菱镁矿品位对MgO膨胀剂组成结构及性能的影响

通过对煅烧菱镁矿尾渣与二级菱镁矿所得MgO膨胀剂(MEA)组成、微观结构、活性及膨胀特性的研究,探讨了低品位菱镁矿制备MEA的可行性。结果表明,菱镁矿尾渣中方解石、白云石及铁元素等杂质的存在使MEA中f-CaO含量较高,方镁石含量较低;菱镁矿尾渣MEA中MgO晶粒为条状颗粒,而非二级菱镁矿MEA的球粒状,晶粒尺寸变大,晶粒间排列紧密,MEA颗粒表面有裂纹存在;柠檬酸法检测低品位菱镁矿所制MEA活性时应调整柠檬酸用量;有效膨胀组分含量低的情况下,800℃煅烧掺量为4wt%、6wt%和8wt%及850℃煅烧掺量为8wt%时,掺菱镁矿尾渣MEA水泥浆体的膨胀率比掺二级菱镁矿MEA水泥浆体的膨胀率大。可见,在一定条件下低品位菱镁矿所制MEA膨胀性能较高品位菱镁矿所制MEA好,有利于低品位菱镁矿矿产资源的有效利用。     

高活性氧化镁膨胀剂对UHPC性能的影响

利用一种活性反应时间为41 s的高活性氧化镁膨胀剂(MEA)掺入超高性能混凝土(UHPC),研究了其对UHPC工作性能、力学性能和体积稳定性的影响。采用压汞法对孔隙率及孔结构进行了表征，并利用SEM和EDS对硬化砂浆的微观形貌进行了分析。结果表明，高活性MEA会降低UHPC的流动性和力学性能，但可明显改善早期自收缩，MEA的最大掺量不宜超过胶凝材料总量的12%;MEA会降低早龄期UHPC的孔隙率，并细化其孔径，尤其是小于50 nm的孔，这是导致MEA可以补偿UHPC自收缩的重要原因；微观测试结果表明，MEA在原位水化反应生成密实的Mg(OH)₂,受到抑制的结晶将产生结晶压力，从而导致体积膨胀；由EDS结果可知，无胶结能力的MEA及其水化产物与水泥浆体的界限随龄期的增长而逐渐模糊，UHPC整体趋于密实。     

CaSO4·2H2O-C3A压实体水化产生膨胀应力的机理

本工作采用自行设计的一套膨胀应力测试装置测试了在三维约束条件下CaSO_4·2H_2O-C_3A压实体在40℃的水溶液、饱和Ca(OH)_2溶液和1 mol/L NaOH溶液中水化生成钙矾石过程中产生的膨胀应力,并测试了压实体中水化生成的钙矾石的吸水肿胀应力。结果表明,CaSO_4·2H_2O-C_3A压实体在水溶液、饱和Ca(OH)_2溶液和1 mol/L NaOH溶液中水化生成钙矾石产生的最大膨胀应力为23.9 MPa、27.3 MPa和26.4 MPa,在水溶液中水化膨胀应力最小,表明Ca(OH)_2溶液和OH~-均会促进钙矾石产生的膨胀应力;生成的钙矾石45℃干燥再吸水,在约束条件下40℃的吸水肿胀应力分别为1.23 MPa、1.27 MPa和1.26 MPa,远小于钙矾石形成过程产生的膨胀应力,表明钙矾石吸水肿胀应力对CaSO_4·2H_2O-C_3A压实体水化膨胀应力的贡献很小,钙矾石形成时产生的膨胀应力主要源于结晶压力。     

纤维素醚-膨胀珍珠岩耦合作用下水泥浆体早期水化规律

利用水化放热速率、XRD、FT-IR、DTG和Ca(OH)2含量测试手段,研究了羟丙基甲基纤维素醚和膨胀珍珠岩两种保水因子单掺和耦合作用条件下水泥浆体的早期水化规律及二者的作用机理。结果表明羟丙基甲基纤维素醚能够显著降低水泥浆体早期水化放热速率峰值,且能延缓诱导期和加速期出现的时间,对水泥浆体中后期水化没有明显的延缓效应。膨胀珍珠岩可以降低早期水化放热速率峰值,效果较羟丙基甲基纤维素醚差,但对水泥水化无延缓效应。当二者耦合作用时,具有显著的叠加效应。水化12h时,羟丙基甲基纤维素醚和膨胀珍珠岩能够显著降低水泥浆体中Ca(OH)2含量,较空白样分别降低了43.6%和9.1%。水化1和3d时,水泥浆体中Ca(OH)2含量随二者掺加而降低的趋势变缓。     

离子掺杂对钙质膨胀剂熟料性能的影响

研究了MgO、Al2 O3和CuO三种金属离子氧化物对氧化钙类膨胀剂熟料性能的影响,与未外掺金属离子氧化物相比,分别外掺3％金属离子氧化物后,CuO抑制了膨胀剂熟料反应速率,MgO对膨胀剂熟料反应速率基本无影响,Al2O3加速了膨胀剂熟料的反应速率.采用化学分析、XRD、微量热法对膨胀剂熟料的f?CaO含量、矿物组成及水化历程进行了分析,结果表明,外掺CuO会抑制生料中CaCO3分解为f?CaO,导致膨胀剂熟料反应速率较低;外掺MgO、Al2 O3主要在膨胀剂熟料体系中发生离子置换反应,因Al3+与Ca2+价位不同使体系内部产生缺陷,提高了其膨胀反应速率.     

常温下硝酸铵钙对硫铝酸盐水泥的早强作用

研究了常温下硝酸铵钙对硫铝酸盐水泥浆体的流动度、凝结时间、抗压强度、电阻率及浆体内部温度、水化热、水化产物和孔结构的影响,对硝酸铵钙的早强作用机理进行了分析。结果表明,当硝酸铵钙的掺量从0增大到5%时,水泥浆体的初始流动度明显增大,凝结时间显著缩短,6 h,1,3,7和28 d抗压强度均显著提高,电阻率变化速率曲线峰值出现的时间逐渐提前,水泥浆体内部温度逐渐升高,温峰出现时间提前;其掺量在2%以内时,水泥水化放热速率明显加快,1 d累积放热量略有增大,钙矾石的生成速率及生成量均增大,硬化水泥浆体的平均孔径、总孔体积和孔隙率减小。由于硝酸铵钙能够明显加快硫铝酸盐水泥的水化进程,使其早期强度显著提高,因此可用作早强剂。     

富镁矿渣对油井水泥浆体膨胀性能的影响及水化机理

80℃水浴养护环境下,研究了不同掺量富镁矿渣对G级油井水泥浆体膨胀性能及其他基本性能的影响,考察了40%富镁矿渣掺量下水泥浆体的工程性能,同时研究了富镁矿渣的水化机理。实验结果表明,掺加富镁矿渣的水泥浆体具有微膨胀性能,其中掺40%富镁矿渣的水泥浆1d线膨胀率为0.0035%,28d线膨胀率为0.0255%;富镁矿渣掺量对水泥浆体凝结时间、流动度、密度影响不大;水化放热量和水泥石早期强度(3d前)均随富镁矿渣掺量的增加而降低,而后期强度(28d后)逐渐升高并高于净浆水泥石;硬化体中Ca(OH)2含量随富镁矿渣掺量增加和养护龄期的延长而降低;40%富镁矿渣掺量下,浆体各项工程性能基本满足固井施工基本技术要求。     

电阻率法研究引气剂对水泥浆体化学收缩及氯离子渗透性的影响

研究了引气剂对硅酸盐水泥浆体的电阻率、化学收缩、物理力学性能及氯离子渗透性的影响。结果表明,掺入引气剂使水泥浆体的流动度增大,凝结时间延长,早期水化速率加快,化学收缩增大。水泥浆体的电阻率在凝结前随着引气剂掺量的增加而增大,在硬化后则随着掺量的增加而减小。在28d龄期时,0.04%掺量内的引气剂对硬化浆体的抗压强度影响较小,其强度损失率低于5%,氯离子迁移系数随掺量的增大而减小。随引气剂掺量的变化,水泥浆体的电阻率与化学收缩、抗压强度和氯离子迁移系数均存在很好的定量关系。通过水泥浆体的电阻率发展曲线可以预测其化学收缩、强度与氯离子渗透性的变化规律。     

粉煤灰对水泥基材料水化过程电阻率的影响研究

本工作研究了粉煤灰掺量分别为0%、20%、40%时水泥浆体在72 h龄期内的电阻率、孔溶液离子浓度和孔结构的变化规律。结果表明,不同粉煤灰掺量的水泥浆体电阻率变化曲线会发生交叉,在交点之前,水泥浆体的电阻率随着粉煤灰掺量的增大而增大,在交点之后,随着粉煤灰掺量增大,水泥浆体的电阻率减小;掺入粉煤灰使得孔溶液的pH值降低,液相离子浓度减小,浆体总孔隙率增大。随着粉煤灰掺量的增大,水泥浆体的液相离子浓度变小,而孔隙率变大,受这两个因素的双重影响,不同粉煤灰掺量的水泥浆体的电阻率变化曲线产生交叉。     

电学方法研究掺有窑灰水泥的水化特性

利用非接触式电阻率新方法,研究普通硅酸盐水泥及粉煤灰和粉磨时间分别为1h、3h和4h的窑灰混掺后胶凝材料的水化特性.试验结果表明,窑灰分别粉磨1h、3h和4h后,在同样掺量情况下,对水泥浆体早期电阻率随时间的变化有明显的影响.高碱度和高Cl-、高SO3含量将直接影响到窑灰作为混合材或直接回窑后水泥的早期水化特性.不同掺量的粉煤灰在一定程度上可以平衡窑灰水泥浆体系中的碱,同时窑灰中的碱也可激发粉煤灰的早期活性,在熟料掺量小于50%时仍可获得较高的早期强度.     

Effects of MgO-based expansive additive on compensating the shrinkage of cement paste under non-wet curing conditions

Expansive additives are widely used to compensate the drying shrinkage of cement-based materials to avoid cracking. However, the expansion of conventional ettringite-bearing expansive additive depends strongly on wet curing and is mainly generated at early age, and hence it may not work well in concretes without sufficient water supply or exhibit long-term shrinkage. MgO-based expansive additive, for which less water is needed for the formation of Mg(OH)₂ in comparison to ettringite, was prepared and its compensating effect on the autogenous shrinkage and late age thermal shrinkage of Portland and fly ash cement pastes at low water-to-cement ratio was investigated. The tests were conducted under sealed condition, so that the moisture exchange with the environment was prevented. Results show that, even under the non-wet curing condition, the shrinkages of cement pastes can be compensated effectively. Microstructure analysis by scanning electron microscope indicates that the macro-expansion of cement pastes is probably caused by the locally restrained expansion of MEA due to the hydration of MgO.     

Ca(OH)2解耦法对混合水泥中C-S-H凝胶的半定量研究

基于掺合料反应程度与Ca(OH)2消耗量之间关系的建立,结合水泥水化平衡计算理论,提出混合水泥水化产物中Ca(OH)2量的解耦方法并将其用于混合水泥水化产物C-S-H凝胶半定量计算.采用该法对掺粉煤灰的混合水泥不同龄期水化产物C-S-H凝胶进行了半定量分析研究.     

硬化水泥净浆基于纳米压痕的相态识别与水化程度计算

采用纳米原位压痕手段测量硬化水泥净浆中单一相态的代表性微观力学性能,并采用纳米点阵压痕研究各相态的含量。研究对象囊括水灰比为0.3、0.4、0.5的纯水泥净浆和水灰比为0.3情况下含50%、70%矿渣掺量复合体系,共5种配比,以表征它们的相态分布和微观力学性质的异同点。掺矿渣的试件中含有明显多的复合相,因此提出三相模型测算复合相中未水化物的体积分数。此外,提出基于纳米压痕技术计算纯水泥和掺矿渣水泥试件水化程度的方法,结果吻合于热重分析的结果,其中纯水泥净浆中复合相较少,计算得到的水化程度优于对掺矿渣水泥试件的计算。     

Alongterm study of MgO hydration in cement pastes

The effect of various additives on the longterm hydration of Magnesium Oxide, (MgO) in cement pastes cured in water at 18±2°C up to 12 years was studied by X-ray diffraction (XRD), seanning electron microscopy (SEM) and EPMA. It was found that cement with high MgO content, is stabilized even after a longterm period of hydration by active pozzolans.     

Use of admixtures in organic-contaminated cement-clay pastes

In this work microstructure, porosity and hydration degree of cement-based solidified/stabilized wasteforms were studied before assessing their leaching behaviour. 2-Chloroaniline was chosen as a model liquid organic pollutant and included into cement pastes, which were also modified with different admixtures for concrete: a superplasticizer based on acrylic-modified polymer, a synthetic rubber latex and a waterproofing agent. An organoclay, modified with an ammonium quaternary salt (benzyl-dimethyl-tallowammonium, BDMTA), was added to the pastes as pre-sorbent agent of the organic matter. All the samples were dried up to constant weight in order to stop the hydration process at different times during the first 28 days of curing, typically, after 1 day (1d), 7 days (7d) and 28 days. Then, the microstructure of the hardened cement-clay pastes was investigated by powder X-ray diffraction (XRD). The hydration degree and porosity were studied by thermal analysis (TG/DTA) and mercury intrusion porosimetry (MIP), respectively. For samples cured for 28 days a short-term leach test set by Italian regulation for industrial waste recycling (D.M. 5 February 1998) was performed. The best results showed a 5% release of the total initial amount of organic pollutant.     

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.     

Immobilization of Co(Ⅱ) Ions in Cement Pastes and Their Effects on the Hydration Characteristics

The immobilization of Co(Ⅱ) in various cement matrices was investigated by using the solidification/stabilization(S/S) technique.The different cement pastes used in this study were ordinary Portland cement in absence and presence of water reducing-and water repelling-admixtures as well as blended cement with kaolin.Two ratios of Co(Ⅱ) were used(0.5% and 1.0% by weight of the solid binder).The hydration characteristics of the used cement pastes were tested via the determination of the combined water content,phase composition and compressive strength at different time intervals up to 180 d.The degree of immobilization of the added heavy metal ions was evaluated by determining the leached ion concentration after time intervals extended up to 180 d.The leachability experiments were carried out by using two modes:the static and the semi-dynamic leaching processes.It was noticed that the concentration of the leached Co2+ ions in the static mode of leachability was lower than the solubility of its hydroxide in all the investigated cement pastes.     

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。     

钙矾石的结构变异对膨胀水泥膨胀性的影响

通过DTA,X射线衍射分析和SEM观察及与膨胀率和强度的对比分析,给出了钙矾石稳定存在和结构变异的温度范围及其对砂浆膨胀和强度的影响.结果表明,(1)在干热条件下钙矾石在87-150℃之间发生快速脱水,结构极度扭曲失去晶体特征,但结构并不崩溃分解,遇水后即可恢复.100℃以下的湿热条件下,钙矾石可生成和稳定存在;(2)尽管100℃以下的干燥条件膨胀水泥混凝土的强度不降低,但膨胀会完全丧失,甚至产生负膨胀.故膨胀水泥和自应力水泥不宜在70℃以上的干燥环境和干-湿交替的环境中使用.