硫铝酸盐复合水泥体系水化特征研究

通过正交试验研究了硫铝酸盐复合水泥中不同掺量的普通硅酸盐水泥、石膏、硅灰及粉煤灰对其强度、自收缩以及水化热的影响。结果表明:普通硅酸盐水泥及石膏的掺入显著改变了硫铝酸盐复合水泥水化进程,硅灰及粉煤灰是影响后期强度的主要因素;自收缩试验结果表明普通硅酸盐水泥和石膏是影响硫铝酸盐复合水泥水化早期自收缩的主要因素;水化热测试结果表明粉煤灰和普通硅酸盐水泥在水化前6 h起到显著作用,粉煤灰降低了水化放热,而普通硅酸盐水泥增加水化放热;硅灰及石膏对6~24 h水化放热影响显著。结合XRD及SEM测试结果,表明普通硅酸盐水泥和石膏的存在加速了硫铝酸盐复合水泥水化早期钙矾石生成,随着石膏浓度的下降,发生转晶(AFm),随着后期硫铝酸盐水泥中β-C₂S的水化以及硅灰、粉煤灰的火山灰反应产生C-S-H凝胶,使得体系致密化。     

聚合物水泥复合防腐材料的物理性能

对两种不同硅酸盐水泥分别与丙烯酸酯乳液共同固化形成的复合防腐材料层进行了附着力、耐冲击性、柔韧性和线膨胀系数等物理性能对比试验,研究分析了其性能差异,探索了聚/灰比对复合防腐材料物理性能的影响规律。结果表明:在硅酸盐水泥中加入聚合物乳液共同固化得到的复合材料较之水泥单独水化得到的固化产物,在粘附性、耐冲击性和柔韧性等方面均有了显著的提高,特别是当聚/灰比R>0.3时,聚合物乳液对复合材料性能的改善更加明显;在相同聚/灰比条件下,NE-1硅酸盐水泥/聚合物复合材料相比P·O 52.5硅酸盐水泥/聚合物复合材料的性能更为优异;当R>0.5时,聚合物水泥复合材料的性能不再随丙烯酸酯乳液用量的增加有较为明显的提高,因此建议聚/灰比的适宜范围为0.3~0.5。     

全尾砂-棒磨砂新型胶凝充填材料的制备

将某镍矿选矿全尾砂代替部分棒磨砂作为骨料,采用正交试验和神经网络预测模型,制备以铁矿渣粉为活性材料、以脱硫灰、生石灰为主要激发剂的全尾砂-棒磨砂新型胶凝充填材料,分析了该材料的微观结构及其水化产物。结果表明:全尾砂添加质量分数为30%时,新型胶凝充填材料3 d、7 d和28 d的抗压强度分别达到1.73 MPa、4.22 MPa和6.93MPa,比水泥分别提高了8.13%、51.8%和34.0%,满足镍矿的充填强度指标。新型胶凝充填材料的主要水化产物为C-S-H凝胶,团絮状C-S-H凝胶形成结构密实的胶凝体,将骨料紧密粘结在一起形成较高的力学强度。用这种新型胶凝充填材料可实现30%的全尾砂利用率。     

低温环境下赤泥地聚合物抗硫酸盐侵蚀机理研究

通过将内掺不同质量分数硫酸镁和硫酸钠的赤泥地聚合物和普通硅酸盐水泥试件在(5±1)℃的条件下长期浸泡,定期观测试件外观变化,并对长期浸泡后的试件取样进行XRD衍射和FT-IR光谱分析,研究了内掺不同种类和不同质量分数硫酸盐对赤泥地聚合物的侵蚀破坏过程与作用机理,并与同等条件下普通硅酸盐水泥抗硫酸盐侵蚀性能及机理进行了对比。结果表明:当试件内掺硫酸镁和硫酸钠时,赤泥地聚合物发生了石膏型硫酸盐膨胀破坏,而普通硅酸盐水泥则分别发生了TSA型硫酸盐侵蚀破坏和石膏型硫酸盐膨胀破坏。赤泥地聚合物内部孔隙液pH值高,水化产物中C-S-H凝胶钙硅比低和水化生成的铝硅酸盐类物质化学性质稳定是其在长期低温硫酸盐侵蚀环境下未发生TSA型硫酸盐侵蚀破坏的主要原因。     

矿渣水泥水化产物平衡体系的研究

通过分析硅酸盐水泥熟料矿物组成、水化特性,矿渣的化学组成和水化过程,研究了普通矿渣水泥、碱矿渣水泥水化产物平衡体系的稳定性,并根据矿渣水泥系统水化产物稳定存在的条件,研制了适用于高掺量矿渣水泥的复合外加剂。     

低水灰比对硅酸盐水泥水化程度的影响

研究了低水灰比硅酸盐水泥的水化程度，并利用XRD和SEM分析了其水化产物的微观结构。结果表明在低水灰比条件下，水泥的水化程度较低，其硬化水泥浆体中存在较多的未水化水泥；同时由于自身的密实性增强和体系的低孔隙率，使水泥水化产物的结晶、生长情况也受到影响。     

赤泥复合充填材料浸出行为及固化机制

针对赤泥高碱性、化学成分复杂、资源化利用率低的问题,以赤泥协同粉煤灰等多固废制备矿山充填材料,对比研究赤泥复合材料配比对充填体抗压强度的发展规律,采用XRD、SEM等微观分析手段揭示充填材料水化机制,通过淋溶试验、毒性浸出试验探明充填体固碱机制、浸出行为及毒害离子固化机制。结果表明：赤泥复合材料质量比为赤泥∶粉煤灰∶水泥=3:7:0.4时,充填体3、7、28天抗压强度分别为0.76、1.35、1.87 MPa,材料成本为78.08元/吨,满足矿山充填开采要求。在赤泥-粉煤灰-水泥的协同互锁作用下,充填体生成了以水化硅酸钙(C-S-H)凝胶、钙矾石、钠系菱沸石为主的水化产物,且赤泥∶粉煤灰质量比越小,粉煤灰比表面积越大,充填体结构越致密,固碱效果越好。钙矾石和C-S-H凝胶通过物理固封和化学结合的形式,使赤泥复合材料毒性离子浸出浓度满足固废要求。     

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。     

高温堵漏剂的微观结构与堵漏机理

利用XRD、TG和SEM-EDS对XAN-RC高温堵漏剂在模拟实际作业环境的高温高压条件下水化的水化产物和硬化浆体微观结构进行了分析,对其高温堵漏机理进行了讨论.在高温高压条件下,除普通的硅酸盐水泥的水化反应外,XAN-RC高温堵漏剂中还存在硅质或硅铝质抗高温添加剂与硅酸盐水泥水化生成的Ca(OH)2之间的二次水化反应.初始水化生成的水化硅酸钙凝胶并不能转化为纤维状晶体;只有二次水化反应才能生成纤维状晶体,从而形成致密浆体,大幅度提高其高温粘结强度.     

Cr~(3+)、Pb~(2+)在不同水泥水化体系中的固化

研究了重金属离子Cr~(3+)和Pb~(2+)对硅酸盐水泥、硫铝酸盐水泥及混掺水泥(普通硅酸盐水泥与硫铝酸盐水泥进行混掺)三种水泥的浆体凝结时间和力学性能的影响,并借助X射线衍射技术(XRD)和电感耦合等离子体发射光谱(ICP)等研究了水泥水化产物特征、重金属元素在水泥浆体中的固化方式与溶出特性。结果表明:Cr~(3+)对三种水泥均产生促凝作用,而Pb~(2+)对普通硅酸盐水泥和混掺水泥产生缓凝作用,对硫铝酸盐水泥产生促凝作用。Cr~(3+)和Pb~(2+)的掺加引起AFt和Ca(OH)_2形成量的变化,影响程度与水泥品种有关,掺加Cr~(3+)的28d浆体中有新相Ca_2Cr(OH)_7·3H_2O生成。所研究的三种水泥中,硅酸盐水泥对Cr~(3+)的固化效果最好,当Cr~(3+)掺量为1%时,其Cr~(3+)浸出浓度仅为0.177mg/L;而硫铝酸盐水泥对Pb~(2+)的固化效果最好,当Pb~(2+)掺量为1%时,其Pb~(2+)浸出浓度仅为0.0064mg/L。     

利用工业废渣制备软土固化剂的可行性探讨

就如何高附加值地利用工业废渣制备软土固化剂进行了技术效果、经济效益及生产方式等方面的可行性探讨。基于固化土结构形成过程的特点及其对固化剂组成的特殊需求,提出了利用工业废渣制备固化剂的设计思想,给出了固化剂配比实例,与水泥进行了性价比对比分析,并初步探讨了利用工业废渣产业化生产固化剂宜采取的生产经营方式。认为只要能根据形成固化土结构对固化剂组成材料的特殊需求针对性地选择适当的工业废渣,就能够制备出高性价比的软土固化剂;宜根据拟加固土的性质个性化设计制备固化剂,采用多组分组配式生产方式以及设计、生产、销售一体化的经营模式。     

钢渣-矿渣基全尾矿充填胶结材料的研究

以冶金废渣钢渣、矿渣及电厂废渣脱硫石膏为主要原材料,添加少量的硅酸盐水泥及激发剂,制备了一种新型的钢渣～矿渣基全尾矿充填胶结材料。通过系统试验,确定了制备钢渣-矿渣基全尾矿充填胶结材料的最优配比及影响其性能的显著性因素。结果表明,采用钢渣-矿渣基全尾矿充填胶结材料制备的充填体在胶砂比为1;9、固体浓度约为68％时,28天抗压强度可达到2．5MPa以上。钢渣-矿渣基全尾矿充填胶结材料的固体废弃物含量高达90％以上,且成本明显低于普通水泥,因此会产生较好的环境和经济效益。     

Damage mechanism of composite cemented backfill based on complex defects influence

In order to reduce mining waste discharge and realize efficient application of tailing material in underground backfilling, the characteristics and mechanism of backfill damage is analyzed, and also the composed behavior and failure characteristic of cemented backfill. Five types of backfills were tested under uniaxial compression loading in SHT4206 electro‐hydraulic servo testing system. Based on the experimental results, the damage constitutive equations of cemented backfills with five cement?tailing ratios were proposed on the basis of damage mechanics and then validated. Research shows that the damage growth rate of backfills with lower cement?tailing is lower before peak value of stress, but it grows more rapidly after that. In addition, four backfill combination schemes were designed for mechanical test. Combining with research results on fracture characteristic of different backfills, a defects coupled constitutive model based on continuum damage mechanics was established. Research shows that the piecewise nonlinear model can well embodies effect of complex defects in backfills on the stress‐strain curve. Accuracy of the model is well verified by measured curve of backfill composite members. The results of this work provide a scientific basis for failure process prediction of backfills and reasonable matching design of framed filling.     

Cemented paste backfill of sulphide-rich tailings: Importance of binder type and dosage

In this study, the influence of binder type and dosage on the mechanical properties and microstructure of cemented paste backfill (CPB) was investigated using ordinary Portland cement (OPC), Portland composite cement (PCC) and sulphate resistant cement (SRC). The CPB samples of OPC and PCC were observed to lose their unconfined compressive strengths (UCSs) after 56 days. This could be associated with the sulphide moiety of the tailings, i.e. the attack on hydration products by sulphate and acid internally generated via the oxidation of pyrite present. In this respect, those CPB samples of sulphate resistant-based cements (SRC and a mix of OPC and SRC) maintained good long-term strengths and stability (i.e. no loss of strength). Increasing binder dosage (5–7 wt.%) improved the UCSs of CPB samples up to 1.9-fold with no loss of strength at >5 wt.%. Decreasing water-to-cement ratio appeared to produce a beneficial effect on the UCSs of CPB samples. SEM studies have provided further insight into the microstucture of CPB and confirmed the deleterious formation of gypsum as the expansive phase. These findings have demonstrated the practical importance of binder type/dosage and water-to-cement ratio for the short- and long-term mechanical performance of CPB.     

Arsenic stability in arsenopyrite-rich cemented paste backfills: a leaching test-based assessment

Arsenic (As) is a toxicant in tailings from sulphur deposits. It represents an environmental risk because of its high solubility. Tailings can be mixed with water (typically 25%) and a low proportion of hydraulic binder (3-7%) to produce a cemented paste backfill (CPB), stored in underground mine openings. CPB is a tailings storage technique, but it could also provide environmental advantages by stabilization of polluting elements such as As. Tailings from Casa Berardi mine (QC, Canada) contain As (3800 ppm), mainly in arsenopyrite form. For this study, three different CPBs were synthesized in laboratory using Casa Berardi tailings and three different binders. These pastes were submitted to various leaching tests after 28 days of curing. The results indicate that As is released at higher concentration for a fly ash-based CPB than for slag- and Portland cement-based CPB. However, at lower pH, As is better stabilized in fly ash-based samples. These differences can be explained by a variation of solubility of As-compounds in each CPB. Several mechanisms of As release occur, as diffusion and/or dissolution/precipitation. The accelerated weathering test results show that sulphide reactivity is buffered by the neutralizing minerals contained in CPB, and influence the As release behaviour by decreasing the oxidation of As-bearing sulphides.     

A novel method to evaluate the setting process of cement and asphalt emulsion in CA mortar

Cement and asphalt mortar (CA mortar) is the key component in the structure of Shinkansen slab track and serves as the elastic shock-absorber. A new method was put forward to evaluate the setting process of cement and asphalt emulsion (CAE) in CA mortar. It was noted that the setting process was governed by several factors such as cement types, cement/asphalt emulsion ratios (C/AE ratio). Results also indicated that the setting process of CAE was faster, the higher proportion of cement content was; the early age strength and the separation rate of CA mortar could be improved by using cement of high early age strength and rapid hydration rate, or a blended cement with ordinary Portland cement partially replaced by sulfoaluminate cement, or by increasing C/AE ratio. Nevertheless, the replacement ratio of ordinary Portland cement by sulfoaluminate cement should not exceed 15% and C/AE ratio should be not less than 0.8.     

钢渣改性硅酸盐水泥-水玻璃双液注浆复合材料的试验研究

研究了钢渣掺量、单浆液水胶比、双浆液体积比对钢渣改性硅酸盐水泥-水玻璃双液注浆复合材料工作性能影响规律。确定了钢渣改性硅酸盐水泥单浆液的最佳水胶比为0.6~0.8,平均粒径为20.4 μm的钢渣在改性硅酸盐水泥单浆液中的最佳质量分数为50%~80%,钢渣改性硅酸盐水泥单浆液与水玻璃单浆液的最佳体积比范围为4：1~6：1。根据以上参数所配制的钢渣改性硅酸盐水泥-水玻璃浆液硬化后在水中养护3天,早期强度均>40 MPa,软化系数也均>0.8。     

Effects of mix composition and water–cement ratio on the sulfate resistance of blended cements

This paper presents an experimental investigation on the sulfate resistance of blended cements containing various amounts of natural pozzolan and/or Class-F fly ash. The performance of blended cements was monitored by exposing the prepared mortar specimens to a 5% Na₂SO₄ solution for 78 weeks. For comparison, an ordinary Portland cement (produced with the same clinker as blended cements) and a sulfate resistant Portland cement (produced from a different clinker) were also used. In addition to the cement chemistry, water–cement (w/c) ratio of mortars was another parameter selected that will presumably affect the performance of mortars. The experimental results of expansion measurements showed that the effect of w/c ratio was more pronounced for the low sulfate resistant cements with higher C₃A amounts, while the blended cements were less affected by an increase in the w/c ratio.     

Prediction of chloride ingress and binding in cement paste

This paper summarizes recent work on an analytical model for predicting the ingress rate of chlorides in cement-based materials. An integral part of this is a thermodynamic model for predicting the phase equilibria in hydrated Portland cement. The model’s ability to predict chloride binding in Portland cement pastes at any content of chloride, alkalis, sulfates and carbonate was verified experimentally and found to be equally valid when applied to other data in the literature. The thermodynamic model for predicting the phase equilibria in hydrated Portland cement was introduced into an existing Finite Difference Model for the ingress of chlorides into concrete which takes into account its multi-component nature. The “composite theory” was then used to predict the diffusivity of each ion based on the phase assemblage present in the hydrated Portland cement paste. Agreement was found between profiles for the Cl/Ca ratio predicted by the model and those determined experimentally on 0.45 water/powder ratio Portland cement pastes exposed to 650 mM NaCl for 70 days. This confirms the assumption of essentially instantaneous binding where quasi-equilibrium is established locally. This does not imply steady state diffusion however. It simply implies that incremental increases in the concentration of diffusing ions in the pore solution will rapidly re-equilibrate with the hydrates present locally, where, the greater the ratio of bound to free ions, the greater the buffering effect which slows down the rate of ingress. In the case of chlorides, this buffering effect is greatest at high contents of AFm (AFm is aluminium ferrite compounds with a single (mono) formula unit CaX.) phase and low alkali metal contents.     

Material properties of portland cement paste with nano-montmorillonite

The nano-montmorillonite, which has characteristics of high aspect ratio and interaction between polymer chains and dispersed nanolayers, has been widely used in the development of new reinforced nanocomposite polymers to improve their mechanical properties. Since a potential pozzolanic reaction may occur between Portland cement paste and high amount of silicon dioxide (SiO₂) in nano-montmorillonite, the effects of introduction of montmorillonite to Portland cement-based material on the improvement of matrix properties of cement paste is of great interest in the construction industry. In this study, a liquid-form of nano-montmorillonite particle with a planar diameter of about 100 nm were incorporated into the Portland cement paste at five different dosages and analyzed at four different ages to identify the nanosizing effects on material properties of such cement-based composite. Experimental results show that the composite with 0.60% and 0.40% of added nano-montmorillonite by weight of cement have the optimum compressive strength and permeability coefficient, respectively, in which the increase of compressive strength is about 13.24%, and the decrease of permeability coefficient about 49.95%. Microstructural properties through the analyses of XRD, DSC, NMR, and MIP also indicate that the microstructures of cement paste with nano-montmorillonite contain more dense solid material and more stable bonding framework.