Variation in the Composition of C-S-H Gel in Portland Cement Pastes Cured at Various Temperatures

Variation in the composition of C-S-H gel, the main hydration product of portland cement, cured at various temperatures, was studied using scanning electron microscopy with energy dispersive X-ray spectroscopy. Samples of two cement pastes were cured isothermally under water at 10°, 30°, and 60°C for one year. For the inner-product C-S-H gel of both cement pastes, increased curing temperature decreased the Ca/Si and Al/Ca ratios, but increased the S/Ca ratio. The Al/S and (Al + Fe)/S ratios decreased with increased curing temperature. Sulfur, probably in the form of sulfate ions, could be sorbed by the C-S-H gel at higher temperatures.     

硬化水泥浆体中C-S-H凝胶体内纳米孔的稳定性分析

运用毛细管张力、表面自由能及弹性力学理论,建立了硬化水泥浆体中C-S-H凝胶体内纳米孔的失稳坍塌模型;根据Gibbs自由能理论从二维饱和孔隙水状态下分析了孔洞的稳定性.结果表明,当孔径在纳米量级范围内变化时,孔洞越大形状越圆越稳定,进入微米量级后,发生坍塌的可能性很小;当孔径一定时,水化产物的弹性模量越大则孔洞越稳定.     

Hydration and Strength Development in Tricalcium Silicate Pastes Seeded with Afwillite

The formation of afwillite in tricalcium silicate pastes initiated by ding with crystals was studied to determine the effects on development of tensile strength. Afwillite forms in pastes only when fresh surfaces of both tricalcium silicate and afwillite seed are exposed by initial grinding. Higher early strengths reflect increased rates of hydration in seeded pastes, but strengths at later ages are lower than those of untreated pastes. At all ages tensile strength is lower at a given degree of hydration in seeded pastes than in unseeded ones; this behavior is considered to result from changes in pore-size distribution which occur as afwillite forms. Afwillite initially forms concomitantly with calcium silicate hydrate gel but later arises from conversion of the gel.     

Proposed Structure for Calcium Silicate Hydrate Gel

Calcium silicate hydrate gel is a very poorly crystalline material that is the main product of reaction of portland cement with water. Evidence is presented for a disordered layer structure, in which most of the layers are structurally imperfect ones of jennite (Ca₉Si₆O₃₂H₂₂), and others are similarly related to 1.4-nm tobermorite (Ca₅Si₆O₂₆H₁₈), both structures being modified by omission of many of their silicate tetrahedra. The evidence comprises conditions of formation, silicate anion type, Ca/Si ratio, H₂O/Ca ratios and densities for various drying conditions, thermogravimetric curve, X-ray powder and selected-area electron diffraction patterns, and results of analytical electron microfcopy.     

Effect of Lime on Hydration of Pastes Containing Gypsum and Calcium Aluminates or Calcium Sulfoaluminate

Chemical reactions responsible for ettringite formation in the commercial expansive cements are reviewed. X-ray diffraction analyses of the hydrated expansive compounds showed that in the presence of Ca(OH)₂ and CaSO₄ the tricalcium aluminate hydrated very slowly and the monocalcium aluminate quickly, whereas the calcium sulfoaluminate hydrated at a uniform rate during the early hydration period. Scanning micrographs are presented which show that ettringite formed in the presence of Ca(OH)₂ is colloidal. It is proposed that colloidal ettringite can adsorb large quantities of water, thereby causing slump loss in fresh concrete and expansion in hardened concrete.     

29Si NMR Spectroscopy of Silicate Anions in Hydrothermally Formed C-S-H

Hydrothermal treatment of lime–silica mixtures under saturated steam pressures below 200°C usually gives C-S-H as an initial product, which reacts further to give crystalline calcium silicate hydrates. In this paper, C-S-H was hydro–thermally prepared using CaO and silicic acid at Ca/Si ratios of 0.3 to 2.0 and 120° to 180°C for 2 h. The C-S-H was examined mainly using ²⁹Si NMR by the magic angle spinning gate proton decoupling and cross polarization magic angle spinning methods. XRD for all of the C-S-H showed bands at 0.304, 0.280, 0.183, and 0.166 nm. NMR results showed that all of the C-S-H contained single chains of silicate anion, which became progressively longer as the Ca/Si ratio decreased, i.e., as the system became richer in silica. This was independent of the preparation temperature. The 0.8 ratio preparations at 180°C contained small amounts of double-chain structure of 1.1-nm tobermorite. The reaction processing in the lime- silicic acid mixtures is also discussed.     

Structural Properties of Calcium Silicate Pastes: I, Effect of the Hydrating Compound

The chemical and physical properties of C₃S, β-C₂S, a C₃S/C₂S blend, and portland cement pastes cured at 25°C were investigated. The H₂O specific surface areas of the calcium silicate samples follow a common linear relation when plotted against a CIS ratio. The β-C₂S had higher capillary porosity and N2 surface area, resulting from increased mesopore volume at the expense of micropores. All calcium silicate pastes had similar polysilicate content vs time curves, indicating an aging process which is not sensitive to the starting composition of the hydrating calcium silicate. The polysilicate content of portland cement was much lower than that of the corresponding calcium silicate pastes. Strength-capillary porosity relations for the various systems are discussed.     

水热合成水化硅酸钙(C-S-H)的制备与表征

本论文以高纯氧化钙与白炭黑为原料,通过水热法合成了水化硅酸钙(C-S-H).采用XRD、SEM对分别选取温度为100℃、120℃、150℃、180℃水热反应6h的水化硅酸钙样品,与150℃分别反应2h、6h、10 h的样品做了物相变化与显微结构的分析,结果表明在低于120℃时产物为结晶度较低的凝胶,随着温度的升高,水化硅酸钙凝胶的结晶度逐渐提高,在150℃和180℃时,生成结晶度较高的托勃莫来石和硬硅钙石;反应时间从6h延长到10h只提高了晶体的结晶度,而没有改变晶体结构.这一结果对改善蒸压制品的蒸压制度具有重要的指导意义.     

Structural Properties of Calcium Silicate Pastes: II, Effect of Curing Temperature

The chemical and physical properties of C₃S pastes cured at 4°, 25°, and 65°C were investigated. The 65°C paste had lower H₂O surface area and larger capillary pore volume than the 25°C paste. The structure of the gel in the 4°C paste changes markedly with increased hydration. These changes were reflected in an increase in H₂O surface area, decrease in C/S ratio, and decrease in the diameter of the mesopores. The degree of silicate polymerization increased with time and temperature of curing. In addition, the 4°C paste had a significant amount of monomer in the gel, which polymerizes with time.     

Communications of the American Ceramic Society Estimation of Thermochemical Data for Calcium Silicate Hydrate (C-S-H)

Calcium silicate hydrate (C-S-H) can be viewed as a solid solution, 0.833Ca(OH)₂.SiO₂.0.917H₂O-xCa(OH)₂, at equilibrium at 30°C. On this basis, the change in Gibbsfree energy (ΔG_r) in the solid-solution reaction was calculated from solubility duta for C-S-H in water. The change in ΔG_r with real ratio decreased notably for the higher calcium contents (CaO/Si0₂1.7; ×0.867). Thermochemical values for C-S-H (CaO/SiO₂=1.7) were estimated to be ΔH°=-2890 kJ/mol, ΔG°=-2630 kJ/mol, and S°=200 J1/mol.K at 298 K .     

介孔水化硅酸钙微球的形貌控制及载药性能研究

以氢氧化钙和正硅酸四乙酯为原料,采用共沉淀法制备出了一系列的水化硅酸钙(CSH),通过X射线衍射(XRD)、扫描电子显微镜(SEM)等探讨了不同的酒精添加量和有机溶剂添加对CSH的物相和形貌的影响。结果表明;随着酒精添加量的增加CSH的分散性逐渐变好,采用丙三醇作为有机溶剂可以得到分散较好CSH微球。对CSH进行了布洛芬(IBU)载药研究,利用热重-差热分析、Brunauer-Emmett-Teller法和红外光谱表征(FT-IR)合对其在不同载药时间的CSH载药量、比表面积、孔容和表面基团等进行了分析。发现在12 h后载药量达到116.78%,有望成为较好的药物载体材料。     

Hydration of Tricalcium Silicate

The kinetics of paste, bottle, and ball-mill hydration of 3CaO SiO₂ and the effects of additions of electrolytes and alcohols were studied. Paste and bottle hydrations proceed through periods of induction, acceleration, and decay. If 3CaO SiO₂ is hydrated in an excess of H₂O, as in bottle hydration, the reaction rate is lower than that for paste hydration. The ball-mill hydration rate is much the highest and is controlled by the removal of the hydrate layer coating the 3CaO SiO₂ particles. Electrolytes always accelerate and alcohols retard the reaction rate. Experimental results are discussed with reference to modern theories of the 3CaO SiO₂ hydration mechanism.     

硅酸盐水泥-矿渣复合浆体的水化反应进程研究

为考察矿渣对水泥水化进程的影响,系统研究了在不同的养护龄期、水胶比、矿渣掺量条件下,水泥-矿渣复合浆体的矿渣反应程度、非蒸发水含量、Ca(OH)2含量、孔隙率和力学性能.根据实验结果,研究了复合浆体中矿渣反应程度和非蒸发水含量的变化规律,探讨了矿渣的掺入对Ca(OH)2含量的影响,提出了水化反应进程中水泥与矿渣对Ca(OH)2的供求模式,分析了矿渣与水泥的叠加与互补效应,确定了矿渣的最佳掺量范围和最大掺量范围.上述结果可为矿渣在水泥基材料中合理有效地利用提供一定的科学依据.     

Analytical Electron Microscopy of Cement Pastes: I, Tricalcium Silicate Pastes

One hundred sixty-one particles of C-S-H from C₃S pastes aged 1 to 180 days were analyzed. For pastes made from two C₃S samples, the mean Ca:Si ratios were 1.52 and 1.61, respectively. The overall range of Ca:Si ratios was 1.21 to 1.96; most of the variation is considered to represent real differences in composition between individual particles. No significant correlations with curing time, degree of reaction, or morphological type of C-S-H were found.     

Early Hydration of Tricalcium Silicate

The hydration of tricalcium silicate (C₃S) in the preacceleration stages was studied. The C₃S particles carry a positive charge during the early stages of hydration. Following a rapid hydrolysis of C₃S, calcium ions adsorbed on the Si-rich surface of C₃S particles, greatly reducing their further dissolution, thus initiating the induction period. The [Ca²⁺] and [OH^-] continue to increase at lower rates and, because Ca(OH)₂ crystal growth is inhibited by silicate ions, become supersaturated with respect to Ca(OH)₂. When the supersaturation reaches a value of ∼1.5 to 2.0 times the saturation concentration, nuclei are formed, and rapid growth of Ca(OH)₂ and C-S-H is initiated. These products act as sinks for the ions in solution, thus enhancing the further dissolution of C₃S.     

Kinetics of the Hydration of Tricalcium Silicate

The hydration of tricalcium silicate was followed at a water/C₃S ratio of 0.7 between 5° and 50°C by determining free lime and combined water. Free lime was estimated by the o -cresol method, whereas combined water was calculated from the amount of free water remaining in the paste as determined by extraction with methyl ethyl ketone. The ratio of free lime to combined water was constant throughout the hydration; this ratio indicated that CSH(II) may be represented as 1.68CaO · SiO₂· 2.58H₂O. When maximum supersaturation of the solution with Ca^2+] is attained, the induction period terminates and the reaction proceeds rapidly, probably as the result of propagative surface nucleation-growth of CSH(II). Kinetic equations were derived for these reactions. When the surface of C₃S is entirely covered by CSH(II), the reaction becomes slow and is controlled by diffusion of water. Constants involved in the kinetic equations are evaluated and discussed.     

Structure of Calcium Silicate Hydrates Formed in Alkaline-Activated Slag: Influence of the Type of Alkaline Activator

The influence of the alkaline activator (NaOH, waterglass, or Na₂CO₃) on the structure of the hydrated calcium silicate formed in alkali-activated slag (AAS) cement pastes has been investigated by FTIR, ²⁹Si and ²⁷Al magic-angle scattering nuclear magnetic resonance, and TEM/EDX techniques. In all cases, the main product formed after 7 d of activation, with activators giving an Na₂O concentration of 4%, is a semicrystalline calcium silicate hydrate with a dreierkette-type anion. In these structures, linear finite chains of silicate tetrahedra ( Q ² units) are linked to central Ca-O layers, and tetrahedral aluminum occupies bridging positions in the chains. The main chain length and the amount of aluminum incorporated in the tetrahedral chains depend on the activator used. The detection of Q ³ silicon entities in alkaline-activated slags is discussed in relation to the possible formation of cross-linked structures that may be responsible for increased flexural and compressive strengths in AAS mortars.     

蒸汽养护条件下甲酸钙/纳米C-S-H复合对粉煤灰-水泥体系早期水化的影响

本文研究了蒸汽养护条件下,甲酸钙/纳米C-S-H(NC)复合对粉煤灰-水泥体系早期抗压强度的影响,并结合XRD、DSC-TG、MIP、SEM及FTIR等手段分析了其影响机理。结果表明:蒸汽养护条件下掺入甲酸钙能显著提高粉煤灰-水泥体系的早期抗压强度,且掺量为1.5%(质量分数)时效果最佳;甲酸钙能促进水泥和粉煤灰水化,提高水化产物的生成速率,降低粉煤灰-水泥体系的孔隙率和总孔容;在掺入甲酸钙的基础上掺入NC可进一步提高体系抗压强度,且随着NC掺量的增加而提高;NC能促进水化产物生成,提升水化程度,细化孔结构,提高体系致密度。