Effect of M/P and Borax on the Hydration Properties of Magnesium Potassium Phosphate Cement Blended with Large Volume of Fly Ash

The effect of the borax content and magnesia to phosphate ratio(M/P) on the hydration properties of the magnesium potassium phosphate cement(MKPC) with large volume of fly ash was investigated, and a five-hydration-stage for MKPCs was proposed. The results show that MKPC sets rapidly with less than 8% of borax, which is unfavorable to the application of MKPC on construction. Adding more than 8%(including 8%) of borax results in a secondary hydration peak for MKPC, in which the process of hydration can be divided into five stages, namely, pre-induction period, induction period, acceleration period, deceleration period and stable period. M/P ratios could not change the multi-step reactive stages but higher M/P ratios could accelerate the hydration. Borax tends to impact the formation of Mg-containing hydrated products.     

磷酸镁水泥的研究

用氧化镁（MgO）和磷酸二氢铵(NH     

Influence of Nano-SiO_2 Addition on Properties of Sulphoaluminate Cement Based Material

The influences of different nano-SiO_2(NS) contents on the mechanical properties and rheological behavior of sulfoaluminate cement(SAC) based composite materials were studied.Results show that with increasing content of NS,the apparent viscosity,and shearing strength of fresh paste gradually increase but the fluidity decreases.With a dosage of 3.0%NS,the tensile and flexural strengths of mortars at 56 days were increased by 87.0%and 84.6%,respectively,compared with that in the absence of NS,indicating that the toughness of hardened mortars is significantly improved.Besides,the exothermic peaks of hydration are obviously increased and will earlier occur,and the second and the third peaks appear 2.61 hours and 2.56 hours earlier,respectively than that in the absence of NS,and the hydration of SAC before 8 hours is accelerated.The forming mechanism of strengths was revealed by scanning electron microscopy(SEM),hydration heat,X-ray diffraction(XRD) and derivative thermogravimetry(DTG).The micro-aggregate filling effect and nucleation effect at early age and weak pozzolanic effect at late age of NS make the microstructure more compact,which obviously enhances the strength of SAC mortars.     

Influence of MgO/MgCl2 molar ratio on phase stability of magnesium oxychloride cement

Formation, solution and phase change of hydration products in MgO-MgCl₂-H₂O system was studied with thermodynamics method, and resistance to water immersion and phase change of magnesium oxychloride cement with different MgO/MgCl₂ molar ratio was experimented. The results show that pH value of immersion solution of cement paste has a remarkable influence on phase stability of hydration products. A higher pH value leads to a lower solubility and a better phase stability of hydration products. When the solution pH value is higher than 10.37, the precipitation of much Mg(OH)₂ crystal induces a worse phase stability of hydration products. With the increasing MgO/MgCl₂ molar ratio (lower than 6), the more amount of MgO in the hydration products enhances the alkalinity of solution and the phase stability is improved. However, when the MgO/MgCl₂ molar ratio is higher than 6 and the excessive MgO exsits in the hydration products, the cement paste may be damaged by the excessive crystallization stress of a great deal of Mg(OH)₂ formation. Funded by the National Natural Science Foundation of China(No. 50078019)     

聚合物-水泥基注浆材料早期流变及水化特性

为制备满足复杂地层加固工程需求的高性能水泥基注浆材料,探究以偏铝酸钠(SA)、聚羧酸(Sp)及高吸水性树脂(SAP)为组分的聚合物体系及其掺量对新拌水泥浆体流变特性与泌水率的影响,并采用水化放热监测与倒置荧光显微技术,对不同体系下水泥浆体早期水化进程及微米级颗粒的悬浮分散形态进行分析.结果表明:新拌水泥浆液流动性和泌水率与SA、SAP掺量呈负相关,随Sp掺量增加而提高. Sp及SAP延缓了水泥早期水化进程,改性样延迟近1 h进入水化诱导期,诱导期内水化放热速率显著降低.在不同掺量SA的促凝效应、Sp的分散效应以及SAP的"水库"作用下,新拌水泥浆液表现为初始及经时流动度大于200 mm的高流态期可分别被控制在10、20、30 min内且析水率小于5%(稳定性浆液),接近临界期时流动度陡降、流变参数突增并迅速凝结的流变特性.结合微观结构观测结果,建立了新拌水泥浆体流变演化模型,揭示多聚合物协调效应下水泥浆体呈现分散-储水-流变-水化的早期流变机制.     

缓凝剂对建筑石膏结构与强度的负面影响

利用SEM扫描电镜、MIP压汞测孔技术等测试手段．系统深入地研究了柠檬酸、多聚磷酸钠、骨胶3类常用典型缓凝剂对建筑石膏水化早期液相过饱和度、晶体形貌以及硬化体孔结构的影响,研究了石膏强度损失的内在原因和机制．结果表明：缓凝剂降低了胶凝材水化早期液相过饱和度,改变了二水石膏结晶习性和晶体形貌,晶体明显粗化,晶形也由针状转变为短柱状,大大削弱了晶体间的搭接,硬化体孔径增大,大孔比例明显增加,孔结构劣化,并最终导致建筑石膏强度的大幅度降低．强度损失与其缓凝效果基本成正比,掺量越高,缓凝时间越长,强度损失越大．     

配合比参数对脱硫灰磷酸盐快速修复材料性能的影响

为解决混凝土结构快速修复及脱硫粉煤灰的资源化利用,提出利用脱硫粉煤灰、凝灰岩机制砂制备磷酸盐快速修复材料(MKPC).采用单因素试验方法研究了30℃高温下配合比参数对流动性、凝结时间和力学性能的影响,结合功效系数法确定满足多项指标的优化配合比参数.试验结果表明:MKPC流动度随着碱酸比、硼砂用量、水胶比、砂胶比及脱硫灰掺量的增大,依次呈抛物线型增加、指数衰减、线性增加、指数增长及指数衰减的变化规律;凝结时间随着碱酸比的增加呈线性递减变化,随硼砂用量、水胶比及脱硫灰掺量的增加呈指数增长型变化规律;1 h力学性能随着脱硫灰掺量的增加呈线性递减变化,随硼砂用量、水胶比及脱硫灰掺量的增加呈抛物线型变化规律.优化出的MKPC体系配合比参数满足快速修复现场施工要求.     

Influence of elevated curing temperature on the properties of cement paste and concrete at the same hydration degree

Three different curing temperatures(20 ℃, 40 ℃, and 60 ℃) were set, so that the nonevaporable water(w_n) contents of plain cement pastes cured at these three temperatures were measured to determine the hydration degree of cement. Tests were carried out to compare the pore structure and strength of cement paste, as well as the strength and permeability of concrete under different temperature curing conditions when their cements were cured to the same hydration degree. The experimental results show that either at a relatively low hydration degree(w_n=15%) or high hydration degree(w_n=16.5%), elevated curing temperature has little influence on the hydration products of cement paste, while it has a negative influence on the pore structure and compressive strength of cement paste. However, this negative effect is weaker at high hydration degree. The large capillary pore(100 nm) volumes of cement pastes remain almost the same at high hydration degree, regardless of curing temperatures. As for the concrete, elevated curing temperature also has negative influence on its compressive strength development, at both low hydration degree and high hydration degree. And this negative effect is stronger than that on cement paste's compressive strength at the same hydration degree. On the whole, elevated curing temperature has little influence on the resistance of concrete to chloride ion penetration.     

矿粉对水泥和混凝土性能的影响

为了探寻矿粉细度及掺入量对水泥和混凝土性能的影响,通过试验测试方法,分析了矿粉和水泥的基本性质,研究了超细矿粉和普通矿粉的掺量对水泥基材料标准稠度、凝结时间、流动度和力学性能的影响.结果表明：普通矿粉使水泥净浆标准稠度需水量下降,而超细矿粉则增加标准稠度需水量,两种矿粉都使水泥净浆凝结时间略微延长.普通矿粉可以改善水泥净浆的流动度,超细矿粉的加入则降低了水泥净浆的流动度.普通矿粉和超细矿粉降低水泥净浆早期（7 d）抗压强度,提高后期（28 d）抗压强度,掺10％～50％的普通矿粉的水泥净浆28 d抗压强度提高2.9％～9.7％,掺入超细矿粉28 d抗压强度提高3.9％～20.1％,普通矿粉和超细矿粉的最佳掺量为10％～30％;两种矿粉替代10％～50％水泥所配制的混凝土的强度得到了明显的提高.     

硼掺合料对水泥浆体性能的影响

研究了不同含硼添加剂对水泥浆体凝结时间、抗压强度、抗折强度、结合水含量及碱度的影响,并采用XRD和SEM测试手段分析了硬化浆体微观结构,着重考察了硼元素的引入方式对水泥水化性能的影响。研究表明:硼砂、硼酐及硼玻璃粉对水泥浆体性能的影响存在很大差异。硼砂具有明显的缓凝作用;硼酐稍延缓了水泥的凝结时间,但严重影响了水泥石的力学性能,主要可能是硼酐中可溶性硼与水泥水化后的钙离子形成致密的水化硼酸钙膜,覆盖在水泥颗粒表面,阻止了水泥颗粒与外部溶液的接触,使水泥水化反应无法正常进行;而硼玻璃粉对水泥的凝结时间和力学性能均不存在不良影响。     

Ultra high early strength self-compacting mortar based on sulfoaluminate cement and silica fume

The influences of silica fume and aluminum sulfate on hydration process of sulfoaluminate cement were carried out by ring flow, setting time, hydration heat, XRD and DTG analyses. In addition, mortar mixtures with different functional additives have been studied through compressive strength, flexural strength, volume stability at early age and porosity characterization tests. The results show that the addition of silica fume and aluminum sulfate reduces the fluidity and shortens the setting time of sulfoaluminate cement paste, promoting hydration process and increasing hydration products at early age. In the case of appropriate proportion of mortar, the inclusion of hydroxy propyl methyl cellulose, dispersible polypropylene fiber and organic silicon kind of defoamer can control segregation and bleeding, improve mechanical strength and volume stability at early age, and modify the pore distribution of sulfoaluminate cement mortar, respectively. The sulfoaluminate cement mortar can carry out gravitational grouting in the absence of outside force, the compressive strength of 2 hours and 24 hours have reached 26 and 58 MPa respectively, and have good microexpansion and tiny pore distribution characterization.     

磷酸盐水泥对137Cs的固化性能

以含95％MgO的重烧镁砂、磷酸盐和硼砂为原料,制备了磷酸盐水泥,研究其对137Cs的固化性能。通过XRD衍射分析、SEM电镜扫描等手段对固化体物相组成及显微结构进行分析,参照国家标准“放射性废物固化体长期浸出试验”（GB7023—86）对固化体进行抗浸出性能试验。结果表明,当以磷酸氢二铵为原料时,137Cs的加入会降低磷酸盐水泥固化体的抗压强度,137Cs的含量越多,强度损失越小;当以磷酸二氢铵为原料时,随着137Cs的加入,强度先减小后增大,掺量为1．6％时强度甚至超过了空白体系;以磷酸二氢钾为原料时,137Cs的加入会使强度减小,减小程度和掺量关系的规律性不明显。以磷酸二氢铵、磷酸二氢钾为原料的固化体抗压强度明显优于以磷酸氢二铵为原料的固化体。以磷酸二氢铵为原料的固化体,137Cs的42d浸出率和累计浸出分数低至2．1×10-4（em·d11）和7．74×10^-3cm,强度值和浸出率均优于国家标准相关要求,表明了磷酸盐水泥对137Cs有良好的固化效果。     

基于水化动力学模型的水泥基材料温度效应

为探究温度对水泥浆水化过程的影响,采用等温量热仪测试了水泥浆样品在20,30和40 ℃的水化放热量和水化放热速率,获得了水化度α和表观活化能Ea并利用Krstulovic-Dabic模型计算了相应阶段动力学参数K和n,探讨不同温度的水泥浆体的水化机理。结果表明,水化动力学参数随温度升高显著增大,水泥浆在20~40 ℃的水化表观活化能Ea为37.63 kJ/mol,且升高温度促进0~72 h内水泥水化度的增长。20 ℃下的水泥浆具有NG-I-D过程,而30 ℃和40 ℃下的水泥浆只具有NG-D过程,表明升高温度使水化阶段的持续时间缩短,且反应速率加快。研究可为水泥基材料在不同环境温度下施工时控制浇筑时间以及掌握强度的发展趋势,提供一定的理论依据。     

电阻率法研究磷及石灰对水泥凝结硬化的影响

用非接触式电阻率测试仪研究了不同含量的可溶磷及石灰对水泥早期水化过程中电阻率的影响。结果表明:可溶磷使得水泥早期的电阻率降低,水化进程推迟,且随着可溶磷含量的增加,电阻率呈逐步降低趋势;单独添加石灰对水泥早期水化影响较小;石灰中和可溶磷后可补偿可溶磷的对水化的延期危害,其电导率随时间变化规律与未添加磷、石灰的水泥基本一致。     

原料及配比对磷酸镁水泥性能影响的研究

采用磷酸二氢铵、磷酸二氢钾和磷酸氢二铵作为引入磷的材料,不同细度的重烧镁砂以及不同掺量硼砂作为缓凝剂,通过测定其标准稠度需水量、凝结时间和抗压强度,结合X射线衍射分析和扫描电镜分析,研究了不同的磷酸盐原料及配比对磷酸镁水泥性能的影响。结果表明,磷酸盐水泥的凝结时间和强度随原料及配比变化有较大差异,磷酸二氢钾与磷酸二氢铵的性能较为接近,而采用磷酸氢二铵既加大了标准稠度用水量,也大幅度延长了凝结时间;同时采用磷酸氢二铵试样的强度相对也远小于采用磷酸二氢钾与磷酸二氢铵的试样;硼砂作为缓凝剂也可明显延长磷酸镁水泥的凝结时间。     

高锰酸钾氧化去除水中三氯生动力学研究

为了揭示高锰酸钾氧化去除水中三氯生的动力学规律,通过烧杯试验研究得出高锰酸钾氧化三氯生的反应速率常数,同时探讨高锰酸钾浓度、pH、温度等因素对反应速率常数的影响.试验结果表明：不同高锰酸钾浓度下,三氯生能够被迅速氧化,氧化三氯生的反应符合二级反应动力学,二级反应动力学常数K=0.331 6 mL.s-1.mol-1.p...     

早强型聚羧酸减水剂的合成及性能研究

以丙烯酸(AA)、异丁烯醇聚氧乙烯醚(HPEG)、甲基丙烯磺酸钠(SMAS)等为单体,分别采用丙烯酰胺(AM)、羟甲基丙烯酰胺(HAM)取代部分丙烯酸,通过水溶液聚合法制备出具有早强功能的聚羧酸系减水剂,并探讨了合成条件对水泥净浆流动度的影响.研究结果表明:在单体摩尔比n(AA)∶n(HPEG)∶n(SMAS)=4∶1∶0.36、反应温度为80℃、过硫酸铵(APS)用量为单体总质量的3%时,制备出的聚羧酸减水剂的分散性能较优.当AM取代为18%时,对提高混凝土的早期强度效果较佳,AM比HAM具有更好的早强效果.     

缓凝剂对石膏作用效果的影响

缓凝剂在石膏中作用效果如何,取决于石膏pH值、石膏细度、石膏品种、石膏水灰比及水化温度等诸多因素,主要考察了石膏pH值、石膏细度和石膏品种对缓凝剂作用效果的影响.结果表明:石膏pH值、石膏细度和石膏品种不同,缓凝剂对石膏凝结时间和强度的作用效果不同.     

聚羧酸系高效减水剂PC的合成及性能研究

以甲基丙烯酸、聚乙二醇1000、对甲苯磺酸、对苯二酚、过硫酸铵和甲基丙烯磺酸钠为原料,采用两步法合成出新型聚羧酸系高效减水剂(简称PC)。将合成的PC与目前广泛使用的萘系高效减水剂(简称FDN)相比,具有更加优异的性能,具体表现为:在掺量很少情况下,水泥净浆就具有较高的流动度;当掺量相同时,其对水泥净浆流动度远超FDN。此外,它与水泥的相容性好,具有缓凝及明显抑制水泥净浆流动度经时损失性能,对混凝土也能表现出显著的减水增强性,是一种性能优良,适合于配制高强、超高强混凝土的高效减水剂。     

粉煤灰混凝土绝热温升的试验研究

目的 研究不同粉煤灰的掺量和不同水肢比条件下粉煤灰混凝土的绝热温升和胶凝材料水化速率的发展规律．方法 利用混凝土绝热温升仪测试混凝土绝热温升．结果 在水胶比0．53条件下，混凝土的绝热温升值随着粉煤灰掺量的增加而下降；在水胶比0．25条件下。绝热温升值先随着粉煤灰掺量的增加而增大，当掺量达40％以后绝热温升值开始下降。混凝土中胶凝材料的水化速率峰值随粉煤灰掺量增加而下降．结论 粉煤灰混凝土的绝热温升受水胶比和粉煤灰掺量共同影响，低水胶比条件下只有适当增加粉煤灰的掺量才能降低粉煤灰混凝土的绝热温升；高水胶比条件下。粉煤灰混凝土的绝热温升随粉煤灰掺量增加而下降。