不同温度下合成沸石对铝酸钙水泥水化行为的影响

铝酸钙水泥的水化行为与物相组成、粉体粒径、水化温度、外加剂等因素密切相关。已有研究发现沸石结构矿物对铝酸钙水泥的水化行为影响显著,而作用机制有待进一步研究。本文采用XRD、SEM、FTIR、综合热分析以及电导率测试方法,系统研究了不同养护温度(20 ℃、25 ℃、30 ℃和40 ℃)下合成沸石对铝酸钙水泥水化行为的影响及作用机理。结果表明,合成沸石对铝酸钙水泥水化行为的影响与不同养护温度下离子浓度有关。在20 ℃养护时,铝酸钙水泥的溶解程度较低且沸石具有超高的比表面积及离子吸附能力,离子浓度难以达到饱和,延长了诱导期,从而延缓了铝酸钙水泥的水化;在25~40 ℃养护时,沸石的微孔结构和超高比表面积为水化产物提供更多成核位点,进而促进了铝酸钙水泥的水化。此外,合成沸石的引入有效消除了铝酸钙水泥在25 ℃养护时的异常凝结行为。     

20℃下碳酸钙微粉对铝酸钙水泥水化行为的影响

采用板状刚玉颗粒和细粉、α-Al₂O₃微粉、碳酸钙微粉、铝酸钙水泥（CAC）等原料制备了刚玉质浇注料,研究了20℃下碳酸钙微粉对CAC水化速率、水化产物的相组成和显微结构的影响,同时也探究了碳酸钙微粉加入量（0～1.5%,w）对CAC结合刚玉质浇注料养护过程中强度的影响。结果表明：在20℃下,未加入碳酸钙微粉时,CAC水化速率较慢,水化产物主要为针柱状的CAH₁₀;加入碳酸钙微粉后,CAC水化速率明显提升,且其主要的水化产物从针柱状的CAH₁₀转变成片状的C₄ACH₁₁。碳酸钙微粉的引入加速了CAC的水化,使得水化产物数量增多,CAC结合浇注料的养护强度显著提升。     

制止铝酸钙水泥水化过程

铝酸钙水泥与水反应使无水相溶解,并伴随着水合化合物的成核和结晶长大。由于这个过程的不稳定性,为了测定这些材料的相变动力学,需要采取适当的方法来制止其水化过程。本次研究采用丙酮和微波干燥来收回游离水以抑制进一步反应。将水泥试样在37℃下放置1～15天,用X射线衍射来量化其物相。介绍并讨论这些方法的优点和缺点。用微波制止成型试样的水化过程,材料经预先研磨,能有效收回水泥游离水。建议将这种方法应用在铸铁工厂领域、牙髓黏固粉和其他方面的研究。     

铝酸钙水泥的异常凝结行为

硅酸盐水泥的水化速率总是随水化温度升高而增大。而在18～30℃范围内，铝酸钙水泥的水化速率随温度升高而降低，这就是所谓的铝酸钙水泥的异常凝结行为。通过比较工业铝酸钙水泥与合成纯铝酸钙的凝结行为，证明这种行为是铝酸钙水泥本身具有的，而不是掺入物引起的。铝酸钙水泥的异常凝结行为与其水化严物的结构、成核及生长等因素有关。本文还指出了对于这一现象有待进一步研究的问题。     

水化放热曲线在研究铝酸钙水泥和浇注料中的应用

为了预测水泥或浇注料的凝结性和强度发展趋势,取1500g按一定程序搅拌好的水泥胶砂或浇注料,迅速倒入模具中,振动10s后置入j-型热电偶,由计算机绘制出其水化放热曲线。浇注料的水化放热曲线形貌不仅能反映水泥的矿物组成和反应活性,而且能反映浇注料中其他原材料(如骨料、氧化铝或二氧化硅微粉和外加剂等)和作业环境对水泥及浇注料的影响,为此可用于水泥与浇注料流变特性的研究和控制,同时也为浇注料用原材料的甄选提供了一种有用的工具。     

蒸汽养护对组成不同水泥水化特性影响

研究了蒸汽养护和标准养护条件下混合材掺量不同的水泥力学性能差异,并利用XRD、SEM、DSC等测试方法对组分不同水泥水化产物及水化特性等进行对比分析。结果表明,与20℃标准养护相比,85℃常压蒸养下水泥水化产物基本相同,且水化产物数量远高于前者,并有钙矾石(AFt)稳定存在;混合材掺量适宜的水泥样品中有亚稳态水化硅酸钙(C_9S_6H_(18))的形成,这可能是蒸养强度差异的主要原因之一。混合材掺量不同,水化产物形貌也存在明显差异。混合材掺量高达50%时,水化产物形成数量明显减少,水泥石结构疏松,蒸养强度显著降低。混合材中硅灰的掺入,有利于细化水泥石结构,促进水泥石蒸养强度的发展。     

C80微量热仪在水泥水化研究中的应用

介绍了Ｃ８０微量热仪的工作原理及特点，以及在水泥水化热量方面的应用，特别是在测量外加剂水对化水热的影响方面具有优越性，该仪器灵敏度高，瞬时探测极际达１ｍＪ测量可连续自动进行，可微机采点及数据处理。与目前水化热的测量方法相比，大大减少了人为误差，是水泥水化热测量的理想工具。     

Impact of sand and filler materials on the hydration behavior of calcium aluminate cement

In earlier work, we have observed discrepancies relating to the early hydration of calcium aluminate cement (CAC) when comparing data from heat flow calorimetry of CAC paste with results from mortar strength tests using the crushing method. Here, we investigated on this phenomenon and found that the sand which is used as a filler exerts a major influence on CAC hydration resulting in acceleration. Furthermore, in particular fine filler materials such as, for example, microsilica, fine limestone powder, and especially α- and γ-Al₂O₃ also produced a strong hydration accelerating effect which is dependent on their specific surface area. The mechanism underlying the acceleration is that under alkaline conditions their negative surface charge attracts calcium ions as was confirmed via inductively coupled plasma atomic emission measurements. Such a layer generates favourable conditions for the nucleation of CAC hydration products (C-A-H phases). The resulting crystalline hydrates which form on the surface of the filler particles submerged in CAC cement pore solution were visualized via SEM imaging. This way, specifically selected fillers can significantly accelerate CAC hydration and save precious lithium salts which are commonly used to boost the early strength of CAC.     

亚硫酸钙对水泥水化性能的影响

采用XRD、SEM等测试方法研究了亚硫酸钙(CaSO3.1/2H2O)对水泥水化性能的影响,并与石膏(CaSO4.2H2O)进行了对比.结果表明在水泥中CaSO3.1/2H2O不具有石膏那样的调节水泥凝结时间的作用.掺CaSO3.1/2H2O的水泥试样1d强度比掺CaSO4.2H2O试样显著降低,3d后两者强度相近.60d的抗折、抗压强度与28d相比,增幅很小,有的甚至倒缩.CaSO3.1/2H3O和铝酸盐矿物反应,主要生成片状的C3A.CaSO3.     

One-step synthesis of in situ nanocarbon-containing calcium aluminate cement in reducing atmosphere

In order to overcome the problems caused by poor water wettability/dispersion and oxidation resistance of carbons for improving properties of carbon-containing refractory castables, we prepare in situ nanocarbon-containing cement through the carbon-bed sintering method with calcium citrate tetrahydrate (CCT, C₁₂H₁₀Ca₃O₁₄ · 4H₂O) and Al₂O₃ as raw materials, and FeCl₃ as a catalyst. In this paper, the carbonization process of CCT was analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and thermogravimetric analysis coupled with a FTIR. In addition, the synthesized cement was characterized through XRD, Raman spectroscopy, field-emission scanning electron microscopy, and high-resolution transmission electron microscopy. The results show that the in situ carbon was generated through carbonization of calcium aconitic acid which was generated by pyrolysis of CCT, accompanying with overflowing of H₂O, CO₂, CO, and CH₄. Interestingly, as the sintering temperature increases, the freshly generated carbons were transformed into nanofiber and nanoflake carbons under the action of Fe catalyst. After sintering at 1500°C for 4 hours, the phase compositions of the synthesized product approached to that of the commercial cement Secar71, and the in situ carbons with nanofiber and nanoflake morphologies dispersed in calcium aluminate grains.     

低水泥浇注料中纯铝酸钙水泥和SiO_2微粉的“老化”试验

为了探讨纯铝酸钙水泥结合的低水泥浇注料"老化"的原因和影响因素,将SiO2微粉以及不同粒度、不同物相组成(CA相含量)、不同新鲜程度的纯铝酸钙水泥在温度为(20±1)℃、相对湿度>75%的潮湿环境中摊成厚度为2.5 cm左右的料层,放置一定时间(分别为0、3、7、14、28 d)使其老化,然后分别将它们与特级矾土(≤5、≤0.088 mm)、磷酸盐分散剂和减水剂等其他原料一起配制成浇注料,通过测定浇注料的可工作时间、初始流动性和早期(6 h)养护强度,来表征这些原料的老化速度.结果表明:(1)纯铝酸钙水泥的cA含量和细度越高,其老化速度越快.(2)"新鲜"的铝酸盐水泥比存放一段时间后的水泥的老化速度更快.(3)SiO2微粉的老化会导致浇注料的流动性变差,可工作时间变短.     

温度对高钙粉煤灰水泥基材料水化性能的影响

主要研究了高钙粉煤灰及由其配制的高钙粉煤灰水泥基材料在不同温度下的水化特性。结果表明,高钙粉煤灰中游离氧化钙在不同温度下的水化速度不同,而且,高钙粉煤灰在与水泥一起水化时的水化速度要远慢于其单独水化时的水化速度。合适的养护温度对高钙粉煤灰水泥基材料非常重要,高钙粉煤灰水泥基材料适宜制作蒸养水泥混凝土制品。     

SiO_2微粉对水泥结合刚玉质浇注料中低温化学键变化的影响

以电熔棕刚玉(8~5、5~3、3~1 mm)和电熔白刚玉(≤1、≤0.045 mm)为主要原料,添加α-Al2O3微粉和SiO2微粉制备铝酸钙水泥结合刚玉质浇注料,研究了经110、800和1 000℃热处理后含5%(w)Si O2微粉和不含SiO2微粉浇注料基质中化学键变化与浇注料强度的关系。采用XPS和FTIR研究Si O2微粉与水泥水化产物经110℃烘干和800℃热处理后的化学键变化。结果表明,经110和800℃热处理后,SiO2微粉和水泥水化物之间形成了Si—O—Al结合键。因此,在110~800℃,含Si O2微粉的铝酸钙水泥结合浇注料的强度较高的原因是Si O2微粉与水泥水化物之间形成了Si—O—Al化学键。     

铝酸盐水泥熟料对粉煤灰硅酸盐水泥性能的影响

以铝酸盐水泥熟料、硅酸盐水泥熟料和粉煤灰为原料,探讨了掺加少量铝酸盐水泥熟料对硅酸盐水泥及粉煤灰硅酸盐水泥复合体系水化、凝结和硬化性能的影响。结果表明,在硅酸盐水泥及粉煤灰硅酸盐水泥中掺加铝酸盐水泥熟料,可以明显缩短水泥的初、终凝时间,但复合体系的需水量增加;掺加少量铝酸盐水泥熟料(≤3%)可明显提高硅酸盐水泥的早期强度,但后期强度(28d)有所降低;当铝酸盐水泥熟料的掺量达5%时,水泥的各龄期强度均明显降低。少量铝酸盐水泥熟料掺加到粉煤灰硅酸盐水泥中,复合体系的各龄期强度都明显提高,且早期强度的提高幅度较大。     

Porosity-strength relation in calcium aluminate cement pastes

The compressive strength and the volume porosity of calcium aluminate cement pastes have been studied in order to connect their relationship. The influence of mass fraction of lithium carbonate on compressive strength and porosity of calcium aluminate cement (CAC) has been investigated at different water-cement (w/c) ratios. The functions proposed in the literature for different technical materials were tested on obtained strength and porosity data. Those functions have been a base for further development of more general functional dependence of strength and porosity for cement materials. Thus, we propose the following equation to relate the strength and porosity for CAC pastes:

     

Calcium silicate and calcium aluminate cements for dentistry reviewed

Calcium silicate cements were identified as excellent materials for dentistry, particularly for dental procedures contacting the dental pulp or root system. Both calcium silicate and calcium aluminate cements cause the biomineralization (precipitation of hydroxyapatite [HA] phenomena and shield dental tissues from the underlying cement (a foreign body material). The cements also elute ions to stimulate cytokines that contribute to the healing of the dental pulp or in the tissue surrounding the root of a tooth. The cements serve as a foundation for other dental restorative materials. This paper reviews the cement phases, properties, in vivo reactions, and clinical benefits from the use of calcium silicate and calcium aluminate ceramic cements.