不同类型缓凝剂对建筑石膏的缓凝作用

研究了麦蛋白水解液石膏缓凝剂、柠檬酸、六偏磷酸钠对脱硫石膏的凝结时间、强度损失等的影响,同时也对不同水化环境pH值条件下的缓凝作用的凝结硬化特征进行了分析,并结合XRD和SEM对建筑石膏强度损失的原因和缓凝剂的缓凝机理进行了分析。对比结果表明:凝结时间相近的情况下,麦蛋白水解液对石膏的强度影响最小,而六偏磷酸钠影响最大;麦蛋白水解液对pH值环境适用范围最广,有良好的适应性,并在弱碱条件下缓凝效果最佳,而柠檬酸和六偏磷酸钠分别在酸性和中性条件下缓凝效果最佳;麦蛋白水解液对二水石膏晶体形貌基本没有影响,而六偏磷酸钠和柠檬酸使明显而完整的二水石膏针片状晶体减少。     

掺粉煤灰和不同外加剂对水泥水化放热过程的影响

通过水化热测量研究了掺加缓凝型减水剂、引气剂和粉煤灰对硅酸盐水泥的水化放热过程的影响。结果表明,掺入缓凝型减水剂能不同程度地延缓水泥的水化放热过程,降低水泥的水化热,掺入引气剂对水泥水化放热几乎没有影响,而掺粉煤灰可显著降低水泥水化热。     

化学外加剂对混凝土徐变的影响规律研究

采用自制的徐变加载装置,研究了萘系减水剂、聚羧酸减水剂以缓凝组分、减缩组分对等配合比混凝土徐变的影响规律,结合与混凝土同水灰比浆体非可蒸发水含量及混凝土内部相对湿度演化分析了其影响机理。结果表明,相比萘系减水剂,聚羧酸减水剂能显著降低混凝土的徐变,其中以早强型聚羧酸减水剂的效果最好;减缩剂对混凝土的徐变有降低作用,缓凝组分的掺入对徐变有不利影响;聚羧酸减水剂和减缩组分能通过降低混凝土内部水分传输和向外界扩散来降低徐变;早强型聚羧酸使浆体具有较多的水化产物数量,对强度的增加和徐变的降低有一定好处,缓凝组分的掺入会延缓水化并减少总水化产物数量,降低强度,使徐变增加。     

聚羧酸系减水剂复配β-环糊精对高贝利特硫铝酸盐水泥性能的影响

高贝利特硫铝酸盐水泥(High belite calcium sulphoaluminate cement, HBCSA)是一种新开发的具有低收缩特性的新型胶凝材料,具有强度发展均衡、不易析碱泛白、体积稳定性高和耐久性好等优异性能。但实际应用中发现HBCSA凝结硬化快,常用缓凝剂都难以有效延缓其快速水化的问题,这成为制约其广泛应用的瓶颈。为有效控制HBCSA的凝结时间,扩大其应用范围,本工作将探讨适用于HBCSA的化学外加剂,并揭示HBCSA的水化硬化作用控制机理,提出有效的调控措施。研究发现,将聚羧酸减水剂(Polycarboxylate superplasticizer, PCE)与缓凝组分β-环糊精(β-cyclodextrin, β-CD)复掺到HBCSA净浆或胶砂试件中具有较好的缓凝效果。同时测试了掺加复合外加剂的HBCSA浆体的流动度、凝结时间和各龄期胶砂试件强度,并利用扫描电子显微镜(Scanning electron microscope, SEM)、X射线衍射分析仪(X-ray diffraction, XRD)、总有机碳(Total organic carbon, TOC)分析仪和八通道热导式等温量热仪深入研究复合外加剂对HBCSA性能的影响。研究结果表明:PCE复掺β-CD的加入减缓了HBCSA水化产物中钙矾石的生成速度,从而有效延长了水泥凝结时间,且两者复配对改善HBCSA的流动性和中后期胶砂强度有积极作用。     

掺梳形减水剂水泥浆体早期水化产物形貌研究

为揭示梳形减水剂对水泥早期水化的影响规律,指导工程应用,通过SEM分析,研究了掺用3种典型结构的梳形减水剂的水泥浆体早期水化产物形貌及其电子特征数据。结果表明,梳形减水剂加速了水泥早期水化反应,且丙烯酸类、马来酸类共聚物分别促进了AFt、AFm的形成。因此,梳形减水剂品种对水泥早期水化和混凝土工程性能具有较大影响,应根据使用要求合理选用,必要时与缓凝剂、引气剂或消泡剂复合使用。     

缓凝剂对C3A石膏体系水化历程的影响

利用多种缓凝剂对C3A-石膏体系水化历程进行调控,研究缓凝剂对其水化历程的影响,采用了水化热、XRD和拉曼光谱等测试手段分别表征了水化放热规律及水化历程变化规律。结果表明,三聚磷酸钠对于C3A-石膏体系水化历程的延缓作用最强,而硼酸则能更好地抑制水化放热总量。三聚磷酸钠可抑制石膏的溶出速率,延缓早期水化反应,且难溶性磷酸钙盐的吸附及包裹作用会抑制C3A的溶解水化作用;而葡萄糖酸钠的静电吸附、不溶性钙盐包裹作用以及硼酸的沉淀作用会隔离C3A颗粒与水接触,阻碍了C3A的水化反应。     

缓凝剂对磷酸镁水泥性能及其水化机制影响研究进展

磷酸镁水泥(MPC)作为一种新型无机胶凝材料,具有早期强度高、干缩小、耐久性好等优良性能,在土木结构工程的快速修补和危废快速固化处理等领域有着极大优势.但磷酸镁水泥因强烈的放热反应,凝结速度过快,可施工操作性较低,所以其缓凝技术研究成为了该类材料规模化应用需解决的关键技术之一.缓凝剂的添加,可有效延缓磷酸镁水泥的凝结速度,改善其可施工操作性.本文基于国内外磷酸镁水泥缓凝剂研究,综述了几种常用的缓凝剂(硼砂(B)、硼酸(BA)和三聚磷酸钠(STP))对磷酸镁水泥性能(水化热、抗压强度、凝结特性)及其水化机制的影响,对其缓凝机理进行了分析讨论.就当前缓凝剂改性MPC研究中的优势及不足,并结合实际应用需求展望其今后研究和发展方向,为MPC后续缓凝研究提供文献支撑.     

杂质对磷石膏应用性能的影响

磷石膏是一种含有磷、氟等杂质的化学石膏,其中杂质对磷石膏的应用性能产生了不利影响,限制了其实际应用.由于杂质的存在,磷石膏脱水温度较天然石膏低,当其用作水泥缓凝剂时,在粉磨温度下可能脱水生成半水石膏和无水石膏,影响水泥性能;磷石膏和天然石膏制备的半水石膏胶结材料微观结构与物理性能之间存在较大差异.现有磷石膏预处理研究大多偏重于宏观性能的比较,而对杂质影响机理的研究较为欠缺,因此很有必要对其进行系统的基础研究.     

有机膦酸类化合物在混凝土工程中的应用及缓凝机理研究进展

通过掺加具有水化热抑制作用的外加剂来降低胶凝体系的水化放热量及放热速率是减少混凝土中温度裂缝的重要措施。相对于葡萄糖酸钠和糖钠等常用缓凝材料,有机膦酸类化合物对硅酸盐水泥具有更为有效的水化热抑制作用和缓凝作用。过去几十年,有机膦酸类化合物在国外常被作为缓凝材料应用于工民建、油田固井和一些有特殊要求的混凝土工程中。在我国,有机膦酸类化合物主要应用在油田固井混凝土工程中,近年来在越来越多的工民建混凝土工程中也有所应用,但是其应用范围仍然十分有限。有机膦酸类化合物具有以下特征:(1)在一定掺量范围内可大幅降低硅酸盐水泥的水化放热速率和放热量,改善硅酸盐水泥水化放热过程;(2)有机膦酸类化合物对水泥熟料含量的变化不敏感,与硅酸盐水泥、聚羧酸减水剂和萘系减水剂均具有较好的适应性;(3)在一定掺量范围内,有机膦酸类化合物可改善混凝土拌合物性能,提高混凝土长期力学性能;(4)有机膦酸类化合物的主链结构具有高温稳定性,适用温度达200℃以上,在高温环境下其对硅酸盐水泥仍具有较强的缓凝作用。有机膦酸类化合物对硅酸盐水泥水化的影响较复杂,目前硅酸盐水泥缓凝机理尚不十分明确。不同学者对此持有不同的观点。其中一种观点认为:有机膦酸类化合物首先促进水泥中Ca~(2+)溶解,在富铝层表面促进水泥矿物水化,进而促进铝酸三钙(C_3A)的水化;接着与水泥中Ca~(2+)结合,在硅酸三钙(C_3S)表面形成半透水的稳定螯合物,抑制C_3S的水化,从而抑制水泥的进一步水化。而另一种观点认为:有机膦酸类化合物有效抑制了钙矾石凝胶向晶体转变的成核和生长过程,并认为延缓钙矾石晶体的生长是导致硅酸盐水泥缓凝的主要原因。本文从有机膦酸类化合物在混凝土工程中的应用着手,总结了有机膦酸类化合物对硅酸盐水泥水化动力学的影响以及缓凝机理的研究进展。基于此,为进一步扩大有机膦酸类化合物在混凝土工程中的应用范围,提出了应进一步研究有机膦酸化合物对混凝土力学性能、体积稳定性、热力学性能和耐久性能的影响,同时应进一步研究有机膦酸类化合物对硅酸盐水泥水化动力学的影响及缓凝机理。     

粉刷石膏的研究

研究了分别以柠檬酸、柠檬酸与普通硅酸盐水泥复合物作缓凝剂,调节粉刷石膏的凝结时间,并对比2种缓凝体系对石膏抗折、抗压强度的影响.比较不同保水剂（聚乙烯醇、羧甲基纤维素）以及相同量的保水剂在不同工艺流程下保水效果上的区别.探索了有机保水剂和无机保水剂对粉刷石膏的保水性的影响.结果表明,柠檬酸与普通硅酸盐水泥的复合缓凝剂比单纯的柠檬酸更能有效地延缓建筑石膏的凝结,同时建筑石膏的抗折、抗压强度降低幅度减小.     

矿物外加剂对丁苯聚合物/水泥复合胶凝材料凝结硬化过程的影响及机制

为了比较沸石、纳米二氧化硅和稻壳灰这3种矿物外加剂对丁苯聚合物/水泥复合胶凝材料凝结硬化过程作用的差异,分别采用这3种矿物外加剂为调凝材料,并从凝结时间、早期强度、水化进程以及水化产物等角度比较3种矿物外加剂对丁苯聚合物/水泥复合胶凝材料的影响。结果表明,3种矿物外加剂都能促进复合胶凝材料的凝结硬化,大幅缩短凝结时间,提高早期强度。但3种矿物外加剂的调凝效果互不相同,调凝机理也有差异:沸石对AFt的生成有较大的促进作用,它不仅能促进C3A的水化,自身也能与Ca(OH)_2反应生成AFt和CSH凝胶;而纳米二氧化硅和稻壳灰对C3S水化的促进作用较强,自身也会与Ca(OH)_2反应生成CSH凝胶。     

Properties of shrinkage-reducing admixture-modified pastes and mortar

A comprehensive study on the influence of a shrinkage-reducing admixture (SRA) on properties of ordinary Portland cement and shrinkage-compensating cement has been conducted. The properties investigated include: electrical resistivity, hydration heat rate, free shrinkage and restrained shrinkage cracking. It is found that the shrinkage-reducing admixture (SRA) can reduce the free shrinkage and postpone the occurrence of shrinkage crack significantly. The SRA has also an effect to retard the hydration process of Portland cement under normal condition. However, under semi adiabatic condition, it seems that SRA accelerates the hydration process. A new concept of the hardening ratio, ρ _H , is proposed in the study. It is indicated that the hardening ratio, ρ _H , and compressive strength development have very good linear relationship.     

Admixtures in cement: a study of dosage rates on early hydration

The authors have shown from earlier work that the electrical response of cement paste to an alternating electrical field can be used as a technique for monitoring hydration and phenomena such as setting and hardening. This paper demonstrates an area in which the technique could prove effective, by showing the influence of a range of commercial admixtures on electrical response. It is clearly indicated that admixtures have a definite effect on the response characteristics.     

Solid state NMR investigations on the role of organic admixtures on the hydration of cement pastes

The influence of different inorganic additives and organic admixtures on the hydration and hardening of Portland cement (CEM I 42.5R) were studied on a nanometer scale by advanced solid state NMR methods. Added quartz was found to be partially attacked by the alkaline media of the cement paste. Even small amounts of organic admixtures strongly influence the hydration and crystallization process of the cement paste. Methyl cellulose, poly(vinyl acetate co vinyl alcohol), poly(ethylene oxide), poly(acrylic acid) and poly(acrylamide) modify the hydration of the calcium aluminum oxides. Major changes in the inorganic structure were detected for low amounts of citric acid and tartaric acid which suppress silicate condensation and strongly alter calcium aluminum oxide hydration. Within this study several solid state NMR methods like 1D magic angle spinning (MAS), 2D exchange and 2D double quantum NMR were applied for the detection of ¹H, ²⁷Al and ²⁹Si nuclei. Thus, cement pastes, inorganic additives and organic admixtures could be monitored individually. The findings on a molecular level as provided by NMR are related to changes in the mechanical properties of the cement pastes.     

Effect of gypsum type on properties of cementitious materials containing high range water reducing admixture

In this study, the effect of cement gypsum type on properties of the properties of cement paste, mortar and concrete mixtures containing high range water reducing admixture (HRWR) was investigated. Two different types of cement prepared from the same clinker but containing either calcium sulfate hemihydrate or dihydrate as retarder were used. The fresh and hardened (compressive strength and drying-shrinkage) properties as well as static and dynamic rheological behavior of the mixtures were investigated. Compared to the mixtures containing dihydtate, the fresh and rheological properties of mixtures were negatively affected when cement-containing hemihydrate was used. However, hemihydrate utilization had a positive influence on the early compressive strength. The adverse effects on fresh properties were more significant in paste mixtures. These negative effects decreased in the mortar and concrete mixtures. The presence of hemihydrate in cement was found to increase the drying-shrinkage.     

新型水溶性高分子土体固化剂的性能及机理研究

本文研究了水溶性高分子土体固化剂对土体室内CBR及回弹模量的影响。试验表明 ,分子量越小 ,其固化性能越好 ,特别对Ca2 + 含量为 2 %左右的土体具有优异的土体固化效果。同时初步探讨了高分子固化剂的固化机理     

金尾矿蒸压加气混凝土水化机理和微观结构分析

为明确金尾矿蒸压加气混凝土制品的水化机理和微观结构的内在关系,通过对比硬化坯体(NAC)、蒸压恒温养护0 h(AAC-0)和蒸压恒温养护8 h(AAC-8)的3组样品的XRD谱、IR谱图分析其水化产物种类的变化,并对比SEM照片分析了其微观结构变化.研究结果表明,随着蒸压养护过程的进行,坯体内的水化产物出现阶段性变化,最终由富钙型水化硅酸钙向托贝莫来石转化,由于托贝莫来石生成的局限性和同步性,导致微观孔壁结构出现明显的分层现象,后生成的托贝莫来石层使孔结构成为中空的刚性球,作为"骨料",起到骨架和支撑的作用.     

Simulation of the microstructure formation in hardening self-compacting cement paste containing limestone powder as filler via computer-based model

With the development of concrete technology, fillers are widely used in high performance concrete to improve its properties. Among them, limestone powder is popularly added in self-compacting concrete to gain good flowability. However, by lack of experimental data, several materials properties after the addition of limestone powder are still not sure, which actually yield some uncertainty for the further use of limestone powder in cement-based materials. In this study, by employing computer-based model, the microstructure of self-compacting cement paste containing limestone as filler is simulated and further used to investigate the role of limestone in hardening materials. To gain this goal, thermometric isothermal conduction calorimetry, thermal analysis and backscattered electron image acquisition were applied to understand the hydration kinetics with the addition of limestone filler. After that, a computational materials model based on HYMOSTRUC was developed to simulate the formation of microstructure in materials containing limestone powder. The predictive ability of the model was validated with the experimental test results. Then the developed model was employed to investigate the influence of several variables, such as water to cement ratio, limestone filler content and fineness, on the microstructure formation in hardening materials. The numerical experiments show that the addition of limestone filler could result in a denser microstructure at the initial hydration stage. With the proceeding of hydration, the limestone powder has a decreasing influence on the microstructure, and could obstruct somewhat the formation of a denser microstructure at later hydration stage. And it is found that computer-based modelling is an effective method to provide insights into the material behaviour, by relieving researchers from numerous repeated experiments.     

水泥混凝土中钙矾石膨胀及抑制的研究进展

从晶体成长理论和吸水膨胀理论两方面阐述了钙矾石的膨胀机理,论述了钙矾石膨胀的抑制机理,介绍了目前国外结晶化抑制剂的研究进展、一些抑制剂的效果以及影响抑制剂效果的因素,并对这些抑制剂及其效果进行了总结,最后展望了我国钙矾石抑制剂的研究前景.