纳米CaCO3对硅酸盐水泥水化特性的影响

为研究纳米CaCO3对硅酸盐水泥水化特性的影响,利用微量热仪法测试了不同掺量纳米CaCO3对硅酸盐水泥水化放热影响,利用差示扫描热分析-热重(DSC-TG)法分析了其水化产物中Ca(OH)2含量与结合水量,并研究不同掺量纳米CaCO3对水泥基材料力学性能的影响.结果表明,在本试验条件下,纳米CaCO3的掺入促进了水泥的水化放热速率,水化放热亦随之增加;随着纳米CaCO3掺量增大,硅酸盐水泥水化生成的Ca(OH)2含量与化学结合水量皆增加;掺入纳米CaCO3水泥基材料的抗折和抗压强度提高,掺量为1.5％(质量分数)时对水泥基材料的力学性能提高最为显著.研究结果显示纳米CaCO3加速了硅酸盐水泥的水化.     

高掺量混合材复合水泥的水化性能

通过水化微量热、化学结合水测定和X射线衍射、热重-差热分析、扫描电镜等测试方法研究了3种高掺量矿渣、粉煤灰、石灰石复合水泥的水化性能,并与硅酸盐水泥的水化进行了对比。结果表明：高掺混合材复合水泥的水化放热特征与硅酸盐水泥有明显不同,早期水化反应速度低于硅酸盐水泥,但后期由于矿渣、粉煤灰的二次水化反应使其水化速度增长较快。主要的水化产物亦为水化硅酸钙凝胶、钙钒石和Ca(OH)2晶体,但Ca(OH)2含量明显低于硅酸盐水泥浆体中的Ca(OH)2含量。     

钛渣活性特征及激发活性技术研究

采用XRD、SEM、NMR等微观测试方法,探讨水泥-钛矿渣-激发剂胶凝材料体系的水化机理.研究结果表明:钛矿渣由于氧化钛含量较高,导致CaO、SiO2量相对减少,水化活性降低.一般的机械活化和化学激发手段激发钛矿渣水化活性有限,采取复合活化激发方法及大掺量激发时,方可促使钛矿渣满足S75标准.试块中水化产物形貌明显致密化,Ca(OH)2晶体消失,胶凝体系中出现Afm相,且组群状和链状C-S-H量增多,钛矿渣水化速率加快.     

晶体源对碱矿渣水泥力学性能的影响

为改善碱矿渣水泥基材料的脆性,以水玻璃为碱组分的碱矿渣砂浆为对象,研究掺入晶体源Al2 O3、A1(OH)3、Ca(OH)2以及引气剂后碱矿渣砂浆的力学性能.结果表明:掺入Al2O3与Al(OH)3,没有改善碱矿渣砂浆的脆性;掺入Ca(OH)2的碱矿渣砂浆3d折压比有较大提高,随龄期延长,折压比有所降低,但仍高于基准碱矿渣砂浆;引气剂与Ca(OH)2复掺时,对碱矿渣砂浆脆性改善明显,随龄期延长,韧性增加更多;单掺Al(OH)3与Ca(OH)2,以及复掺引气剂可以提高碱矿渣水泥水化产物的结晶程度.     

硅酸盐水泥-矿渣复合浆体的水化反应进程研究

为考察矿渣对水泥水化进程的影响,系统研究了在不同的养护龄期、水胶比、矿渣掺量条件下,水泥-矿渣复合浆体的矿渣反应程度、非蒸发水含量、Ca(OH)2含量、孔隙率和力学性能.根据实验结果,研究了复合浆体中矿渣反应程度和非蒸发水含量的变化规律,探讨了矿渣的掺入对Ca(OH)2含量的影响,提出了水化反应进程中水泥与矿渣对Ca(OH)2的供求模式,分析了矿渣与水泥的叠加与互补效应,确定了矿渣的最佳掺量范围和最大掺量范围.上述结果可为矿渣在水泥基材料中合理有效地利用提供一定的科学依据.     

粒化高炉矿渣的水化机理探讨

以上海梅山钢铁公司的矿渣为研究对象,探讨粒化高炉矿渣在无激发剂存在的条件下的水化机理,并建立矿渣水化反应过程的化学模型。为矿渣的大规模、无害化、资源化和高附加值利用奠定理论基础。研究表明:在没有化学激发剂存在的条件下,梅山矿渣的水化产物是水化硅酸钙C2SH(C)、水化硅酸钙2CaO·SiO·(2￣4)HO和钙铝黄长石22Ca2Al(Al,Si)2O7。初期的水化过程是矿渣中的Ca2 等网络改变体阳离子与水中的H之间的置换,随着这种置换反应的进 行,溶液中的pH值不断升高,当pH高到一定程度时,矿渣颗粒表面上的HSiO4的溶解度将提高,溶解了的各种形态4的硅酸离子和溶液中的Ca2 、OH反应生成水化硅酸钙凝胶。     

大掺量矿渣石膏水泥基复合材料的水化特性

通过测试宏观抗压强度,同时采用XRD和TG-DTA技术对大掺量矿渣石膏水泥基复合材料的水化特性进行了研究,研究表明:大掺量矿渣石膏水泥基材料早期强度远低于纯水泥,但其强度发展较快,尤其是7～28 d阶段,28 d强度基本达到42.5 MPa水平,90 d龄期强度除SG-4试件均超过纯水泥水平.试件早期强度随着熟料含量的增加而增长,而后期强度并不遵循这一规律,水化后期主要是矿渣粉中活性Al2O3与活性SiO2参与水化反应,提高了体系抗压强度.SG系列水化产物主要为C-S-H凝胶和AFt,而纯水泥试样有大量Ca(OH)2而几乎无AFt存在.熟料含量对早期水化产物数量影响较大,而对水化产物种类及水化后期产物数量影响不大.     

石膏掺量对以矿渣为掺合料的普通硅酸盐水泥性能的影响

采用水泥胶砂及直接测温法,研究了石膏掺量对以矿渣为掺合料的P·O42.5R水泥的强度及早期水化历程的影响.结果表明:适当增大石膏掺量,可显著激发矿渣微粉早期活性,使P·O42.5R水泥水化温峰升高,1d及3d水化热增大,3d及28d抗压强度提高;但是石膏掺量不宜过大,否则,P·O42.5R水泥的早期水化速度及强度会重新降低.XRD及SEM分析表明:在合适石膏掺量的情况下,P·O42.5R水泥净浆早期的Ca(OH)2(CH)和钙矾石(enttrigite,AFt)生成量大幅度提高,凝胶体增多,孔洞减少,结构较致密.     

矿渣-水泥复合胶凝体系低温水化动力学研究

研究了低温下矿渣-水泥复合胶凝体系的水化反应特性和水化反应动力学.研究表明:低温下,复合胶凝体系的水化放热速率随着矿渣掺量的增加和环境温度的降低而下降;非蒸发水含量随着矿渣掺量的增加呈现降低的趋势;对已有水泥水化动力学方程进行计算,得到了低温条件下复合胶凝体系的动力学参数以及不同阶段反应速率和水化度间的关系,通过计算获得的动力学参数,可以对低温条件下复合胶凝体系不同反应阶段水化反应程度进行预测;在水化早期,复合胶凝体系中矿渣水化程度较低,消耗少量Ca(OH)2,使生成C-S-H凝胶的Ca/Si降低较少.在水化后期,复合胶凝体系中矿渣水化消耗较多的Ca(OH)2,使生成C-S-H凝胶的Ca/Si降低较多.矿渣掺量为50％时,硬化浆体C-S-H凝胶的Ca/Si远小于纯水泥体系.     

不同矿物掺合料对蒸养水泥水化产物与力学性能的影响

为探讨矿物掺合料对预制装配式混凝土水化产物与力学性能的影响,采用20％的镍铁渣粉、锂渣粉、钢渣粉与矿渣粉分别取代水泥,在早期80℃蒸养7h条件下制备了水泥净浆与砂浆,对比研究了镍铁渣粉、锂渣粉、钢渣粉与矿渣粉对7h和28 d龄期蒸养水泥水化产物和力学性能的影响.结果 表明:除了C-S-H与Ca(OH)2外,7h蒸养水泥的水化产物主要为AFm与Ca4Al2O6(CO3)0.5(OH)·11.5H2O,28 d蒸养水泥的水化产物主要为Ca4Al2O6(CO3)0.5(OH)·11.5H2O和Ca4Al2O6(CO3)·11H2O,矿物掺合料对蒸养水泥水化产物种类影响较小;掺镍铁渣粉、锂渣粉、钢渣粉、矿渣粉后,7h蒸养水泥的化学结合水含量分别达到了纯水泥的93.27％、102.22％、90.24％、102.22％,28 d蒸养水泥的化学结合水含量分别达到了纯水泥的93.76％、95.08％、86.27％、95.68％,掺锂渣粉与矿渣粉可以显著提高7h蒸养水泥的水化程度,掺钢渣粉的效果最差;此外,掺锂渣粉、钢渣粉、矿渣粉改变了蒸养7h水泥浆体C-S-H的形貌,除了纤维状C-S-H外,掺锂渣粉水泥浆体中还有蜂窝状C-S-H形成,掺钢渣粉水泥浆体与掺矿渣粉水泥浆体中还有球形与薄片状C-S-H形成;掺锂渣粉可以提高早期80℃蒸养7h水泥胶砂的抗压与抗折强度,但四种矿物掺合料均不能改善28 d蒸养水泥胶砂的力学性能.     

Activation of blast furnace slag by a new method

Blast furnace slag is used as supplementary cementing material for the production of blended cement and slag cement. Its latently hydraulic properties can be activated by several methods. Most applications employ the use of high pH values in the pore solution (> 13.0) to accelerate the corrosion of the glass network of the slag.It is shown in this work that activation is also possible by lowering the pH to a range between 11.8 and 12.2 by the addition of calcium hydroxide and soluble calcium salts. Among the salts investigated in this study are calcium chloride, calcium bromide, calcium nitrate, calcium formate, and calcium acetate. Other salts can be used alternatively as long as they are able to increase the calcium ion concentration and thus reduce the pH in the pore solution via the calcium hydroxide equilibrium. Complex formation of organic anions with calcium ions in the pore solution is a serious handicap when using organic calcium salts.This concept was tested on a particular slag improving its early compressive strength. It was possible to increase the strength of mortar bars produced from the pure slag from 3 MPa to 25 MPa after seven days by adding calcium hydroxide, calcium carbonate and calcium acetate. The early strength of slag cement containing 80% slag was increased from 6 to 16 MPa after two days by adding calcium chloride. The final strength was increased from 36 to 53 MPa after 28 days (water/cement-ratio = 0.40, 20 °C).Analytical data is included to demonstrate that application of the aforementioned concept is able to increase heat liberation and degree of slag consumption.     

改良钙法处理豆制品废水除磷的试验研究

针对豆制品废水磷含量高的特点,提出对传统钙法的改良。实验探讨了不同含钙离子试剂的投加量和投加比,对处理出水磷含量和pH值的影响。改良钙法(即联合Ca(OH)2和Ca CO3),通过控制两种试剂的投加比等试验找到使得豆制品废水的出水pH值在允许的排放范围内、改善沉降性能的工艺参数:在pH值为6.5且磷度为15.21 mg/L的豆制品废水情况下,投加0.5 mL浓度为5%石灰溶液投,反应10 min后,再投加2.5 mL饱和碳酸钙溶液,反应10 min。添加混絮凝剂,静置沉淀后上清液的磷去除率可达99.01%,此时出水pH值为8.43,符合排放标准。     

水侵蚀对钢渣沥青混合料动态模量影响研究

利用钢渣代替石灰岩沥青混合料粗集料,采用Superpave旋转压实制备钢渣沥青混合料.测量不同水侵蚀循环次数(0次、1次、2次、3次、4次、5次)后,不同温度和荷载作用频率下两种沥青混合料的动态模量.分析了不同水侵蚀循环次数对钢渣沥青混合料动态模量的影响,并利用XRD和SEM技术手段观察胀落物的物相组成和微观形貌变化,分析了钢渣沥青混合料性能劣化机理.实验结果表明,未受水侵蚀的钢渣沥青混合料试件,其动态模量明显高于普通沥青混合料;经过水侵蚀5次后,钢渣沥青混合料0 ℃和20 ℃的动态模量明显衰减,但残余动态模量仍大于普通沥青混合料;水侵蚀对钢渣沥青混合料的高温动态模量影响明显高于普通沥青混合料.通过XRD与SEM分析发现,钢渣沥青混合料性能劣化的主要机理是由于钢渣水化生成氢氧化钙(Ca(OH)2)、碳酸钙(CaCO3)和水化硅酸钙(C-S-H),使试件局部发生膨胀开裂,从而加剧了水的浸入,导致混合料性能衰减.     

钢渣水化产物的特性(英文)

用X射线衍射分析、水化热的测量、化学结合水量的测定、孔结构的测定、扫描电镜观察及强度测试研究了钢渣的水化产物的特性。结果表明:钢渣硬化浆体中主要含有水化硅酸钙(C–S–H)凝胶、Ca(OH)2、惰性组分[RO相、铁酸二钙(C2F)和Fe3O4]和未水化的胶凝相[硅酸三钙(C3S)和硅酸二钙(C2S)];总体而言,钢渣的水化过程与水泥的水化过程相似;钢渣早期的水化速率远低于水泥,但钢渣后期,尤其是90d之后的水化速率高于水泥的。钢渣水化产生的C–S–H凝胶不具有良好的胶凝性能,凝胶之间的相互黏结也不牢固,因此钢渣砂浆的强度很低。     

一种新型烟气净化剂─—混合有机钙盐

制备了一种新型烟气净化剂─—混合有机钙盐。在模拟工业条件的喷雾干燥型反应器中,９００～１１００℃温度范围内,混合有机钙盐的快速脱硫的钙基利用率＞ＣａＡｃ２＞Ｃａ（ＯＨ）２＞ＣａＣＯ３：混合有机钙盐的脱硝利用率约是ＣａＡｃ２的２．５倍,而ＣａＣＯ３和Ｃａ（ＯＨ）２基本看不出脱硝能力。在实验条件下温度升高,净化剂的脱硫利用率略有增加,醋酸钙和混合有机钙盐的最佳脱硝温度大约在１０００℃;较低的氧浓度既有利于脱硫也有利于脱硝;有机钙净化剂的硫酸化能提高其脱硝能力。     

Simultaneous CO2 capture and thermochemical heat storage by modified carbide slag in coupled calcium looping and CaO/Ca(OH)2 cycles

The simultaneous CO_2 capture and heat storage performances of the modified carbide slag with by-product of biodiesel were investigated in the process coupled calcium looping and CaO/Ca(OH)_2 thermochemical heat storage using air as the heat transfer fluid. The modified carbide slag with by-product of biodiesel exhibits superior CO_2 capture and heat storage capacities in the coupled calcium looping and heat storage cycles. The hydration conversion and heat storage density of the modified carbide slag after 30 heat storage cycles are 0.65 mol·mol~(-1) and 1.14 GJ·t~(-1), respectively, which are 1.6 times as high as those of calcined carbide slag. The negative effect of CO_2 in air as the heat storage fluid on the heat storage capacity of the modified carbide slag is overcome by introducing CO_2 capture cycles. In addition, the CO_2 capture reactivity of the modified carbide slag after the multiple calcium looping cycles is enhanced by the introduction of heat storage cycles. By introducing 10 heat storage cycles after the 10 th and 15 th CO_2 capture cycles, the CO_2 capture capacities of the modified carbide slag are subsequently improved by 32%and 43%, respectively. The porous and loose structure of modified carbide slag reduces the diffusion resistances of CO_2 and steam in the material in the coupled process. The formed CaCO_3 in the modified carbide slag as a result of air as the heat transfer fluid in heat storage cycles decomposes to regenerate CaO in calcium looping cycles, which improves heat storage capacity. Therefore, the modified carbide slag with by-product of biodiesel seems promising in the coupled calcium looping and CaO/Ca(OH)_2 heat storage cycles.     

电石水解制备复合钙基吸附剂及其循环吸附CO2的特性

利用电石水解制乙炔工艺制备新型电石渣CaO/Ca12Al14O33复合钙基吸附剂,考察了Ca12Al14O33含量、碳酸化和煅烧再生温度对CaO转化率和多循环吸附CO2的影响,并与分析纯CaCO3和传统电石渣进行了比较,对其表面形貌、比表面积和孔结构进行了分析. 结果表明,新型复合钙基吸附剂在多循环煅烧/碳酸化过程中具有较好的多循环吸附CO2的性能. Ca12Al14O33有效减缓了吸附剂烧结现象. 20次循环后,自制电石渣吸附剂的CaO转化率仍保持在48%以上.     

电石渣中高钙相的水力旋流法富集

用水力旋流器分离和富集电石渣中含不同元素的物相,对富集效果进行分析. 结果表明,富集后溢流主要为含Ca物相[Ca(OH)2和CaCO3],底流主要为含Si, Al, Fe和Mg物相(SiO2, Al2SiO5, Fe3O4和MgSiO3). 溢流中Ca元素由41.73%(w)提高到61.78%(w),富集度在50%以上,底流产物中Si, Al, Fe和Mg比富集前分别提高了15.33%, 6.89%, 3.20%和1.13%. 在入口水流速4000 cm/s的条件下,离心力和斯托克斯力共同提供的剪切力(66.2 kg/cm2)大于电石渣中含Ca物相和含Si, Al, Fe和Mg物相的相间粘附力(45.3 kg/cm2)是使电石渣团聚颗粒在旋流场内解聚的主要原因. 含Ca物相颗粒平均粒径小于75 mm,含Si, Al, Fe和Mg物相颗粒平均粒径约为106~180 mm,含Ca物相颗粒的径向运动速度小于含Si, Al, Fe和Mg物相颗粒的运动速度是电石渣高钙相在水力旋流场中富集的原因.     

Calcium deficiency identified as an important factor limiting maize growth in acid ultisols of eastern Nigeria

Poor maize growth in unlimed acid soils of eastern Nigeria was investigated with a view to identify the main factors responsible for infertility in such soils. Surface soils collected from 4 sites in the region were amended with (i) CaSO₄ (ii) Ca(OH)₂ and (iii) MgCO₃. Maize was grown in each soil, including an untreated check, in the greenhouse for 4 weeks and tops and roots dry matter were measured.Although CaSO₄ depressed the pH of the soil, it caused a highly significant increase (p = 0.01) in the yield of dry matter of tops and roots and a non-significant increase in the uptake of P and Ca. Exchangeable Al was virtually eliminated when the soil was amended with MgCO₃ but maize growth in this soil was drastically inhibited and symptoms of severe calcium deficiency were observed. Higher yield increases, arising from soil amendment with Ca(OH)₂ relative to CaSO₄ were ascribed to better Ca nutrition rather than reduction in the level of exchangeable Al. Uptake of P and Ca was significantly increased (p = 0.05) by liming with Ca(OH)₂.The results suggest that Ca deficiency is a more serious growth-limiting factor than Al toxicity in the soils tested. The implication of this finding is that much money can be saved by using industrial wastes of relatively low neutralizing value, like cement fluke dust and basic slag, as soil amendments rather than the costly ocnventional liming materials.     

Preparation and characterization of epoxy/slag composite for cement slurry applications

In this study, epoxy/slag composites (ESCs) were prepared by using diglycidyl ether of bisphenol‐A epoxy resin, water‐quenched granulated blast furnace slag as filler, phenolic aldehyde amine as hardener, and titanate as coupling agent. The properties of ESC, including chemical structure, thermal stability, wetting properties, and morphological structure, were investigated by using Fourier transform infrared spectroscopy, thermogravimetric analysis, a contact angle meter, scanning electron microscopy, and energy dispersive spectrometry. The results show that ESCs possess excellent thermal stability, hydrophilicity, and good compatibility with cement slurry compared to pure epoxy. In addition, the applications of ESC in a cement slurry were also investigated. It was found that the fluidity, free water, fluid loss, and content of Ca(OH)₂ decreased, while the compressive strength increased with the incorporation of slag into the epoxy matrix. These features were attributed to the pozzolanic reaction of slag by consumption of Ca(OH)₂ to form calcium silicate hydrate (C‐S‐H) gel which contributed more to the compressive strength of set cement. Finally, lightweight cement containing ESCs exhibited high strength without affecting the density of the light cement slurry under curing pressure and at high mixing rate compared with lightweight cement made of floating beads. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43359.