硫铝酸钙-贝利特水泥熟料的低温制备及其水化性能研究

以煤矸石、脱硫石膏、石灰为主要原料,采用水热合成-低温煅烧方法制备了硫铝酸钙-贝利特水泥熟料,通过X射线衍射(XRD)、扫描电镜(SEM)等分析了水热合成物、煅烧试样及水化产物的矿物相,利用等温量热仪测定了水泥早期水化放热随时间的变化,并测定了水泥的力学性能。结果表明:在120℃下水热合成前驱体后再经煅烧,可在1 050℃低温下制成硫铝酸钙-贝利特水泥熟料。与一步法相比,该低温水泥的早期水化放热速率较高。当水泥中的二水石膏掺量为13%(质量分数)时,水泥1d、28d的抗压强度分别为30.2 MPa和57.3 MPa,28d的水化产物主要为长纤维状的AFt。     

A TRIBOCHEMICAL STUDY ON THE GRINDING PROCESS OFβ-C_2S

对水泥矿物之一β-C_2S 的粉磨过程进行了摩擦化学研究,用X 射线微观应力测定法和正电子湮没技术(PAT)测定了粉磨过程中β-C_2S 晶格畸变和结构缺陷的变化,从形变的微观机制对测试结果进行了探讨。测定了不同粉磨时间样品的比表面积,粒径分布和水化放热速率,解释了不同大小颗粒水化活性差异的原因。     

β-C_2S粉磨过程的摩擦化学研究

对水泥矿物之一β-C_2S 的粉磨过程进行了摩擦化学研究,用 X 射线微观应力测定法和正电子湮没技术(PAT)测定了粉磨过程中β-C_2S 晶格畸变和结构缺陷的变化,从形变的微观机制对测试结果进行了探讨。测定了不同粉磨时间样品的比表面积,粒径分布和水化放热速率,解释了不同大小颗粒水化活性差异的原因。     

硫铝酸钙改性硅酸盐水泥应用研究进展

硫铝酸钙改性硅酸盐水泥熟料兼具硅酸盐水泥熟料和硫铝酸盐水泥熟料的优良性能,同时该种水泥熟料对粉煤灰等火山灰类材料具有超强的活性激发效果,这使得硫铝酸钙改性硅酸盐水泥具有广阔的应用前景。主要概括了硫铝酸盐改性硅酸盐水泥的性能及水化特性,综述了该种水泥与不同矿物掺合料的复合性能以及与化学外加剂的适应性,提出了硫铝酸钙改性硅酸盐水泥存在的问题及改善措施。     

掺杂对高胶凝性水泥熟料矿物形成影响的研究进展

高胶凝性水泥熟料矿物体系是制备高性能水泥的关键技术之一.C3S是水泥熟料中最主要的胶凝相,而非硅酸盐类矿物C4A3(-S)也具有较强的胶凝性.因此提高水泥熟料胶凝性的关键在于熟料中C3S含量及其活性的提高,或在传统硅酸盐水泥熟料矿物体系中引入非硅酸盐类矿物(C4A3(-S)).通过探讨化学掺杂对水泥熟料中C3S和C4A3(-S)矿物的形成及共存的影响,综述了掺杂对高胶凝性水泥熟料矿物形成的影响的研究.     

硫铝酸盐水泥和丁苯乳液对水泥基修补材料性能的影响

将硫铝酸盐水泥与硅酸盐水泥复合,并引入丁苯乳液作为聚合物改性剂制备高性能修补材料,研究硫铝酸盐水泥和丁苯乳液对修补材料的强度、凝结时间和黏度的影响和作用机制。结果表明:硫铝酸盐水泥明显提高复合水泥的早期强度,缩短初凝和终凝时间,增大黏度;适量丁苯乳液能在复合水泥浆体中形成网状结构,提高力学强度;丁苯乳液中的羧基能够减小熟料矿物铝酸钙、硅酸三钙和硅酸二钙的水化速率,复合水泥净浆的初凝和终凝时间均明显延长,黏度减小。     

石灰石粉对硅酸盐水泥水化的影响

石灰石粉被广泛应用到水泥混凝土中,其在水泥体系中是否能产生活性效果仍存在争议。本文通过掺入30%石灰石粉与不掺石灰石粉组进行对比试验,采用扫描电镜(SEM)、能谱分析(EDS)以及X射线衍射分析(XRD)进行微观分析,结果表明:石灰石粉能够加速水泥中C3S的水化,以及能够与C3A反应生成水化碳铝酸钙,并且会阻止钙矾石向单硫型水化硫铝酸钙的转变。     

低质高碳粉煤灰制备粉煤灰贝利特水泥及其特性研究

利用含碳量高、火山灰活性较低的堆存粉煤灰为原料,用水热合成-低温煅烧方法制备粉煤灰贝利特水泥,研究了配合料CaO掺量与在97℃±2℃下的蒸养时间、煅烧温度和煅烧时间对前驱物和粉煤灰贝利特水泥的组成及其基本物理力学性能的影响。结果表明:在97℃±2℃蒸养和800℃煅烧,粉煤灰中的莫来石和石英几乎不与CaO发生反应;800℃煅烧的粉煤灰贝利特水泥熟料中主要水硬性矿物为α’L-C_2S和C_(12)A_7,当煅烧温度达900℃或更高时,贝利特以活性较低的β-C2S存在,并且熟料中有水化活性很低的钙铝黄长石形成。CaO掺量为30%的石灰-粉煤灰配合料在97℃蒸养10h后经800℃煅烧1h,制得28d抗压强度达到30.2 MPa的粉煤灰贝利特水泥。粉煤灰贝利特水泥凝结快,可用于快修工程,但其需水量大,硬化浆体结构相对疏松,孔隙率较大。     

铜离子掺杂对水泥水化的影响机理

本文研究了铜离子对熟料矿相种类、结构和水化进程的影响机理。结果表明:铜离子对水泥水化进程的缓凝抑制作用按照影响机理分为两个阶段:第一阶段,铜离子掺杂导致水化体系中Ca~(2+)浓度降低,早期氢氧化钙(Cu(OH)_2)结晶形成受阻,破坏了反应溶液的高碱性环境,且钙矾石(Aft)的形成速率减小、生成量减少,诱导期延长,水化产物间无法快速搭接形成网状结构,水泥浆体凝结硬化受阻;第二阶段,铜离子造成C_3S晶粒异常长大,水化反应活性降低,水泥浆体结构变得疏松、孔隙率增大,从而导致其后期强度显著降低,且孔隙中分布晶体尺寸较大的钙矾石,相互穿插,形成水泥浆体中的薄弱联结。     

Si-Mn矿粉粒度对复合胶凝体系水化机理和力学性能的影响

为了实现Si-Mn矿渣的高效利用,通过气流分级机将Si-Mn矿粉分为D50=6.9μm、17.9μm和56.4μm三个不同的粒度区间.采用等温量热仪(TAM air)、X射线衍射(XRD)仪、全自动压汞仪(MIP)、扫描电子显微镜-能谱(SEM-EDS)分析测试技术,研究了Si-Mn矿粉粒度对复合胶凝体系水化行为和微观结构的影响,并对其胶砂强度进行了评价.结果表明:各粒度区间的Si-Mn矿粉均能促进游离石灰、铝酸盐相和C3 S等矿物的早期水化(30 min)放热速率;水化后期,Ca(OH)2和熟料衍射峰强度随着Si-Mn矿粉粒度减小而显著降低;掺入细粒度的Si-Mn矿粉可增加硬化复合胶凝材料浆体凝胶孔数量,有效降低最可几孔径和总孔隙率;SEM-EDS结果进一步证实了硬化浆体孔结构的优化是由于细粒度Si-Mn矿粉表面生成了大量低钙硅比的C-S(Al,Mg)-H水化产物.值得注意的是:D50=6.9μm和17.9μm的Si-Mn矿粉掺量高达30％时,复合胶凝材料的胶砂强度超过了GB 175标准中42.5等级水泥的技术指标.因此这些粒度区间的Si-Mn矿粉可以被建议作为绿色水泥的生产和高性能混凝土配制中的矿物掺合料.     

预分解磷石膏制备贝利特-硫铝酸盐水泥

研究磷石膏在低温还原-高温氧化气氛下的分解特性,并将分解后的磷石膏作为钙源代替石灰石制备贝利特-硫铝酸盐水泥。结果表明:在碳硫比(C/S)为2,CO_2-950℃-1h/空气-1 200℃-1h的分段煅烧条件下,磷石膏分解率可达87.69%,且SO_2在900~1 200℃内集中释放。将分解率为87.69%的磷石膏代替部分石灰石烧制贝利特-硫铝酸盐水泥熟料,其主要矿相有C4A3珔S、C2S和C4AF,及少量C2AS,水泥净浆3d抗压强度为41.4 MPa。每生产1t贝利特-硫铝酸盐水泥熟料可消纳约0.98t磷石膏,减少石灰石用量近50%。     

循环流化床固硫灰渣低收缩水泥的制备及性能

通过分别使用循环流化床(CFBC)固硫灰、渣代替部分原材料制备低收缩水泥熟料,加入质量分数为10%的石膏即得到CFBC固硫灰、渣低收缩水泥,然后利用X射线衍射、扫描电镜等方法研究水与水泥的质量比(简称水灰比)对CFBC固硫灰渣低收缩水泥水化程度、抗压强度和线性膨胀率的影响。结果表明,随着水灰比的增加,CFBC固硫灰渣低收缩水泥的主要水化产物钙矾石数量增多,未水化的硅酸二钙含量减少,水化程度增大;而该水泥线性膨胀率与水灰比呈正比关系,抗压强度与其呈反比关系;利用固硫灰制备的水泥早期膨胀率随着水化时间而增大,但后期由于石膏量的不足,膨胀率则随着水化时间而减小。     

铅锌尾矿用于中热水泥的制备

本文采用铅锌尾矿为原料烧制中热硅酸盐水泥,并与用粘土配料烧制的中热水泥进行对比。用差热分析测定熟料的易烧性;用X射线衍射分析研究了熟料的矿物组成;依据国标GB2022-80测量了中热水泥的水化热;通过砂浆和净浆实验测定了中热水泥水化后的强度;并用X射线衍射和扫描电镜对水化产物进行了分析。实验结果表明,使用铅锌尾矿来配料,可以提高熟料的易烧性,矿物形成良好。熟料掺入4%的石膏制得水泥,其性能符合GB200-2003规定的强度等级42.5中热硅酸盐水泥的各项标准,并且其后期强度高于用粘土配料的试样。     

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.     

Relation between cement composition and compressive strength of pure pastes

In Europe, cement paste compressive strength models are frequently described by a power law similar to that of Féret. The French LCPC has also adopted this mathematical approach in its recent concrete mixture proportioning model. However the coefficient k and exponent b of the adopted power law were calibrated with only one Portland cement clinker, starting from pure pastes with various concentrations. These parameters do not take into account the chemical properties of the clinker. The purpose of this work was to check if the clinker chemical nature had an influence on the mechanical performances of the pastes (at 28 days). Complementary tests with eight cements coming from six different cement plants were then carried out. The mathematical treatment of the results made it possible to connect coefficient k to the silica content of the clinkers and more particularly to their C₃S rates. It is linked to the strength of hydrated cement paste. Thus, the suggested approach significantly improves the accuracy of paste strength calculation. These results can be used to calculate concrete strength.     

Utilization of steel slag for Portland cement clinker production

The aim of the present research work is to investigate the possibility of adding steel slag, a by-product of the conversion of iron to steel process, in the raw meal for the production of Portland cement clinker. Two samples of raw meals were prepared, one with ordinary raw materials, as a reference sample ((PC)(Ref)), and another with 10.5% steel slag ((PC)(S/S)). Both raw meals were sintered at 1450 degrees C. The results of chemical and mineralogical analyses as well as the microscopic examination showed that the use of the steel slag did not affect the mineralogical characteristics of the so produced Portland cement clinker. Furthermore, both clinkers were tested by determining the grindability, setting times, compressive strengths and soundness. The hydration products were examined by XRD analysis at 2, 7, 28 and 90 days. The results of the physico-mechanical tests showed that the addition of the steel slag did not negatively affect the quality of the produced cement.     

Examination of the jarosite-alunite precipitate addition in the raw meal for the production of sulfoaluminate cement clinker

The aim of the present research work was to investigate the possibility of adding a jarosite-alunite chemical precipitate, a waste product of a new hydrometallurgical process developed to treat economically low-grade nickel oxides ores, in the raw meal for the production of sulfoaluminate cement clinker. For that reason, two samples of raw meals were prepared, one contained 20% gypsum, as a reference sample ((SAC)Ref) and another with 11.31% jarosite-alunite precipitate ((SAC)J/A). Both raw meals were sintered at 1300 degrees C. The results of chemical and mineralogical analyses as well as the microscopic examination showed that the use of the jarosite-alunite precipitate did not affect the mineralogical characteristics of the so produced sulfoaluminate cement clinker and there was confirmed the formation of the sulfoaluminate phase (C4A3S), the most typical phase of this cement type. Furthermore, both clinkers were tested by determining the grindability, setting time, compressive strength and expansibility. The hydration products were examined by XRD analysis at 2, 7, 28 and 90 days. The results of the physico-mechanical tests showed that the addition of jarosite-alunite precipitate did not negatively affect the quality of the produced cement.     

碳化与氯盐复合作用下水泥浆体的微结构演变

为了阐明碳化与氯盐复合作用下硬化水泥浆体的微结构,基于X射线计算机断层扫描成像(X-CT)和电子探针微区分析(EPMA)技术探明了氯盐对水泥浆体碳化速率的影响,测定了碳化作用下水泥浆体内Cl、S和Na元素的浓度分布。结果表明:氯盐可细化养护龄期为28d的水泥浆体孔结构,提高其密实度并减缓碳化速度;碳化作用下水泥浆体的碳化区易出现裂缝,二氧化碳气体通过这些裂缝扩散到水泥浆体内部进行碳化,致使水泥浆体碳化深度不均匀;碳化过程中Cl、S和Na元素向非碳化区迁移和浓缩,初始均匀分布的元素在碳化区含量减少,在非碳化区含量升高。所得结论为混凝土结构耐久性设计提供科学的理论依据。     

Reduction of clinkerization temperature by using phosphogypsum

Valorization of phosphogypsum as mineralizer in the burning of Portland cement clinker was studied in our laboratory. X-ray fluorescence, optical microscope technique and powder X-ray diffraction were then used to characterize the synthesized clinker and its raw mixture in terms of chemical composition and clinker mineralogical composition. The effects of phosphogypsum on structural and morphological properties of clinker minerals and on the presence of alite were followed by scanning electron microscopy combined with microprobe analysis. The addition of phosphogypsum to the cement raw mixture shows that the burning temperature decreases and therefore improves the production process of clinker. The addition of 10% phosphogypsum permits a complete clinkerization at low burning temperature (1200 degrees C), instead of 1470 degrees C, which increases the cement factory efficiency by 25% and extends the service life of furnace fire brick. Structural and morphological analysis of clinker produced under the new conditions show that phosphogypsum preserve perfectly the crystalline structure of silicate phases, which leads to the improvement of physical and mechanical properties of cement.