0.274 204 77.48 0.51
0.20 7.572 0.332 161 55.99 0.39
Mixed-cured, 0 7.558 0.248 469 156.95 1.00
28 d 0.01 7.573 0.234 474 168.62 1.09
0.05 7.566 0.267 379 146.22 0.98
0.08 7.561 0.253 293 99.08 0.68
0.10 7.570 0.312 239 85.42 0.60
0.12 7.569 0.257 181 64.79 0.46
0.15 7.587 0.307 125 41.85 0.31
0.20 7.583 0.283 82 26.18 0.20
DHP 1 P=C
CaOH2 content % 100% 1
DHCH
Table 3
The integrated results of XRD diffraction peak of Ca4Al2Fe2O10
P/C d-value FWHM Max. Integ. Integ:int:1 P=C
() () int. int. Integ:intP=C0
Wet-cured, 0 7.297 0.238 361 86.33 1.00
3d 0.05 7.275 0.236 326 78.84 0.96
0.10 7.291 0.186 359 83.52 1.06 Fig. 4. XRD curves of SBR-modified cement pastes at 2 range of 1719.
0.20 7.281 0.206 336 84.56 1.18
Wet-cured, 0 7.268 0.184 320 68.19 1.00
7d 0.05 7.268 0.205 280 58.69 0.90
3.2. XRD analysis
0.10 7.289 0.189 298 62.64 1.01
0.20 7.284 0.201 290 74.52 1.31
Wet-cured, 0 7.288 0.222 225 51.72 1.00 Fig. 3 exhibits the XRD curves of SBR-modified cement
28 d 0.01 7.284 0.223 185 44.09 0.86 pastes with different curing ages and P/C at 2 range of 8
0.05 7.311 0.191 234 51.24 1.04 13. The diffraction peak at about 9.1 strengthens with P/
0.08 7.311 0.190 222 46.58 0.97
C, which relates to the diffraction of (100) crystal plane of
0.10 7.294 0.200 211 48.13 1.02
0.12 7.305 0.195 250 54.97 1.19 ettringite [23]. The strengthening of the peak with P/C is
0.15 7.295 0.191 257 58.50 1.30 more apparent at longer curing ages. The diffraction peak at
0.20 7.289 0.191 304 66.86 1.55 about 11.6 is corresponding to the C4AH13. This peak is not
Mixed- 0 7.286 0.214 253 55.45 1.00 observed at the XRD curves of the modified pastes hydrated
cured, 0.01 7.303 0.184 260 55.67 1.01
for 3 d, implying no or only a little C4AH13 in these sys-
28 d 0.05 7.299 0.234 221 49.26 0.93
0.08 7.291 0.191 218 46.72 0.91 tems. The diffraction peak becomes obvious with curing age,
0.10 7.293 0.202 241 50.45 1.00 while weakens with P/C. The diffraction peak of (020) crys-
0.12 7.297 0.186 279 59.68 1.21 tal plane of Ca4Al2Fe2O10 at about 12.1 fades with curing
0.15 7.302 0.184 294 63.18 1.31 age, showing that the degree of cement hydration reinforces
0.20 7.298 0.215 307 64.74 1.40
with hydration time.
1748 R. Wang et al. / Cement and Concrete Research 36 (2006) 17441751
that of DSC analysis. A previous paper showed that the strength Similarly, the diversity of the structural environment of the
of mixed-cured modified mortars is higher [19], which indicates [AlO6]9 octahedron makes the peak at 8 ppm broad. With the
that the strength of the polymer-modified mortars is influenced increment of P/C, the peak for [AlO6]9 octahedron at 8 ppm
by both the cement hydration and the formed polymer film. weakens and a sharp symmetric peak appears at 3 ppm. It
Because it is well known that mixed cure is more helpful for the means that the environment of the [AlO6]9 octahedron becomes
polymer film development [24]. more homogeneous.
The 27Al NMR spectra of SBR-modified cement pastes
27
3.3. Al NMR analysis hydrated for 28 d with different P/C are laid in Fig. 6. The peak at
8 ppm corresponding to [AlO6]9 octahedron at the 27Al NMR
Fig. 5 displays the 27Al NMR spectra of SBR-modified cement spectra is sharper than that of the modified pastes hydrated for
pastes hydrated for 3 d with different P/C. Tetrahedron and 3 d, which indicates that the structural environment symmetry of
octahedron are the forms of aluminum-oxide polyhedrons in the the [AlO6]9 strengthens with hydration time. When P/C is 20%,
SBR-modified cement pastes from the appearance of the peaks at the peak for [AlO6]9 octahedron splits evidently; and a sharp
50 ppm, corresponding to [AlO4]5 tetrahedron, and at 8 ppm, symmetric peak appears at 3 ppm. It is seen that the sharp
corresponding to [AlO6]9 octahedron. And the peak at 8 ppm symmetric peak at 3 ppm becomes evident for the modified
is stronger, indicating that the octahedron is prominent. The pastes with different curing ages. That may be some [AlO6]9
chemical shifts of both the [AlO4]5 and [AlO6]9 hardly change octahedron separates from the three dimensional structure net of
with P/C and curing time. Note that Al3+ still exists in tetrahed- [SiO4]4 tetrahedron and distributes outside of the net indepen-
ron after participating in the three dimensional structural net of dently [25].
[SiO4]4, but its structural environment changes. There may be It can be drawn that the effect of a small SBR dosage on the
four [SiO4]4 tetrahedrons or three [SiO4]4 tetrahedrons and a structure of Al3+ in SBR-modified cement pastes is slight. How-
[AlO4]5 tetrahedron, or other modulating ions. The depression ever, the state of Al3+ in the modified pastes changes obviously
of the symmetry of structural environment results in the broad- and the combination of Al3+ with [SiO4]4 tetrahedron is re-
ness of the peak of [AlO4]5 tetrahedron at 50 ppm [25]. strained at the addition of 15% SBR.
29
3.4. Si NMR analysis