Influence of New Compound Admixture on Shotcrete Performance

To analyze the influence of new compound admixture on shotcrete performance, the ordinary Portland cement pr425 was used as matrix components. The optimum proportion of admixture was obtained by analyzing the influence of content on cement setting time and compressive strength. The microstructure of cement test block and the mechanism of reducing dust of composite macromolecule admixture were analyzed by scanning electron microscopy and infrared spectroscopy. It was shown that the ratio of polyacrylic acid was 0.02%. The ratio of J85 accelerator was 5%. The ratio of bentonite was 4.5% in composite admixture. The most optimal content of admixture in the slurry was 7%. The compound coagulant formed by additive together with C_3 A, C_4 AF which provided nucleation for hydration and crystallization of C_3S and C_3S, and played an active role to promote the activity of the mineral admixture in cement, and increased the elastic modulus of C-S-H gel and accelerated the hydration process of portland cement. Bentonite and polyacrylic acid promote the wettability, cohesiveness and workability of cement paste in the process of hydration. The formation of cement test block gel was even. The interface between the matrix phase and the aggregate phase was not obvious which ensured the matching between the matrix and the aggregate phase. The addition of bentonite formed hydrogen bonds in cement paste and improved the cohesiveness of the system. The J-85 accelerator promoted the combination of aluminate and gypsum which hindered the formation of calcium carbide around the cement particles which made cement rapid condensation. Polyacrylic acid mainly changed the strength of hydroxyl absorption peak in cement paste to improve the initial strength of cement test block. The addition of new admixtures promoted the process of cement hydration to be more thorough and affected the later strength development of concrete by affecting the formation of calcium carbonate stone.     

聚羧酸减水剂对不同晶型C3S早期水化放热的影响

采用水化微量热仪研究了不同类型聚羧酸减水剂对不同晶型C3S水化放热特性的影响。结果表明:单斜晶系(M)C3S、三方晶系(R)C3S的水化放热速率峰值相比三斜晶系(T)C3S显著降低,且水化放热峰出现延迟,MC3S的水化放热峰延迟最明显。三种晶型C3S的3d水化放热总量由大到小为:TC3S、MC3S、RC3S。不同分子结构的甲氧基聚乙二醇甲基丙烯酸酯系聚羧酸减水剂,主链越短,支链越长,对TC3S的水化延迟作用越大。乙烯基聚乙二醇醚系聚羧酸减水剂对三种晶型C3S的水化放热过程延迟作用由大到小为:RC3S、MC3S、TC3S。对水化放热曲线进行的Krstulovic-Dabic模型研究表明,C3S的水化过程为NG-D类型水化历程。     

钢渣-矿渣-水泥复合胶凝材料的水化性能和微观形貌

通过测定矿渣和钢渣部分取代水泥构成的钢渣-矿渣-水泥复合胶凝材料(SBC-CCM)的物相组成和80h内的水化热,研究了SBC-CCM试样的微观形貌和水化性能,并用正交试验结果分析了SBC-CCM中钢渣-矿渣的最佳掺量和比例。结果表明:SBC-CCM的水化过程和水化产物的物相组成与硅酸盐水泥的相似,矿渣在水化早期参与反应,钢渣在水化早期呈惰性;SBC-CCM的80h水化放热量和放热速率均低于水泥相应的数值;正交试验结果表明水胶比对SBC-CCM强度的影响最显著,矿渣-钢渣的最佳质量比为2∶1。     

石灰石粉铝酸盐水泥复合体系的水化反应

石灰石粉具有水化活性,能与硅酸盐水泥中的C₃A、铝酸盐水泥中的CA、CA₂等铝酸盐矿物发生反应,水化产物为水化碳铝酸钙。利用微量热仪法、胶砂强度和X射线衍射（XRD）,研究不同比例的石灰石粉铝酸盐水泥复合体系的水化反应,结果表明：石灰石粉会加快铝酸盐水泥的水化进程,水化过程诱导期缩短,放热速率峰值下降;复合体系中石灰石粉占比越高,早期水化反应速率越快,但水化反应放热量越低;相对而言,复合体系中石灰石粉掺量为20%时石灰石粉参与反应程度最高,且掺量为20%时石灰石粉对复合体系强度有显著贡献。随复合体系中石灰石粉比例增加,铝酸盐水泥水化产物越来越不明显;石灰石粉掺量为20%~40%时,水化碳铝酸钙XRD特征峰相对最明显,复合体系中石灰石粉与铝酸盐水泥存在一个最佳的比例范围。研究表明,石灰石粉与铝酸盐水泥间会发生明显的水化反应,石灰石粉与铝酸盐水泥复合有望制得一种新型胶凝材料。     

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。     

Effect of Fly Ash and Silica Fume on Hydration Rate of Cement Pastes and Strength of Mortars

The effect of fly ash and silica fume on hydration rate and strength of cement in the early stage was studied. Contrast test was applied to the complex cementitious system to investigate the hydration rate. Combined with mechanical strength, the influence of fly ash and silica fume during the hydration process of complex binder was researched. The peak of the rate of hydration heat evolution and the mechanical strength decreased as the ratio of fly ash increased, however, as the ratio of silica fume increased, the peak of the rate of hydration heat evolution and the mechanical strength increased obviously. When the ratios of fly ash and silica fume are 10% and 5%, the peak of the rate of hydration heat evolution is the highest. At the same time 7 days of flexural and compressive strength are the highest as 8.89 MPa and 46.52 MPa, respectively. Fly ash and silica fume are the main factors affecting the hydration rate and the mechanical property.     

Hydration Kinetics of Municipal Solid Wastes Incineration(MSWI) Fly Ash-Cement

Hydration heat behavior and kinetics of blended cement containing up to 20% MSWI fly ash were investigated based on its hydration heat evolution rate measured by isothermal calorimeter. Kinetics parameters, N and K, and hydration degree, Ca(OH)_2 content, were also calculated and analyzed. According to the experimental results, the induction period was elongated, the second heat evolution peak was in advance, and the third hydration heat peak could be detected due to MSWI fly ash pozzolanic reaction. The hydration reaction rate was controlled by nucleation kinetics in the acceleration period and then by diffusion in the decay period, but in the deceleration period, the hydration experienced a dual controlling reaction of autocatalytic chemical reaction and diffusion. The hydration rate of blended cement was faster. Ca(OH)_2 content increased before 14 days.     

Analysis of Hydration Mechanism and Microstructure of Composite Cementitious Materials for Filling Mining

To obtain the compositions and microstructure of hydration products of cementitious material in different hydration ages and its growth law of filling strength, the optimal proportion of composite cementitious material was determined according to the chemical composition of cement clinker which was composed of the Portland cement 32.5R, CSA 42.5 sulphoaluminate cement and two gypsum(CS). The characterization of composite cementitious materials in different hydration ages was conducted by NMR, XRD and SEM techniques. The mechanism of hydration was explored. It is shown that the compressive strength of the test block increases gradually with the increase of hydration age. The microstructure of composite cementitious material can be changed from Al-O octahedron into Al-O tetrahedron in the hydration process. The hydrated alkali alumi niumsilicate formed with Si-O tetrahedron and Al-O tetrahedron. The degree of polymerization of Si-O tetrahedron gradually increased, and the structural strength of cementitious materials continued to increase. The diffraction peak of clinker minerals gradually decreased with the extension of hydration age. The CaSO_4 completely hydrated to produce Aft during hydration which resulted in high early strength of cementitious material. The early hydration product of composite cementitious materials was Aft with a needle bar structure. The main middle and last hydration products were CSH gel and CH gel with dense prismatic shape. The microscopic pore of composite cementitious material gradually decreased and improved the later strength of filling block. The strong support was provided for mined-out area.     

水泥高强化的选择性水化理论及其应用研究

本文综合前人的研究结果,提出了硅酸盐水泥高强化的选择性水化理论。即通过调整硅酸盐水泥中各矿物的水化速率,延缓C_3S水化,增加C_3A、C_4AF形成钙矾石的速率,就可达到高强化的目的。同时提出了实现选择性水化的具体措施,并通过实验确定了最佳参数值,使硅酸盐水泥强度得到了大幅度的提高。     

预填埋相变材料对混凝土水化热温升的降低效果

为了探讨能安全有效地降低混凝土水化热温升的方法,采用自制保温装置测量了普通混凝土构件和预填埋相变材料的混凝土构件内部相同位置温度随时间的变化,对预填埋相变材料降低混凝土内部温升效果的影响因素进行了计算和分析。研究结果表明:填埋相变材料后混凝土的内部温度与相变材料的填埋量、比热、相变热、相变温度,混凝土的比热、密度和初始温度,胶凝材料的用量和水泥水化热等因素相关。采用填埋相变材料的方法能够降低混凝土的内部温度峰值,延缓温度峰值的出现时间,但不能降低混凝土内部的后期温度。     

Effects of citric acid on hydration process and mechanical properties of thermal decomposed magnesium oxychloride cement

In order to make full use of salt lake magnesium resources and improve the strength of the thermal decomposed magnesium oxychloride cement(TDMOC), the effects of citric acid on the hydration process and mechanical properties of TDMOC was studied. The hydration heat release at initial 24 h and strengths at 3, 7, and 28 days of TDMOC specimens were conducted. The hydration products and paste microstructure were analyzed by XRD, FT-IR and SEM, respectively. The results showed that citric acid can not only reduce the 24 h hydration heat release and delay the occurring time of second peak of TDMOC, but also produce more 5Mg(OH)2·MgCl 2·8H2O and less Mg(OH)2 in hydration process of TDMOC. More perfect and slender crystals were observed in the microstructure of the TDMOC pastes with citric acid. The results demonstrated that citric acid as an additive of TDMOC can decrease the hydration heat release and increase the compressive strength and flexural strength of TDMOC. The possible mechanism for the strength enhancement was discussed.     

粉煤灰-脱硫石膏水泥基材料水化活性及微结构

采用DTA—TG、XRD、SEM以及宏观水化收缩和强度试验等手段研究了粉煤灰一脱硫石膏一水泥三元复合胶凝体系的水化过程、活性效应及微观结构等,根据试验结果总结了复合胶凝材料的水化动力学过程。结果表明,粉煤灰一脱硫石膏水泥石的钙矾石吸热峰强于基准样;在各组分相互活性激发和外掺激发剂作用下,粉煤灰一脱硫石膏水泥石中2次水化效应明显;SEM、XRD表明水泥石早期有明显的钙矾石生成,同时粉煤灰颗粒的表面侵蚀现象明显,进一步说明复合胶凝体系的早期活性得到有效激发,硬化后综合性能得到有效保证。且宏观收缩及强度试验也从侧面印证了微观试验结果。粉煤灰一脱硫石膏水泥基复合胶凝材料体系的研发可大量消耗燃煤电厂的工业废渣,具有显著的“绿色”效应。     

Coupled effect of cement hydration and temperature on hydraulic behavior of cemented tailings backfill

Cemented tailings backfill(CTB) is made by mixing cement, tailings and water together, thus cement hydration and water seepage flow are the two crucial factors affecting the quality of CTB. Cement hydration process can release significant amount of heat to raise the temperature of CTB and in turn increase the rate of cement hydration. Meanwhile, the progress of cement hydration consumes water and produces hydration products to change the pore structures within CTB, which further influences the hydraulic behavior of CTB. In order to understand the hydraulic behavior of CTB, a numerical model was developed by coupling the hydraulic,thermal and hydration equations. This model was then implemented into COMSOL Multiphysics to simulate the evolutions of temperature and water seepage flow within CTB versus curing time. The predicted outcomes were compared with correspondent experimental results, proving the validity and availability of this model. By taking advantage of the validated model, effects of various initial CTB and curing temperatures, cement content, and CTB's geometric shapes on the hydraulic behavior of CTB were demonstrated numerically. The presented conclusions can contribute to preparing more environmentally friendly CTB structures.     

The Competitive Adsorption Characteristics of Welan Gum and Superplasticizer in Cement Mortar

Welan gum has been widely used in oil cement and grouting materials for its excellent rheological properties and anti-bleeding,and most of all,being friendly to the environment.However,when welan gum was added,the fluidity of mortar decreased sharply,so it should be used together with a superplasticizer to enable good workability.With its powerful charge density in the molecular structure,the competitive adsorption between welan gum and other admixtures happened remarkably during the addition process.Consequently,we experimentally studied on the bleeding rate and rheological properties of cement slurry,fluidity and mechanical properties of mortar with welan gum mixed with superplasticizer,aiming at understanding the competitive adsorption phenomenon by application of welan gum mixed with superplasticizer.By measuring the hydration heat and zeta potential,the mechanism of interaction of welan gum with superplasticizer was deduced and explained.The results showed that it could ensure a good dispersion effect when welan gum is mixed with the two kinds of superplasticizer.Welan gum had little impact on the naphthalene superplasticizer,but did have a substantial influence on polycarboxylate.In practice,adding welan gum after PCE acted with cement for 2 min could effectively avoid the competitive adsorption and then achieve better performance.On this viewpoint for mortar with PCE,new delay release welan gum needs further research and development.     

普通可燃性装饰材料燃烧特性的实验研究

对实际火灾过程中可燃性装饰材料(窗帘布、三合板、五合板和木板块)燃烧时的热释放速率、质量损失速率和着火时间与材料的几何尺度、外界加热辐射热流强度之间的关系进行了研究。结果表明,着火时间随加热强度增加而减少,且在低加热强度下的递减速度较快,在较高加热强度下变化不大;薄体材料(窗帘布)的热释放速率呈单峰状,且随着辐射热流强度增加,热释放速率峰值先增加后减小,质量损失速率逐渐减小;厚体材料(三合板、五合板和木板块)的热释放速率和质量损失速率呈双峰状,低加热强度下第1个峰值比第2个峰值大,高加热强度下第2个峰值比第1个峰值大,2个峰值差值也增大;较高辐射热流强度下出现可燃物表面碳化,可导致热释放速率和质量损失速率降低。     

水泥粒径分布对混凝土绝热温升影响的模拟

为了模拟水泥粒径分布对混凝土绝热温升过程的影响,建立了一个基于水化深度的水化模型．该模型假定混凝土中水泥水化过程由水化深度控制,且水化深度随时间的发展与颗粒粒径无关;通过水泥等温放热曲线试验推导得出最大水化深度的存在;假定温度对水化过程的影响满足Arrhenius公式．通过混凝土绝热温升仪测定了3种不同初始温度下的绝热温升曲线,以此得到水化模型所需的基准水化速率曲线．最后将建立的水化模型用于模拟混凝土的绝热温升曲线,结果表明:基于水化深度的水化模型能够准确模拟水泥粒径分布和初始温度对混凝土绝热温升的影响．     

Effects of LiAl-layered double hydroxides on early hydration of calcium sulphoaluminate cement paste

As a 3D micro-nano material, layered double hydroxides have been widely used in many fields, especially for reinforced composite materials. In this paper, LiAl-LDHs was obtained by a hydrothermal method. In order to investigate the effects of LiAl-LDHs on the early hydration of calcium sulphoaluminate (CSA) cement paste, compressive strength, setting time and hydration heat were tested while X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scaning electron microscopy (SEM) and differential scanning calorimetry (DSC) analysis were employed. The results indicated that LiAl-LDHs could significantly improve the early compressive strength and shorten the setting time of calcium sulphoaluminate cement paste with 3wt% concentration. Besides, the hydration exothermic rate within 5 h was accelerated with increasing LiAl-LDHs content. Moreover, the addition of LiAl-LDHs did not result in the formation of a new phase, but increased the quantity of hydration products providing higher compressive strength, shorter setting time and denser microstructure.     

铝泡沫和石墨泡沫强化石蜡相变传热的数值模拟

针对有机相变材料石蜡导热系数低的问题,通过添加多孔介质的方法以强化石蜡相变传热,并运用CFD软件对石蜡相变传热系统进行二维数值模拟.模拟结果表明:铝泡沫和石墨泡沫都能有效提高相变材料传热速率,铝泡沫的强化传热效果明显高于石墨泡沫的传热效果.随着孔隙率减小,多孔介质/石蜡复合材料的有效导热系数增大,传热速率加快,凝固需要的时间缩短.并且,孔隙率越小,经过相同凝固时间,装置内对应点温度越低.     

Hydration mechanism of sulphoaluminate cement

The feasibility of sulphoaluminate cement (SAC) utilization in support mortar was studied. Setting time and strength of as-received sulphoaluminate cement (SAC) paste were examined, hydration kinetics behavior was determined through Isothermal Calorimeter, and hydration mechanism was investigated by X-Ray diffraction analysis (XRD) and field emission scanning electron microscopy analysis(FSEM). Results showed that as-received SAC contained 61% of anhydrous calcium sulfate (3CA·CaSO4) and dicalcium silicate (C2S). The strength after 1 day or 3 days grew to 68.6% or 85.7% of that after 28 days respectively, while most of hydration heat was released within 1 day. The emergency of three exothermic peaks at acceleration stage was found and hydration kinetics model was established choosing the terminal time of the first exothermic peak at accelerating stage as the beginning of accelerating stage. XRD analysis suggested that large amount of ettringite (AFt) was produced at early age and FSEM observation revealed that ettringite (AFt) formed in sulphoaluminate cement (SAC) paste was characterized of different morphology which was proved to be caused by different ion concentrations.     

Nano-treatment of Autoclaved Aerated Concrete Waste and Its Usage in Cleaner Building Materials

Autoclaved aerated concrete waste (AACW) was used as a raw material to prepare nucleation seed for acceleration of Portland cement.Nano AACW seed with median particle size of 324 nm was prepared by wet grinding method.Both the electrical conductivity and pH value of nano AACW suspension were obviously improved.Both the setting times and intensity of the main hydration heat peak were promoted by nano AACW,indicating the possibility of AACW suspension as nucleation seed.The early age compressive strength before 3 days was also clearly improved by nano AACW,with no negative effect on the late age strength.Furthermore,the reduced CH content with dosage of nano AACW indicates that nano AACW not only plays a role of nucleation seed in cement hydration,but also has a certain pozzolanic reaction.