140℃高温下SiO2晶态对硅酸三钙水化产物的影响

目前，在G级油井水泥中加入SiO₂是降低其水化产物在温度高于110℃下力学性能衰退的主要手段。然而，SiO₂晶体形态不同，导致水泥水化产物不同，耐高温性能也不同。为了探究SiO₂晶体形态对水泥水化产物的影响，笔者以油井水泥的主要成分硅酸三钙(C₃S)为研究对象，采用核磁共振、X射线衍射、热重分析和扫描电镜以及能谱等手段分析了晶体SiO₂(石英砂)和非晶体SiO₂(微硅)对C₃S水化产物的影响。结果表明：SiO₂通过填充孔隙以及转化水化产物，能有效防止C₃S水化产物在高温下强度衰退，以及孔隙度和渗透率的增加。微硅比石英砂更活跃，能迅速与Ca(OH)₂发生火山灰反应生成次生水化硅酸钙。此外，SiO₂还能将高钙硅比的水化硅酸钙(针硅钙石(Ca₂SiO₃(OH)₂)、羟硅钙石(Ca_...     

超细镁渣微粉-水泥复合胶凝材料的性能及水化机理

镁合金被誉为“21世纪绿色工程金属结构材料”,我国皮江法炼镁所得镁渣规模庞大、亟待解决，制备建筑材料是消纳镁渣的重要渠道，但国内外相关研究屈指可数，且普遍以镁渣耦合其他固废及水泥制备复合胶凝材料为主，鲜有针对镁渣-水泥简单体系的细致研究，故镁渣水化及其对水泥水化的影响机制尚未明确。本工作通过探究超细镁渣微粉-水泥复合胶凝材料(MS-C)新拌浆体和硬化浆体的性能、组成及结构演化规律，分析超细镁渣微粉对MS-C水化进程的影响机制，进一步揭示镁渣-水泥的协同水化机理。镁渣中的硅酸二钙以低活性γ-C₂S为主，超细粉磨是发挥其填充效应的关键途径，掺入30%的超细镁渣粉使水泥中1 000 nm以上孔含量由7.98%降低至6.83%。在减水剂作用下，MS-C浆体的流动性随超细镁渣微粉掺量的增大而增大，在无减水剂时其作用相反。低掺量超细镁渣微粉的水化及弱胶凝作用可增大其填充效应对强度的贡献，并促进Ca(OH)₂和C-S-H凝胶的生成，使得低超细镁渣微粉掺量的MS-C获得优于纯水泥的28 d力学性能。本研究获得了超细镁渣微粉-水泥水化特性的基础结论，为提高镁渣...     

纳米SiO2改性聚合物水泥基复合材料早期微观结构及性能

利用纳米SiO₂(nano SiO₂)早期可促进聚合物水泥基复合材料水化速率、提升其力学性能、改善其界面过渡区(ITZ)性能及优化其孔隙结构等特点,借助XRD、SEM、EDS、显微硬度(MH)及压汞(MIP)等试验,揭示了nano SiO₂对聚合物水泥基复合材料早期性能影响的微观机制。结果表明:当nano SiO₂掺量为2wt%时,聚合物水泥基复合材料的力学性能最优,3 d和7 d龄期抗压强度分别为57.5 MPa和67.3 MPa,较仅仅掺加聚合物的水泥基复合材料分别提高了12.7%和13.9%;nano SiO₂的掺入改变了聚合物水泥基复合材料水化产物数量及微观形貌。对于ITZ性能,nano SiO₂掺入后,聚合物水泥硬化浆体-骨料的ITZ厚度减小,形貌变得更加致密;ITZ的钙硅比因nano SiO₂的加入变小而其显微硬度变大;此外,nano SiO₂加入后可以进一步填充聚合物水泥基复合材料更加细小的孔隙,使其凝胶孔比例变高,最可几孔径变小,大大优化了聚合物水泥基复合材料的孔隙结构。      

活化煤矸石对水泥水化的影响

研究了活化煤矸石-氢氧化钙体系的水化热、水化产物成分以及活化煤矸石水泥体系的水化过程、水化产物的微结构,结果表明,在石膏的激发下,活化煤矸石能够发生二次水化,与Ca（OH）2反应形成钙矾石、水化硅酸钙、水化铝酸钙等有利于提高水泥石强度的水化产物;活化煤矸石水泥硬化浆体中Ca（OH）2的含量在水化3d时最多,而后随龄期逐渐减少;阐明了活化煤矸石能够降低水化产物中氢氧化钙的含量、抑制氢氧化钙晶体的生长和聚集,并改善水泥石结构．     

自燃煤矸石胶凝材料中钙矾石形成研究

采用XRD分析了自燃煤矸石胶凝材料中活性Al2O3在不同因素影响下水化形成钙矾石的情况.研究结果表明,在相同条件下芒硝存在,时自燃煤矸石中活性Al2O3水化生成钙矾石,而含等量硫的石膏存在时水化浆体中不但有水化产物钙矾石还有未反应的石膏;胶凝体系中不含熟石灰时,活性Al2O3水化首先生成石膏,随着水化的进行再转化成钙矾石,而在有熟石灰时水化则直接生成钙矾石;矿渣促进了自燃煤矸石中Al2O3水化形成钙矾石.     

再生混凝土微粉在碱激发胶材体系中的作用效应研究

再生混凝土微粉(RCP)中含有大量的SiO₂、CaO、Al₂O₃和少量未水化的水泥,通过物理或化学激发后可作为辅助性胶凝材料(SCMs)。再生微粉的资源化利用对节约原料和处置利用废弃物具有重要意义。本工作制备了不同RCP取代率的碱激发胶凝材料,研究了其流动性能、力学性能、微观表征及水化过程。结果表明,RCP的掺入提高了碱激发胶凝材料的流动性,10%～40%取代率下胶凝材料的流动性总体提高了2%～12%;当RCP掺量为10%时,碱矿渣胶凝材料的抗压强度提高了13%;RCP中的非活性颗粒填充了水化产物间的孔隙,形成了密实的微观结构;RCP中非活性颗粒阻碍了碱溶液与矿渣的反应,因此RCP的掺入推迟了碱激发体系第二放热峰的出现,降低了胶凝材料的早期放热速率。     

胶凝材料影响水泥基饰面砂浆泛碱的研究进展

介绍了胶凝材料影响水泥基饰面砂浆泛碱性能的研究进展。研究主要针对水泥基饰面砂浆的泛碱成因,从无机胶凝材料入手,探讨其对砂浆泛碱的影响和抑制泛碱的措施。涉及的无机胶凝材料主要集中在硅酸盐水泥、铝酸盐水泥及其分别或共同与石膏组成的二元和三元体系。水泥基饰面砂浆的抗泛碱主要通过两条途径,一是控制水化时Ca（OH）₂的产生,二是提高砂浆的密实度。     

CaO增强复合胶凝材料的性能

使用重金属污泥制备免烧砖。使用CaO钙源优化配置复合胶凝材料的组分,并调控胶凝浆体中的水化产物和未水化相。先基于免烧砖原料的配合比计算复合胶凝体系的钙硅比(Ca/Si)并控制其值为0.8~1.2,设计添加CaO的免烧砖实验方案。使用核磁共振(NMR)、透射电镜-能谱等手段和PCAS分析软件,研究了CaO使高硅复合胶凝材料性能提高的机理。结果表明：随着高硅胶凝体系Ca/Si比在0.8~1.2范围内的提高,免烧砖的力学性能先提高后降低,Ca/Si比的最佳值为1.0,CaO也有一个最佳调控值。随着Ca/Si比的提高7 d试样的吸水率先降低后提高,28 d试样的吸水率线性降低。随着Ca/Si比的提高,试样中平面孔径大于200 μm的孔隙率递减,分形维数先减小后增大;对于孔径小于200 μm的孔结构,随着Ca/Si比的提高孔径为200~200 μm的孔减少,孔径小于200 nm的孔增多,孔的体积呈减小的趋势。复合胶凝体系能抑制污泥免烧砖70%以上的重金属浸出量。     

基于电阻率和ζ-电位法的低热硅酸盐水泥早期水化特性

为研究低热硅酸盐水泥早期水化特性，采用电阻率测试仪和电声法ζ-电位分析仪分别对低热水泥和普通硅酸盐水泥水化的电阻率和ζ-电位进行测试。结果表明：电阻率和ζ-电位曲线在表征水泥浆体阶段的水化过程上具有较好的一致性。在水化20 min内，低热水泥浆体的ζ-电位与Ca²⁺浓度成正比，ζ-电位的急剧上升与{Ca₆[Al(OH)₆]₂·24H₂O}⁶⁺浓度有关；水化20 min后，浆体中开始形成AFt和CSH,ζ-电位的变化受SO₄^2-与{Ca₆[Al(OH)₆]₂·24H₂O}⁶⁺、Ca²⁺与HSiO₃^-反应速率控制。与普通水泥相比，低热水泥在水化20 min内Ca²⁺溶出速率更快，浆体中AFt形成时间更早；其诱导期持续时间短...     

偏铝酸钠激发石灰石粉的胶凝材料合成机理研究

石灰石在地球上储量丰富。为了对石灰石粉进行高效利用，本工作采用偏铝酸钠与石灰石粉制备胶凝材料，探究了偏铝酸钠掺量对其凝结时间、力学性能的影响，分析了胶凝材料的物相组成、红外吸收特性及微观结构，揭示了石灰石粉的碱激发活化机理。试验结果进一步表明，当偏铝酸钠质量掺量为15%时，浆体在71 min时初凝；掺入20%(质量分数)的偏铝酸钠时，试样3 d抗压强度可达25.3 MPa。偏铝酸钠可促进石灰石粉的缓慢溶解、重结晶，生成层状双氢氧化物Ca₄Al₂(OH)₁₂(CO₃)·5H₂O。然而当掺入过量偏铝酸钠时，Na⁺、Al(OH)₄^-、OH^-等离子无法及时与石灰石进行反应，使得所形成胶凝材料的凝结时间延长。因此，在制备碱激发石灰石粉胶凝材料时，需控制偏铝酸钠掺量在胶凝材料总量的20%以下。本研究为碳酸钙基胶凝材料的高效应用提供重要参考。     

Microanalysis and optimization-based estimation of C-S-H contents of cementitious systems containing fly ash and silica fume

In this study, a new approach to characterize hardened pastes of pure portland cement as well as those containing cement with supplementary cementitious materials (SCM) was adopted using scanning electron microscopy (SEM) and energy dispersive X-ray spectra (EDS) microanalyses. The volume stoichiometry of the hydration reactions was used to estimate the quantities of the primary and secondary calcium silicate hydrate (C-S-H) and the calcium hydroxide produced by these reactions. The 3D plots of Si/Ca, Al/Ca and S/Ca atom ratios given by the microanalyses were compared with the estimated quantities of C-S-H to successfully determine the Ca/Si ratio of eleven different cementitious systems at four different ages using a constrained nonlinear least squares optimization formulation by General Algebraic Modeling System (GAMS). The estimated mass fraction of calcium hydroxide from the above method agreed well with the calcium hydroxide content determined from the thermogravimetric analyses (TGA).     

多壁碳纳米管增强水泥基复合材料的纳米力学性能

采用纳米压痕技术探讨了多壁碳纳米管(MWCNTs)对有骨料水泥基复合材料纳米尺度上力学性能的影响,分别对压痕模量(M)小于50 GPa和压痕硬度(H)小于4.0 GPa的数据进行了统计,对其频率分布进行了Gaussian函数(PDF)的解卷积分峰处理,并对低密度水化硅酸钙凝胶(LD C-S-H)和高密度水化硅酸钙(HD C-S-H)凝胶进行了定量的体积分数计算。结果表明,除LD C-S-H、 HD C-S-H、 Ca(OH)2(CH)外,还出现了一个假相。MWCNTs降低了水化产物中LD C-S-H的体积分数,提高了HD C-S-H的体积分数,提高了C-S-H凝胶的压痕模量,但利用压痕模量和压痕硬度统计结果计算出的各相体积分数存在一定的差异。MWCNTs作为一种纳米晶核,对HD C-S-H凝胶形成起到了一定的诱导作用,从纳观尺度阐释了MWCNTs对水泥基材料的改性机制。     

A hydration study of various calcium sulfoaluminate cements

The present work studies the hydration process and microstructural features of five calcium sulfoaluminate (CSA) cements and a ternary mixture including also ordinary Portland cement (OPC). The pastes were studied with simultaneous differential thermal-thermogravimetric (DTA-TG) analysis, mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM), and expansion/shrinkage tests. The DTA-TG analysis confirmed the role of the hydration reactions involving the main CSA clinker constituent, tetracalcium trialuminate sulfate, which produced (i) ettringite when combined with lime and calcium sulfate, (ii) ettringite and aluminum hydroxide in the presence of calcium sulfate alone, and (iii) monosulfate and aluminum hydroxide in the absence of both lime and calcium sulfate. The MIP and SEM were able to discriminate between expansive (ternary mixture and CSA cement containing 50% gypsum) and non-expansive cements. Expansive cement pastes had (i) a nearly unimodal pore size distribution shifted toward higher radii and (ii) ettringite crystals smaller in size during the first day of curing. In a SEM image of a hardened paste of the CSA cement containing 50% gypsum, a stellate ettringite cluster was observed.     

Micro-structural development of gap-graded blended cement pastes containing a high amount of supplementary cementitious materials

To clarify the strength improvement mechanism of gap-graded blended cements with a high amount of supplementary cementitious materials, phase composition of hardened gap-graded blended cement pastes was quantified, and compared with those of Portland cement paste and reference blended cement (prepared by co-grinding) paste. The results show that the gap-graded blended cement pastes containing only 25% cement clinker by mass have comparable amount of gel products and porosity with Portland cement paste at all tested ages. For gap-graded blended cement pastes, about 40% of the total gel products can be attributed to the hydration of fine blast furnace slag, and the main un-hydrated component is coarse fly ash, corresponding to un-hydrated cement clinker in Portland cement paste. Further, pore size refinement is much more pronounced in gap-graded blended cement pastes, attributing to high initial packing density of cement paste (grain size refinement) and significant hydration of BFS.     

硫酸盐侵蚀溶液pH值对硅酸盐水泥浆体C-(A)-S-H凝胶结构的影响

C-（A）-S-H凝胶的结构不仅受水泥基材料自身组成的影响,更受其所处环境的影响。本文利用固体核磁共振（NMR）并结合去卷积技术,探究硫酸盐侵蚀溶液pH值对硅酸盐水泥浆体中C-（A）-S-H凝胶结构的影响。结果表明:硫酸盐侵蚀过程中,前期进入凝胶中的Al3+后期又会脱出,使凝胶中四配位铝（Al[4]）/Si比值降低。侵蚀溶液pH值的降低促进了凝胶中Al[4]的脱出,使Al[4]的峰位向负值移动;同时也促进了[SiO₄]（[AlO₄]）四面体间的聚合,使C-（A）-S-H凝胶平均分子链长（MCL）增加。此外,侵蚀溶液pH值的降低,促进了浆体的水化,但抑制了浆体中钙矾石（AFt）的生成。      

Effects of mechanical grinding on pozzolanic activity and hydration properties of quartz

To provide basic research into the utilization of mine tailings as supplementary cementitious materials in cement, the pozzolanic activity and hydration properties of quartz-a common mineral phase in mine tailings-after undergoing mechanical grinding were investigated. In this study, a supplementary cementitious material was obtained using the mechanical grinding of quartz. Prolonged grinding resulted in a gradual increase in the pozzolanic activity index and percentage of dissolution in an alkaline solution, as well as a reduction of the relative crystallinity. The particle size appeared to have reached a limit after 80 min of grinding; however, the specific surface area reached its limit after 120 min of grinding, which was mainly due to the continual increase in pore volume of the micropores and mesopores from the grinding process. As an active supplementary cementitious material, the hydration product of ground quartz was an amorphous C-S-H gel in the presence of calcium hydroxide. This study provides a research basis for investigating the pozzolanic activity and hydration properties of ground quartz, which is beneficial to an evaluation of the pozzolanic activity of siliceous mine tailings after mechanical activation.     

Comparative study of accelerated decalcification process among C3S, grey and white cement pastes

This study compared the resistance of Triclinic-C₃S, grey (OPC) and white (WOPC) Portland cement paste to decalcification induced by accelerated leaching in concentrated ammonium nitrate solutions. Paste microstructure was studied with scanning and backscattering electron microscopy (SEM and BSEM) and nitrogen BET surface area techniques. Ca²⁺ leached content was quantified by ICP, XRD and FTIR techniques were used to study phase mineralogy. The conclusions drawn from the findings were that calcium leaching-induced decay in the cementitious materials studied (C₃S, OPC and WOPC), accelerated by immersion in ammonium nitrate, affected the main calcium phases in the samples (CH, C-S-H gel and ettringite), i.e., both the anhydrous and the hydrated phases. The present study showed that the Ca/Si ratio of C-S-H gels declines on a gradient from the sample core outward. Specimen surface area and nanoporosity rose in cementitious materials after Ca leaching-induced decay and subsequently declined as a result of the collapse of the structure of the hydrated cement, and in particular of the C-S-H gel. C₃S paste was impacted more quickly and intensely by leaching than the WOPC and OPC pastes. Further to the findings of this study, the leaching resistance of these three materials, in descending order, is: OPC > WOPC > C₃S.     

Creep analysis of concrete containing rice husk ash

This paper presents an experimental study on the mechanical properties of concrete added with rice husk ash (RHA) as a supplementary cementitious material. The compressive strength, modulus of elasticity and creep were obtained experimentally from specimens with different RHA contents (0%, 10%, 15% and 20% of binder). The results show that the addition of RHA in concrete can improve both the compressive strength and modulus of elasticity and reduce the creep of concrete. The examination of pore micro-structure of hardened concrete using both the mercury intrusion porosimetry and scanning electron microscope techniques demonstrates that RHA particles can react with calcium hydroxide originated from cement hydration to produce additional C-S-H, which can fill voids and large pores and thus reduces the porosity related to capillary pores and voids. In addition, the release of absorbed water, which is retained in the small pores of RHA particles at early days, can improve cement hydration and thus reduce the porosity related to gel pores.