纳米水化硅酸钙的制备及对水泥水化影响的研究进展

随着纳米技术的不断发展,纳米材料逐步开始应用于传统混凝土材料中,以提高混凝土的各项服役性能。纳米水化硅酸钙(纳米C-S-H)是一种新型的早强纳米复合材料,可通过晶核效应加快水泥早期水化速率,显著提高水泥基材料的早期力学性能,从而提高施工效率,满足特殊施工要求。本文系统总结了纳米C-S-H的制备方法,及纳米C-S-H对水泥基材料早期和长期性能的影响规律,探讨了其对于水泥水化过程和水化产物的影响机制,其中重点介绍了采用聚合物分散纳米颗粒制备的C-S-H/PCE(聚羧酸型减水剂,简称PCE)纳米复合材料。     

Effect of polymer latexes with cleaned serum on the phase development of hydrating cement pastes

The effects of polymer latexes on cement hydration were investigated by the combination of isothermal calorimetry, in-situ XRD and Cryo-SEM. Two model latexes with varied amounts of anionic charges were used for measurements after cleaned by dialysis to remove the serum components. This study confirms that in-situ XRD technique can be successfully adapted to hydrating cementitious systems in the presences of polymer latexes to quantitatively follow evolution of mineral phases involved in cement hydration. Results show that both polymers retard aluminate reaction and depress silicate reaction, by delaying the dissolution of C₃A, anhydrite and gypsum and consequently the formation of ettringite, and reducing the dissolution of C₃S and the formation of C-S-H. The anionic colloidal polymers exhibit more pronounced retardation effect on aluminate reaction than on silicate reaction due to stronger electrostatic interaction between the polymer particles and the positively charged aluminate phases. The more charged latex shows stronger retardation.     

Calcium-silicate-hydrates/polycarboxylate ether nanocomposites doped by magnesium: Enhanced stability and accelerating effect on cement hydration

C-S-H/PCE (calcium-silicate-hydrates/polycarboxylate ether) nanocomposites have a significant accelerating effect on early hydration and early strength development of cementitious materials. In this study, magnesium ions are doped into C-S-H/PCE nanocomposites, and it is found that C-S-H/PCE nanocomposites doped by appropriate magnesium ions have much better stability. Besides, the accelerating effects of the modified nanocomposites on early cement hydration also get improved. The doped magnesium ions displace calcium ions and promote the absorption of PCE. Moreover, the incorporation of magnesium ions results in two unique morphologies of nanocomposites, that is, globule and gel. The globules are semi-crystalline similar to C-S-H, while the gels are amorphous and have more branched silicate chains.     

Effect on fresh C-S-H gels of the simultaneous addition of alkali and aluminium

Reducing Portland cement content in cementitious binders offers a means to address the adverse environmental impacts of Portland cement manufacture. This paper investigates the impacts on hydration product chemistry of partially replacing Portland cement with alkali-activated aluminosilicates. Here, short-term effects of soluble alkali and aluminium, likely to be available in an alkali-activated system, on the structure of synthetic C-S-H gels are assessed. .C-S-H gels (synthesized at pH values of over 13) were mixed with different concentrations of aluminium nitrate and sodium hydroxide. The gels were characterized by FTIR, TEM/EDX and XRD 72 h later. The results showed that both alkali and aluminium increased the degree of silicate polymerisation in the C-S-H gels and precipitated a crystalline calcium aluminosilicate phase.     

Alkali binding in hydrated Portland cement paste

The alkali-binding capacity of C-S-H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C-S-H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data reported in literatures concerning thirteen different recipes are analyzed and used as references. A three-dimensional computer-based cement hydration model (CEMHYD3D) is used to simulate the hydration of Portland cement pastes. These model predictions are used as inputs for deriving the alkali-binding capacity of the hydration product C-S-H in hydrated Portland cement pastes. It is found that the relation of Na⁺ between the moles bound in C-S-H and its concentration in the pore solution is linear, while the binding of K⁺ in C-S-H complies with the Freundlich isotherm. New models are proposed for determining the alkali-binding capacities of C-S-H in hydrated Portland cement paste. An updated method for predicting the alkali concentrations in the pore solution of hydrated Portland cement pastes is developed. It is also used to investigate the effects of various factors (such as the water to cement ratio, clinker composition and alkali types) on the alkali concentrations.     

纳米C-S-H对矿粉-水泥体系水化的影响

C-S-H是通用硅酸盐水泥主要的水化产物,对水泥基材料的性能起着十分重要的作用,但水泥水化产物复杂,难以从水化产物中分离出纯净的C-S-H并研究其对水泥基材料的影响。故本文通过双分解法制备了纳米C-S-H(NC)颗粒,并将其掺入矿粉-水泥体系中,通过无接触式电阻率测定仪、X射线衍射仪、差热分析仪(DSC-TG)、扫描电镜、压汞测试仪(MIP)等探究了NC对矿粉-水泥体系水化的影响。研究发现,在1%~4%(质量分数)掺量范围内,掺入NC可缩短基体的凝结时间,并为水泥早期水化提供更多的活性位点,加速水化产物的形成和沉淀,促进水化产物之间的搭接,从而降低了基体孔隙率并使基体早期强度和水化浆体电阻率均有所提升。     

BSE-IA reveals retardation mechanisms of polymer powders on cement hydration

The retardation effects of two polymer powders, styrene butadiene rubber and ethylene-vinyl acetate, on cement hydration and the mechanisms in terms of hydration degree and microstructure characteristics were investigated by the combination of backscattered electron image analysis, scanning electron microscopy, energy dispersive spectrometer, and X-ray diffraction. Results show that the cement hydration can be significantly retarded by both polymers with the reductions in cement hydration degrees and hydration products thickness. Polymers retard cement hydration by agglomerating the polymer particles on the surfaces of cement grains, forming films in different thickness and bonding the calcium ions in the pore solutions. Consequentially, the formation of C-S-H and CH is depressed and the Ca/Si ratios in the hydration product layer are raised. The retardation is enhanced with the increase in polymer content. This work helps understand the retardation effect of polymers on cement hydration in depth, which enables rational development of polymer-modified cement-based materials for further applications.     

Cement hydration and microstructure formation in the presence of water-soluble polymers

Hardening of cement mortars modified with small amounts of water-soluble polymers implies both cement hydration and polymer film formation. In this paper, the effect of the presence of water-soluble polymers on the cement hydration reactions is investigated by means of isothermal calorimetry, thermal analysis, FT-IR spectroscopy and SEM investigation. In spite of an initial retardation of the hydration reactions, a higher degree of hydration is found after 90 days for 1% PVAA, MC and HEC modified mortars, due to a better dispersion of the cement particles in the mixing water. MC also affects the morphology of the Ca(OH)₂ crystals. Polymer bridges are detected between the layered crystals, gluing the layers together and strengthening the microstructure. Additionally, the internal cohesion of all bulk polymer modified cement pastes is improved. In the presence of the polymers, a more cohesive microstructure with a smaller amount of microcracks is created.     

Structure and mechanical properties of aluminosilicate geopolymer composites with Portland cement and its constituent minerals

The compressive strengths and structures of composites of aluminosilicate geopolymer with the synthetic cement minerals C₃S, β-C₂S, C₃A and commercial OPC were investigated. All the composites showed lower strengths than the geopolymer and OPC paste alone. X-ray diffraction, ²⁹Si and ²⁷Al MAS NMR and SEM/EDS observations indicate that hydration of the cement minerals and OPC is hindered in the presence of geopolymer, even though sufficient water was present in the mix for hydration to occur. In the absence of SEM evidence for the formation of an impervious layer around the cement mineral grains, the poor strength development is suggested to be due to the retarded development of C-S-H because of the preferential removal from the system of available Si because geopolymer formation is more rapid than the hydration of the cement minerals. This possibility is supported by experiments in which the rate of geopolymer formation is retarded by the substitution of potassium for sodium, by the reduction of the alkali content of the geopolymer paste or by the addition of borate. In all these cases the strength of the OPC-geopolymer composite was increased, particularly by the combination of the borate additive with the potassium geopolymer, producing an OPC-geopolymer composite stronger than hydrated OPC paste alone.     

马来酸三乙醇胺酯对水泥水化的影响

为克服三乙醇胺早强剂对水泥抗折强度和后期强度的影响,合成了马来酸三乙醇胺酯,并通过背散射电子成像(BSE)和BET分析,研究了马来酸三乙醇胺酯对水泥水化程度、C-S-H含量和水泥水化28 d分形维数的影响。结果表明:马来酸三乙醇胺酯可促进水泥水化尤其是水泥中硅酸盐相的水化;复掺马来酸三乙醇胺酯和聚羧酸减水剂,可显著提高水泥水化产物中C-S-H的含量;三乙醇胺降低了水泥石28 d的分形维数,马来酸三乙醇胺酯单掺及与聚羧酸减水剂复掺则使水泥石28 d的分形维数提高。由此可见,马来酸三乙醇胺酯作为增强型水泥早强剂具有广阔的应用前景。     

C-S-H/PCE凝胶对掺磷渣水泥的低温促凝早强性能研究

探讨C-S-H/PCE凝胶对掺磷渣硅酸盐水泥的低温促凝早强性能的影响,并通过上清液pH值、Ca²⁺浓度和化学结合水量分析其对水化的影响机理。低温下(8℃) C-S-H/PCE凝胶能有效缩短混凝土终凝时间,并提高早期强度,当掺量5%时,混凝土终凝时间缩短近6 h,16 h、24 h和3 d抗压强度比分别为160%、150%和110%,且不影响2.5 h混凝土工作性能。C-S-H/PCE凝胶能使低温下掺磷渣硅酸盐水泥浆体处于高pH状态,加速早期水泥矿相离子溶解,提高Ca²⁺过饱和度,加速后期析晶过程,提高化学结合水量,从而促进掺磷渣硅酸盐水泥的水化,实现低温促凝早强。     

Changes in C3S hydration in the presence of cellulose ethers

The influence of cellulose ethers (CE) on C₃S hydration processes was examined in order to improve our knowledge of the retarding effect of cellulose ethers on the cement hydration kinetics. In this frame, the impacts of various cellulose ethers on C₃S dissolution, C-S-H nucleation-growth process and portlandite precipitation were investigated. A weak influence of cellulose ethers on the dissolution kinetics of pure C₃S phase was observed. In contrast, a significant decrease of the initial amount of C-S-H nuclei and a strong modification of the growth rate of C-S-H were noticed. A slowing down of the portlandite precipitation was also demonstrated in the case of both cement and C₃S hydration. CE adsorption behavior clearly highlighted a chemical structure dependence as well as a cement phase dependence. Finally, we supported the conclusion that CE adsorption is doubtless responsible for the various retarding effect observed as a function of CE types.     

高贝利特硫铝酸盐水泥改性白水泥的物理力学性能与水化作用

白色硅酸盐水泥(白水泥)具有较好的白度,是一种具有装饰效果的胶凝材料。针对该种水泥凝结时间长、早期强度发展慢及收缩变形较大等问题,采用高贝利特硫铝酸盐水泥对白水泥进行改性,系统研究了掺入10%~30%(质量分数)的高贝利特硫铝酸盐水泥对白水泥凝结时间、胶砂强度和自由膨胀率的影响。使用水化微量热仪、XRD、TGA、SEM等方法对复合胶凝体系水化过程、水化产物和微观形貌进行分析。结果表明:高贝利特硫铝酸盐水泥增大了白水泥水化放热率,显著缩短了白水泥的凝结时间;改性后的白水泥水化产物生成了大量的AFt,穿插生长在C-S-H凝胶中,消耗掉了部分Ca(OH)₂,使结构更加致密,强度更高,膨胀性能更好。     

早强型聚羧酸系减水剂对基准水泥早期水化的影响研究

探究早强型聚羧酸系减水剂(ES-PCE)对水泥水化的作用机制,有助于ES-PCE的研发设计与推广应用。本文通过对水泥水化进程、溶解速率、水化产物生长、凝结时间与抗压强度进行表征,分析了ES-PCE与普通聚羧酸系减水剂(PCE)对基准水泥早期水化的影响机理。结果表明:PCE与ES-PCE均会降低水泥悬浮液的溶解速率;PCE的掺入延缓了水泥水化的诱导期与加速期,降低了水化放热量;而ES-PCE仅略微延迟了水泥水化的诱导期,但缩短了加速期,水化放热量基本不变。与基准水泥相比,ES-PCE分别提早了水泥初凝时间10 min和终凝时间85 min。ES-PCE的掺入提高了水泥早期和后期强度,掺0.2%(质量分数)ES-PCE的水泥7 d抗压强度较基准组提高了14%,而同掺量的PCE强度提高仅为前者的一半。PCE与ES-PCE的掺入释放了水泥颗粒团状絮凝结构中的水分,有利于水泥水化,但二者对水化的影响截然相反;PCE分子结构中大量的羧基络合了溶液中的Ca²⁺,抑制了水泥颗粒表面晶核的形成,起到了一定的缓凝作用;然而,ES-PCE分子结构中羧基含量较低,Ca²⁺的络合作用较弱,缓凝效果并不明显,在体系中有效水分增多的情况下,反而促进水泥的水化,起到了早强效果。水灰比为0.4的水泥砂浆中,ES-PCE的掺量适宜控制在0.3%以下,在保证减水率的同时,对水泥早期和后期强度均起到一定的增强作用。     

Early age strength enhancement of blended cement systems by CaCl2 and diethanol-isopropanolamine

The enhancement of the 1 day strength of cementitious systems by a combination of calcium chloride (CaCl₂) and diethanol-isopropanolamine (DEIPA) was studied, particularly in blended cement systems. A combination of quantitative X-ray diffraction with Rietveld refinement (QXRD), scanning electron microscopy (SEM)/backscattered electron image analysis, thermogravimetric analysis (TGA), and isothermal calorimetry were used to investigate the mechanism of strength enhancement by the additives. The additives were found to increase the early age mortar strength by enhancing the cement hydration, with the DEIPA enhancing primarily the aluminate hydration. DEIPA also affected the morphology of portlandite which was formed as thin plates. In parallel, the calcium-to-silica ratio of the C-S-H was found to increase with the use of DEIPA, possibly because of the inclusion of microcrystalline portlandite. After 48 h DEIPA was found to directly enhance the rate of reaction of granulated blast-furnace slag and fly ash.     

C-S-H/solution interface: Experimental and Monte Carlo studies

The surface charge density of C-S-H particles appears to be one of the key parameters for predicting the cohesion strength, understanding the ion retention, the pollutant leakage, and admixture adsorption in hydrated cement pastes.This paper presents a Monte Carlo simulation of the surface-ions interactions that permits the prediction of surface charge density (σ), electrokinetic potential (ζ) and ions adsorption of mineral surfaces in equilibrium with a given electrolyte solution. Simulated results are compared to experimental data obtained by titration, electrokinetic potential measurements and ions uptake in the case of C-S-H suspensions. An excellent agreement is found between simulated and experimental results.The wide spread idea that calcium is a potential determining ion in cement paste systems appears to be incorrect. Instead, the pH controls the charging behaviour of C-S-H nano-particles. This paper also shows to what extent the electrostatic interactions contribute to the measured Ca/Si ratio.     

Insights into early hydration of Portland limestone cement from infrared spectroscopy and isothermal calorimetry

Isothermal calorimetry and diffuse reflectance infrared DR-FTIR spectroscopy are combined to correlate evolutions of spectroscopic signatures with rates of chemical reactions as reflected in the rate of heat emitted during the first 38 h of cement hydration. Portland limestone cement mortar is employed and the analysis is repeated for two different mixing procedures. Intensive blender mixing with quartz sand is found to cause activation of the cement resulting in a faster hydration process. At early stages of hydration, two types of C-S-H are formed. The spectral intensity of the earlier C-S-H is found to saturate, while that of the later form continues to acquire intensity throughout the 38 h of the experiment. Evidences are presented which support the interpretation that the two forms differ mainly in morphology and water content. Simultaneously with the saturation of the early C-S-H, a transient species is observed with DR-FTIR. This species correlates with the observed thermogram fine-structure.     

Poly(lactic acid)/polystyrene bioblends characterized by thermogravimetric analysis,differential scanning calorimetry,and photoacoustic infrared spectroscopy

Bioblends are composites of at least one biodegradable polymer with nonbiodegradable polymer. Successful development of bioblends requires that the biodegradable polymers be compatible with other component polymers. Compatibility can be assessed by evaluating the intermolecular interactions between the component polymers. In this work, the interaction in binary bioblends comprising biodegradable poly(lactic acid) (PLA) and polystyrene (PS) was investigated using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and Fourier transform infrared photoacoustic spectroscopy (FTIR‐PAS). The TGA studies indicated that incorporation of PLA in PS resulted in thermal destabilization of PS. The DSC studies showed that some parameters favored partial miscibility of PS in PLA, while others favored immiscibility, such as the existence of two glass transitions. The FTIR‐PAS spectra revealed the presence of intermolecular n–π interactions between PLA and PS and indicated that the degree of interaction was dependent on the concentrations of the polymers in the bioblends. FTIR‐PAS results computed via differential spectral deconvolution were consistent with, and therefore support, the results of TGA and DSC analyses of PLA/PS bioblends. The degradation kinetics, used to determine the degradation mechanism, revealed a two‐ or three‐step mechanism. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Measurement methods of carbonation profiles in concrete: Thermogravimetry, chemical analysis and gammadensimetry

This paper deals with two experimental methods to determine carbonation profiles in concrete. Gammadensimetry is a non-destructive test method able to measure the total penetrated CO₂ and to monitor the carbonation process during laboratory accelerated tests. The second method is thermogravimetric analysis (TGA) supplemented with chemical analysis (CA): as TGA is performed on a small mortar sample not representative of the whole tested concrete, CA is needed to proportion the sample cement content, the sand content and to correct the TGA results becoming thus representative of the concrete mix. Consequently, TGA-CA gives accurate quantitative profiles in carbonated cementitious materials. Results are reported for an ordinary Portland cement paste, and three concrete mixes, containing siliceous or calcareous aggregates. The CO₂ mass loss due to carbonation occurs from 530 to 950 °C, which overlaps the temperature range of the calcareous aggregate dissociation. To solve the problem, the origin of CaCO₃ is carefully analyzed. Calcium carbonate ensuing from C-S-H carbonation dissociates in a lower temperature range than the more stable one ensuing from portlandite carbonation and from limestone, which enables C-S-H carbonation to be distinguished from calcareous aggregates. Therefore, TGA-CA allows the CaCO₃ ensuing from C-S-H carbonation to be measured and to calculate the portlandite degraded by carbonation. Thus, the total calcium carbonates profiles can be deduced even when calcareous aggregates is present in the concrete mix.     

水泥-粉煤灰-矿粉-偏高岭土四元胶凝材料氯离子固化机理研究

本文在水泥、粉煤灰和矿粉组成的三元胶凝材料基础上掺入第四元矿物掺合料偏高岭土,利用X射线衍射(XRD)和热重分析(TGA/DTG)定性分析了四元胶凝材料水化产物与氯离子固化能力的关系,并在此基础上利用TGA/DTG和Rietveld外标法定量分析不同形态氯离子固化量。研究表明,掺入偏高岭土能够增加体系早期水化反应速率,促进粉煤灰和矿粉早龄期水化,增加了四元胶凝材料水化AFm相(单硫型水化硫铝酸钙)和C-S-H凝胶含量。同时也增加了体系中铝钙摩尔比,使得单硫型硫铝酸钙(Ms)在碳酸盐存在的条件下更加倾向于转化为半碳型碳铝酸钙(Hc)。氯离子等温吸附结果表明,AFm相含量与氯离子固化能力呈正相关。Rietveld外标法结果表明,掺入偏高岭土后四元体系的氯离子化学固化能力提高,物理吸附能力降低,与三元体系相比,氯离子化学固化量提高了94.16%,物理吸附量降低了7.62%,TGA/DTG定量结果表明Rietveld定量分析具有可行性。