钙矾石的形成和稳定条件

本文研究了在C_(12)A_7中加入不同形态和不同量的石膏后,钙矾石的形成和稳定条件,同时研究了液相成分和水化的固相产物。 从液相的化学成分分析结果发现,溶液中[CaO]和[SO_3]的浓度有一突然下降,在加入石膏的条件下,[CgO]浓度从1.0mg/ml降至 0.5mg/ml,而[SO_3]从 1.0mg/ml 降至 0.1mg/ml。至于[Al_2O_3]的浓度,从开始时逐渐上升,而后缓慢下降。与此同时,固相中已形成的钙矾石转变为低硫型水化硫铝酸钙(由 XRD和DTA所证实)。 然而,在含有硬石膏的试样中液相的[SO_3]浓度一开始就很低,所以只有低硫型盐存在。据此作者认为,当W/S比例较大时,如在本实验的条件下为10,钙矾石是通过液相生成的,而钙矾石的稳定条件在很大程度上决定于液相中[SO_3]的浓度,如溶液中[SO_3」的浓度低于1.0mg/ml,则钙矾石不能稳定存在,将转变为低硫型盐。 若在上述系统中加入可以与水化铝酸钙形成复盐的化合物,如CaCO_3,将与 C_(12)A_7反应生成水化碳铝酸钙,则可避免钙矾石的转变。 作者还认为已经生成的低硫型盐,在液相[SO_3]浓度适合的条件下也会转变为钙矾石,不过这还需要继续工作。 文章最后还简短讨论了钙矾石的形成机理及液相中[CaO]、[SO_3]和[Al_2O_3]浓度变化的规律。     

碱对钙矾石结晶及溶解性能的影响

主要通过C3A-CaSO4.2H2O,在不同碱性溶液中钙矾石的形成、晶体形貌变化以及制备得到的纯钙矾石在不同碱性溶液中的溶解来研究碱对钙矾石结晶、溶解性能的影响,并采用XRD、SEM以及ICP等分析方法进行表征.研究结果表明,碱对钙矾石的形成有促进作用,还会影响钙矾石晶体形貌.钙矾石在不同碱性溶液中具有不一致溶特性,OH-对钙矾石中A l(OH)4-、Ca2 和SO42-溶出能力具有抑制作用.     

论形成钙矾石相的膨胀

回顾了各家对硬化水泥浆体中形成钙矾石相引起膨胀的可能原因的看法。它们是:固相体积增大、固态反应、渗透压、吸水肿胀和晶体生长推力(结晶压力)。作者分析了上述论点,并对照与钙矾石相形成有关的水泥硬化浆体的膨胀事实,提出了下面的看法。通过液相(不论液相中 Ca(OH)_2浓度是饱和还是不饱和)形成的钙矾石相,其形成时的固相体积因外界水份的补充而增大,并因晶体交叉生长的结晶压是引起膨胀的根本原因;所提供的膨胀大小与钙矾石相的形态、数量、形成时间有关;硬化水泥浆体的织构、强度、自应力等性能与钙矾石相以及同时形成的对强度起主要作用的凝胶相的形成特点、数量和硬化水泥浆体的限制条件有关。     

钙矾石对Cr6+和Cr2+的固化及稳定性

通过溶液法人工合成钙矾石,分析比较了水化形成过程中钙矾石对Cr6+和Cr2+固化机制及其稳定性.结果表明,Cr6+和Cr2+均可对钙矾石晶格结构产生一定影响,但两者在钙矾石中固化机制并不完全相同.Cr6+挤入钙矾石晶格层间结构,改变了分子对称性,对钙矾石晶体结构有较大影响;而Cr2+对钙矾石晶体结影响较小.在水化液相中重金属离子含量较低时,钙矾石对Cr2+、Cr6+俘获能力较高,且少量Cr2+对钙矾石晶体生长发育促进作用;而重金属离子含量较高时,钙矾石对Cr6+俘获能力明显下降,但对Cr2+的固化能力仍较高.钙矾石对Cr2+固化受环境条件影响较小,同时少量Cr2+在一定程度上有利于稳定碳化条件下钙矾石晶形结构;而钙矾石对Cr6+的固化受外界环境因素影响较大,且碳化、冻融、氯盐侵蚀多因素复合对其固化稳定性有极大影响.     

Al3(SO4)2(OH)5H2O与α-Al2O3晶须的制备及其生长机制

采用液相沉淀及烧结方法制备了Al3(SO4)2(OH)5H2O与α-Al2O3晶须,样品采用XRD、SEM及G-DTA等对样品物相、形貌及热行为进行了表征,结果表明晶须样品的分散性好,粒度分布均匀、表面光滑,Al3(SO4)2(OH)5H2O与α-Al2O3晶须品质优良.又从“生长基元”角度出发,讨论了Al3(SO4)2(OH)5H2O晶须的形成机制,其生长过程是生长基元是八面体[Al-(OH)6]3-与HSO4-往某一晶面稳定叠合生长的结果,Al3(SO4)2(OH)5H2O晶须经热分解后,其形貌不变,最终变为α-Al2O3晶须.     

碱-集料反应的一些理论问题

评述了碱-集料反应的一些理论问题以及活性集料分布规律。碱-硅反应膨胀主要是由渗透压力和钙矾石膨胀所致。碱-硅反应产物组成SiO_2/Na_2O=0—25(分子比)。Ca(OH)_2提供了生成钙矾石膨胀相和R(Na,K)CSH的物质。碱-Kingstone白云岩反应膨胀是碱-硅反应、黄铁矿分解形成钙矾石和蒙脱石吸水膨胀等综合因素引起的。     

AFt@SiO2核/壳结构的制备及其性能研究

钙矾石(AFt,3CaO·Al2O3·3CaSO4·32H2O)因其结构中含有大量结晶水而具备了用于制造阻燃材料的潜质.以Al2(SO4)3·18H2O和Ca(OH)2为原料,在200℃条件下通过水热反应进行钙矾石的合成实验,研究了反应物浓度,反应时间,pH值对反应产物的影响,并使用改进的St?ber法在钙矾石晶体表面包覆SiO2壳层,制备AFt/SiO2核/壳结构.采用XRD、SEM、FT-IR、TG等方法对产物表征测试.结果表明:通过水热法可以快速合成出高纯度,结晶性好的钙矾石晶体,pH=10是钙矾石晶体生长的适宜条件;SiO2壳层的包覆能控制AFt的脱水速率,也会降低AFt的含水率.     

难分解铌钽矿高浓氢氧化钾浸出机理研究

实验研究了难分解铌钽矿在高浓度氢氧化钾溶液中浸出过程的机理。考察了搅拌转速、反应温度、碱矿比、初始氢氧化钾浓度和矿粒度对铌钽矿中铌的浸出速率的影响。结果表明铌的浸出速率与铌钽矿粒径的平方成反比,浸出过程受克-金-布产物层固膜扩散控制,即1 2(1-X)-3(1-X）^2/3=kt,并由阿累尼乌斯方程得到铌的表观活化能为72．21kJ．mol^-1。结合动力学实验结果和电子扫描电镜(SEM)及X-射线能谱(EDAX)分析,进一步证明了在浸出过程中铌钽矿的表面形成了固相产物层,其主要组成元素为铁、锰等,并指出六铌(钽)酸根离子([(Ta,Nb)6O19]^3.)通过固相产物层的内扩散为浸出过程的控制步骤。研究结果为浸出过程的强化提供了依据。     

杂质离子对N_(235)萃取氟、磷性能的影响

以叔胺N_(235)为萃取剂,分别以氯仿-煤油和二甲苯为稀释剂。研究了磷酸中铁、铝、镁、钙、硅等杂质离子的浓度对氟、磷萃取分离性能的影响。结果是;硅的存在有利,铁在[Fe_2O_3]=0.03～0.08 mol·L~(-1)浓度范围内有利,铝在[Al_2O_3]>0.05 mol·L~(-1)时以及用氯仿-煤油为稀释剂时有利,其它条件均不利于氟、磷的萃取分离。     

苯丙共聚物改性硫铝酸钙胶结料-无水石膏复合体系的水化

采用量热仪、X射线衍射仪、热重、扫描电镜、电感耦合等离子光谱等方法研究了苯丙共聚物（SA）对硫铝酸钙胶结料-无水石膏复合体系早期水化的影响。结果表明:SA会延缓水化进程,减少水化加速期钙矾石（AFt）、单硫型水化硫铝酸钙（AFm）和Al（OH）₃ （AH₃）含量,促进AH₃与石膏和氢氧化钙反应生成AFt,并促进水化后期AFt向AFm转变。同时,SA会迅速降低体系孔溶液的表面张力,随着水化反应进行表面张力趋于稳定;SA也提高了孔溶液的p H值,增大OH^–浓度,影响了体系中Ca²⁺、SO₄^2–和[Al（OH）₄]^–的浓度和比例,减小水化初期水化产物的离子浓度积,降低水化产物析出速率,进而延缓水化进程、减少水化产物。     

Influence of solution chemistry on the hydration of polished clinker surfaces—a study of different types of polycarboxylic acid-based admixtures

The influence of two different types of polycarboxylic acid-based superplasticizers (homo- [HP] and copolymer [CP]) on the early hydration of Portland cement clinker is investigated. Polished clinker surfaces are hydrated in aqueous phase extracted from cement paste with and without superplasticizers as well as in saturated Ca(OH)₂/CaSO₄ solution and in deionized water. Scanning electron microscopy (SEM) is used to characterize the early hydration products after 30 min and after 24 h of hydration. Contrary to the hydration reaction with deionized water, in the presence of ionic solutions, the texture and morphology of the clinker surface are significantly altered, and amorphous and crystalline hydration products, mainly ettringite, are formed. The amount and type of ettringite formed are strongly related to solution chemistry and type of superplasticizer. In the presence of superplasticizers, the formation of hydration products and ettringite is reduced and the hydration of the surface is suppressed. Furthermore, the rate of hydration in mortar is studied in the presence of the two admixtures by measuring the temperature evolution as a function of time. The concentration-dependent delay in temperature evolution correlates well with the microscopic observations of different amounts of ettringite formation.     

The impact of Fe dosage on the ettringite formation during high ferrite cement hydration

Illustrating the influence of Fe dosage and temperature on the formation of sulfoaluminate hydrates is of great significance to understand the early hydration process of high ferrite cement under steam curing. Herein, the impact of Fe dosage on the ettringite formation at different temperatures was revealed through the combination of experiments and computational simulations. A Fe dosage no more than 20% conspicuously accelerated the crystal growth of ettringite by increasing the surface energy in the (0 0 1) direction, whereas a higher dosage suppressed the formation of ettringite as the high incorporation of Fe ions into the ettringite crystal was energetically unstable. The chemical environment analysis of Fe in products shows that Fe(OH)₆³⁻, compared with Al(OH)₆³⁻, prefers to participate in the formation of Al₂O₃-Fe₂O₃-mono than ettringite, which is also confirmed by the calculated thermodynamic properties’ results. The understanding of the impact and mechanism of Fe on the formation of ettringite under steam curing conditions plays a pivotal role in the utilization of high ferrite cement.     

Effect of Chloride on the Structure of Fluoroaluminate Glasses Studied by XPS

The effect of chlorine on the structure of AlF₃/YF₃-based fluoride glasses was studied by XPS. The changes in the bonding state of cations with increase of chlorine content were all investigated by measuring the composition-depend- dent changes in the relative concentration and binding energy of related cations. It was proposed that the chlorine replaces the bridging fluorine by which the [AlF _n ] and [YF _m ] polyhedra are connected and result in the formation of [AlF _n-u Cl _u ] and [YF _m-v Cl _v ] polyhedra. In the low BaCl₂ content region (<6 mol%), as many chlorine as possible attack [A1FJ and [YF _m ] polyhedra, and with the increase of chlorine content, they replace more fluorines in [YF _m ] polyhedra, while the number of chlorines in [AIF_n-uCl_u] polyhedra remains a low constant value. In the high BaCl₂ content region (>6 mol %), the chlorines replace more fluorines in the already formed [AlF_n-uCl_u] polyhedra and do not attack other [AlF] polyhedra, while the composition of [YF_m-vCl_v] polyhedra does not change.     

Effect of ettringite on thaumasite formation

Deterioration of cementitious building materials is often caused by sulphate attack where ettringite and gypsum play the most destructive role at moderate ambient temperatures. In contrast, thaumasite [Ca₃Si(OH)₆·12H₂O](SO₄)(CO₃) is mostly observed at comparatively low temperatures of less then 15 °C. This mineral forms from calcium, sulphate, carbonate and silicon. The latter originates from the decomposition of C-S-H which results in deterioration of the hardened cement paste structure. To investigate the effect of ettringite on thaumasite formation, pastes were mixed using synthetic clinker phases, fly ash and nanosilica. Aqueous suspensions were prepared with the ground-hydrated pastes mixed with calcite and either gypsum or sodium sulphate. Following different storage periods, the solid phase was separated by filtration, dried and analysed by XRD using the Rietveld method as well as ESEM and TEM. The liquid phase was analysed by ICP-OES. The results indicate that thaumasite formation occurs through the heterogeneous nucleation of thaumasite on the surface of ettringite, due to the structural similarities of these minerals. This reaction is followed by further epitaxial growth of thaumasite from its components present in solution.     

碱性和无碱液体速凝剂促凝早强作用机理对比研究

碱性和无碱速凝剂掺入水泥后的水化机理不同,导致应用性能存在明显差异。本文通过测试凝结时间和砂浆抗压强度等宏观性能对比了两种速凝剂的应用性能,并通过水化放热分析、XRD定量分析、热重分析和SEM微观形貌观察等微观方法综合分析了两者的早期水化历程。结果表明:碱性速凝剂加入水泥后,[Al(OH)₄]^-加快了水泥中石膏的消耗速度,水化初期生成大量钙矾石(AFt),促进了硅酸三钙(C₃S)矿物的水化,缩短了水泥浆体的凝结时间并提高了砂浆的早期抗压强度,但石膏的加速消耗也使得单硫型水化硫铝酸钙(AFm)和水化铝酸钙(C-A-H)等水化产物提前生成,影响了水泥基材料的后期抗压强度发展;无碱速凝剂加入水泥后,[Al(OH)₄]^-和SO^2-₄在液相中生成了大量AFt,促进了铝酸三钙(C₃A)和C₃S矿物的水化,影响了氢氧化钙(CH)的结晶析出。值得注意的是,SO^2-₄不仅促进了C₃A生成AFt的过程,也延缓了水泥中石膏的消耗及AFm和C-A-H等产物的生成,因此无碱速凝剂的加入除了明显提高早期抗压强度外,后期28 d抗压强度也不受影响。     

吡啶类离子液体在类紫罗兰二烯烯丙位氧化中均相与非均相行为

The combination of relatively low-cost ionic liquids, simple copper salt, and terminal oxidant tert-butyl hydroperoxide provided an efficient and environmentally friendly approach to the preparation of ionone-like dienones. Six pyridinium ionic liquids were evaluated in allylic oxidation of α-ionone and β-ionone. The 60%–70% yields of 3-oxo-α-ionone were obtained with 0.02-0.20 mmol of CuCl2&#8226;2H2O as catalyst, 3-5 mmol of tert-butyl hydroperoxide as oxidant and 1 g of [Bpy]PF6 as solvent for 4-20 h at 60°C. The facile recovery and recycle of catalyst were also achieved. More significantly, peculiar phase behaviors of [Bpy]PF6 and [Epy]PF6 offered the catalytic system advantages of homogeneous reaction and heterogeneous separation. Scanning electron microscope (SEM) images of [Bpy]PF6 provided evidences for the behaviors. Transmission electron microscope (TEM) micrographs showed copper salt nanoparticles catalyst formed and stabilized in pyridinium ionic liquids.     

Recycling and Activity Recovery of Chloroaluminate Ionic Liquid as Catalyst for Alkylation of Benzene with 1-Dodecene

Performances of 1-butyl-3-methylimidazolium aluminium chloride ([BMIM]Cl-AlCl3) ionic liquid as catalyst for the alkylation of benzene with long chain olefins were investigated in a continuous operation mode. A small pilot plant with continuous mixing-reacting-separating-recycling functions, equipped with a static mixer reactor, a tube packed with metal Al thread and a combined liquid-liquid settling phase separator, was introduced as an alternative. The results showed that the continuous fast mixing and separation of ionic liquid catalyst from reactant mixture could be synchronously accomplished within a wider flow rate ratio range of the recycling reaction mixture to the ionic liquid catalyst. The recycling of chloroaluminate ionic liquid was realized. ICP-AES detection results of Al content in the reactants proves that in-situ Al compensation to the reaction system may be an important choice to prolong the stable running time of moisture-sensitive ionic liquid [BMIM]Cl-AlCl3 when feedstock inevitably contains trace water. It suggests that the activity of chloroaluminate ionic liquid is recovered under the in-situ Al compensation operation.     

The C-S-H gel of Portland cement mortars: Part I. The interpretation of energy-dispersive X-ray microanalyses from scanning electron microscopy, with some observations on C-S-H, AFm and AFt phase compositions

Scanning electron microscopy (SEM) microanalyses of the calcium-silicate-hydrate (C-S-H) gel in Portland cement pastes rarely represent single phases. Essential experimental requirements are summarised and new procedures for interpreting the data are described. These include, notably, plots of Si/Ca against other atom ratios, 3D plots to allow three such ratios to be correlated and solution of linear simultaneous equations to test and quantify hypotheses regarding the phases contributing to individual microanalyses. Application of these methods to the C-S-H gel of a 1-day-old mortar identified a phase with Al/Ca=0.67 and S/Ca=0.33, which we consider to be a highly substituted ettringite of probable composition C₆A₂S?₂H₃₄ or {Ca₆[Al(OH)₆]₂·24H₂O}(SO₄)₂[Al(OH)₄]₂. If this is true for Portland cements in general, it might explain observed discrepancies between observed and calculated aluminate concentrations in the pore solution. The C-S-H gel of a similar mortar aged 600 days contained unsubstituted ettringite and an AFm phase with S/Ca=0.125.     

Investigation of the structure of ettringite by time-of-flight neutron powder diffraction techniques

The crystalline structure of ettringite, Ca₆[Al(OH)₆]₂(SO₄)₃·∼26H₂O, was investigated using high-resolution time-of-flight neutron powder diffraction techniques. The powder diffraction data were subjected to Rietveld crystal structure refinement. The resultant ettringite crystal structure confirmed the positions of Ca, Al, and S atoms while permitting a more precise determination of the locations of O and H atomic positions than in previous X-ray and neutron diffraction studies. A discussion of the ettringite hydrogen bonding network is presented, illustrating the role of hydrogen bonding in the stabilization of the ettringite structure.