含钡硫铝酸盐水泥的水化动力学与热力学研究

采用XRD和等温微量热法测试计算含钡硫铝酸盐水泥的水化动力学和热力学过程。结果表明,含钡硫铝酸盐水泥的水化过程主要受扩散过程控制,水化速率变化模式与铝酸钙、硅酸盐水泥类似。水化过程分为加速期、减速期和衰减期:在加速期,水化反应受成核反应控制,属自催化反应;从减速期开始,水化物在颗粒表面形成水化物薄膜,水化反应阻力加大,速率减缓;进入衰减期,水化反应完全受扩散过程控制。     

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。     

普通硅酸盐-硫铝酸盐复合胶凝体系水化性能和机理研究

对普通硅酸盐(P·O)-硫铝酸盐(R·SAC)复合胶凝体系的凝结时间、胶砂强度进行了分析,利用等温量热仪、综合热分析仪(TG-DSC)、扫描电镜(SEM)、X射线衍射仪(XRD)等从水化速率及水化产物微观形貌等方面分析了复合胶凝体系的水化机理。结果表明:当R·SAC掺量约为10%时,复合胶凝体系的凝结时间相比P·O明显缩短,早期强度提高幅度较大,同时也能获得较大幅度的后期强度增长,力学性能较纯组分水泥性能优越。复合胶凝体系的早期水化速率和放热量高于单组分水泥。随着R·SAC的掺入,复合胶凝体系的水化产物中钙矾石(AFt)增多,Ca(OH)₂晶体减少,且AFt的生成量越多,越有利于早期强度的发展,当R·SAC掺量超过30%时,Ca(OH)₂消失。     

复合调凝组分对硫铝酸盐水泥性能的影响及机理

为了有效控制硫铝酸盐水泥(SAC)的凝结时间,研究了硼砂、葡萄糖酸钠、柠檬酸钠单掺和复掺对硫铝酸盐水泥凝结时间和流动性能的影响。结果表明:葡萄糖酸钠与柠檬酸钠以一定质量比复合后可以有效控制水泥浆体的凝结时间,并很好地改善其工作性能和早期强度,而且葡萄糖酸钠与柠檬酸钠复合质量比为5∶1时对硫铝酸盐水泥的缓凝效果最好。水化早期浆体的XRD和SEM分析结果表明,复合调凝组分的加入减缓了钙矾石的生成,并且使得水化产物中CSH凝结的生成数量增多,从而有效抑制了硫铝酸盐水泥的水化速度,并改善了其工作性能。     

低能耗硫铝酸盐水泥的合成及其特性

利用分析纯试剂材料、工业原料及其工业废渣，例如：磷石膏、粉煤灰、高炉矿渣和矾土作为生料组生，合成出含有Ｃ４Ａ３Ｓ、β－Ｃ２Ｓ及ＣＳ的早强快硬低能耗水泥。所研制的物既可单独制备，也可以用Ｃ４Ａ３Ｓ－βＣ２Ｓ－ＣＳ按重量比为１．５：１：！来合成，后者指的是二元和三元体系。研究发现，工业原料中杂质能够降低烧成温度。同时，硫铝酸盐水泥中加入粉煤灰或高炉矿渣渣虽会降低１ｄ强度，却显著地增加了２８ｄ抗压强度。     

砒砂岩对硅酸盐和硫铝酸盐水泥性能的影响

为了研究砒砂岩对硅酸盐水泥和硫铝酸盐水泥物理性能的影响,采用单因素多水平梯度实验,通过不同砒砂岩掺量的对比,测定硅酸盐水泥和硫铝酸盐水泥的凝结时间、标准稠度用水量和胶砂强度等性能。结果表明:砒砂岩对硅酸盐水泥和硫铝酸盐水泥皆有促凝作用,当砒砂岩掺量质量分数为5%时硅酸盐水泥的初凝时间会缩短30%,硫铝酸盐水泥初凝时间缩短47%,硅酸盐水泥和硫铝酸盐水泥的标准稠度用水量分别增加6.6%和21.7%;砒砂岩掺量质量分数为10%时,硅酸盐水泥的3 d和28 d的强度分别增加7.2%和6%,对其力学性能有较大影响;掺入砒砂岩后,硫铝酸盐水泥强度降低,且随掺量增加,抗压强度降幅增大。     

碳纤维硫铝酸盐水泥基机敏复合材料

采用压制成型方法制备了碳纤维硫铝酸盐水泥基复合材料 ( Carbon Fiber Reinforced Sulphoaluminate Cement,简称CFRS ) 。用XRD和孔结构分析仪对复合材料的物相和孔径与孔体积的关系进行了分析,研究了不同碳纤维掺量对复合材料在单调压应力和循环压应力下的机敏性能的影响。XRD和孔结构分析研究结果表明,压制成形的试样水化14天硫铝酸盐水泥水化仍不完全,试样结构致密,孔隙率较小,孔径基本小于0.9μm;单调压应力下机敏测试性能表明,碳纤维掺量为0.3％和0.5％的CFRS试样电容变化率与压应力近似成线性关系,机敏性能较好;循环压应力下碳纤维掺量为0.7％的CFRS试样电容变化率与循环压应力成一一对应关系,表现出较好的机敏特性。      

硫铝酸盐水泥和丁苯乳液对水泥基修补材料性能的影响

将硫铝酸盐水泥与硅酸盐水泥复合,并引入丁苯乳液作为聚合物改性剂制备高性能修补材料,研究硫铝酸盐水泥和丁苯乳液对修补材料的强度、凝结时间和黏度的影响和作用机制。结果表明:硫铝酸盐水泥明显提高复合水泥的早期强度,缩短初凝和终凝时间,增大黏度;适量丁苯乳液能在复合水泥浆体中形成网状结构,提高力学强度;丁苯乳液中的羧基能够减小熟料矿物铝酸钙、硅酸三钙和硅酸二钙的水化速率,复合水泥净浆的初凝和终凝时间均明显延长,黏度减小。     

工业废渣在硫铝酸盐水泥生产中的应用现状

硫铝酸盐水泥具有高早强、低碱度、耐侵蚀等特性,与传统硅酸盐水泥相比具有显著的低碳优势。本文对目前利用含铝、含硫废渣代替天然材料制备硫铝酸盐水泥熟料的矿物形成、水泥性能等作了归纳总结。结果表明,利用这些工业废渣制备硫铝酸盐水泥具有一定可行性,不仅可以降低水泥生产成本,而且有利于水泥的低碳生产。同时也指出,在水泥中引入硫硅酸钙矿物,可以促进废渣利用和水泥性能提高,对于新型低碳水泥的开发具有重要的现实意义。     

不同水灰比下无水硫铝酸钙的水化反应

为澄清无水硫铝酸钙的水化反应机理,利用化学试剂Ca CO3、Al2O3、Ca SO4合成纯度达90%以上的无水硫铝酸钙(C4A3)单矿物,研究其在水灰比为0.3、05、0.7条件下的水化反应,包括不同水化时间的水化产物及变化规律,用X射线衍射仪、综合热分析仪和扫描电子显微镜对水化产物进行分析.结果表明:水化产物为含不同摩尔结晶水的2种单硫型水化硫铝酸钙C4AH12(AFm-12)和C4AH1 4(AFm-14)以及无定形状态的铝凝胶(AH3),整个水化过程未生成钙矾石(AFt);随着水化时间的延长,C4AH12(AFm-12)会逐渐转化为C4AH1 4(AFm-14);水化反应主要集中发生在3~12 h,后期C4AH1 4晶体不断长大.     

Influence of LiAl-layered double hydroxides with 3D micro-nano structures on the properties of calcium sulphoaluminate cement clinker

The effect of LiAl-layered double hydroxides (LiAl-LDHs) with 3D micro-nano structures on the early properties and hydration process of calcium sulphoaluminate cement (CSAC) clinker was investigated. Three LiAl layered double hydroxides (LiAl-LDHs) with different particle size were prepared through a facile solvothermal method. CSAC clinker incorporating LiAl-LDHs with constant water to cement radio were made and tested. The results indicate that a higher content of LiAl-LDHs resulted in a faster hydration rate, a shorter setting time and a higher early compressive strength. Besides, with the decrease of the particle size of LiAl-LDHs, the hydration rate was accelerated with corresponding increase in compressive strength. However, the influence of particle size of LiAl-LDHs on the setting time of CSAC clinker is not significant. Moreover, the addition of LiAl-LDHs did not result in a new phase formed, but increased the quantity of hydration products providing higher compressive strength and shorter setting time.     

掺梳形减水剂水泥浆体早期水化产物形貌研究

为揭示梳形减水剂对水泥早期水化的影响规律,指导工程应用,通过SEM分析,研究了掺用3种典型结构的梳形减水剂的水泥浆体早期水化产物形貌及其电子特征数据。结果表明,梳形减水剂加速了水泥早期水化反应,且丙烯酸类、马来酸类共聚物分别促进了AFt、AFm的形成。因此,梳形减水剂品种对水泥早期水化和混凝土工程性能具有较大影响,应根据使用要求合理选用,必要时与缓凝剂、引气剂或消泡剂复合使用。     

Preparation of calcium sulphoaluminate cement using fertiliser plant wastes

Phosphochalks from fertiliser plants contain significant amount of calcium sulphate along with P(2)O(5) and fluorine. The presence of these impurities makes them unsuitable for most applications and, hence its availability in millions of tons. We demonstrate that it is possible to prepare calcium sulphoaluminate-aluminoferrite based special cements having strength values comparable to ordinary Portland cement (OPC) using these waste chalks. Such cements are insensitive to the presence of impurities in the raw mixture, clinker at low temperatures (1,230 degrees C) and the clinkers produced are soft and friable. An empirical technique has been developed to predict the phase composition of the clinkers given the chemical composition of the starting raw mixture. The proposed low temperature clinkering route appears to be a promising method for converting waste phosphochalks into construction grade cements.     

碳酸化钢渣和矿渣作硅酸盐水泥混合材水化性能研究

通过对钢渣碳酸化前后的硅酸盐相提取及水化放热性能和将碳酸化钢渣和矿渣作为混合材的硅酸盐水泥的胶砂强度和水化产物种类的测定,以及对它们微观形貌的观察,研究了碳酸化钢渣对胶凝体系水化性能的影响.结果表明,碳酸化使钢渣中硅酸盐相的含量由47.06％下降至14.38％;碳酸化促进了钢渣的早期水化,抑制其后期水化;在配比相同的条件下,碳酸化钢渣-矿渣-硅酸盐熟料体系试样的3、28d抗压强度较未碳酸化钢渣-矿渣-硅酸盐熟料体系试样的高;碳酸化生成的CaCO3促进了熟料的水化;碳酸化钢渣促进了胶凝体系中AFt的生成,且生成水合碳铝酸钙.     

Influence of the water to cement ratio W/C on the compressive strength of concrete — An application of the cement hydration equation to concrete

The cement hydration equation was used to determine the influence of the water to cement ratio, W/C, on the compressive strength of concrete up to the end of the hydration age. Using the hydration equation, the equations of the compressive strength of concrete were derived for five values of the ratio W/C equal to 0.50, 0.55, 0.60, 0.65, and 0.70. The curves of variation of the compressive strength versus the W/C ratio for the hydration age of 7, 28, 90 and 5475 days were drawn. Based on these curves a thorough study of the influence of the W/C ratio on the compressive strength of concrete was undertaken.     

超长侧链型聚羧酸梳形共聚物对水泥早期水化的影响

选用了一组超长侧链型聚羧酸梳形共聚物作为水泥体系的分散剂,通过水化热测定、强度试验和扫描电镜等表征手段,研究了超长侧链型聚羧酸梳形共聚物分散剂对水泥早期水化的影响.研究发现,超长侧链型聚羧酸梳形共聚物比普通聚羧酸梳形共聚物具有加速水泥水化、提高水泥基材料强度的作用.扫描电镜得到的形貌结果发现,超长侧链型聚羧酸梳形共聚物的掺入改变了水化产物的形貌,并且侧链越长,呈絮状的C-S-H凝胶和呈针状的钙矾石晶体明显增加.这说明超长侧链型聚羧酸加速了C-S-H凝胶和钙矾石晶体的形成,促进了水泥混凝土体系早期强度的形成.     

石灰石粉对硅酸盐水泥水化的影响

石灰石粉被广泛应用到水泥混凝土中,其在水泥体系中是否能产生活性效果仍存在争议。本文通过掺入30%石灰石粉与不掺石灰石粉组进行对比试验,采用扫描电镜(SEM)、能谱分析(EDS)以及X射线衍射分析(XRD)进行微观分析,结果表明:石灰石粉能够加速水泥中C3S的水化,以及能够与C3A反应生成水化碳铝酸钙,并且会阻止钙矾石向单硫型水化硫铝酸钙的转变。     

Influence of curing temperatures on the hydration of calcium aluminate cement/Portland cement/calcium sulfate blends

In this paper, the effects of curing temperature on the hydration of calcium aluminate cement (CAC) dominated ternary binders (studied CAC: Portland cement: calcium sulfate mass ratio were 22.5: 51.7: 25.8) were estimated at 0, 10, 20 and 40 °C, respectively. Both α-hemihydrate and natural anhydrite were employed as the main source of sulfate. The impacts of temperature on the phase assemblages, morphology and pore structure of pastes hydrated up to 3 days were determined by using X-ray diffraction (XRD), backscattered electron imaging (BEI) and mercury intrusion porosimetry (MIP). Results reveal that the main hydration products are firmly related to calcium sulphoaluminate based phases. Increasing temperature would result in a faster conversion from ettringite to plate-like monosulfate for both calcium sulfate doped systems. When the temperature increases to 40 °C, an extraordinary formation of strätlingite (C₂ASH₈) and aluminium hydroxide is observed in anhydrite doped pastes. Additionally, increased temperature exerts different effects on the pore structure, i.e. the critical pore diameter shifts to finer one for pastes prepared with α-hemihydrate, but changes to coarser one for those made with anhydrite. From the mechanical point of view, increased temperature accelerates the 1-day strength development prominently, while exerts marginal influence on the development of 3-day strength.     

一种新型三元体系磷酸钙骨水泥的制备与性能优化

制备了一种新型磷酸氢钙-部分结晶磷酸钙-磷酸四钙三元体系骨水泥,采用正交试验优化骨水泥组分以提高材料的性能。通过力学性能测试、X射线衍射分析、扫描电镜观察以及反应过程水化放热测定,对比研究了所制备的三元体系骨水泥材料的水化过程和物相组成。结果表明所添加活性磷酸四钙参与水化反应较慢,延长了骨水泥的凝结时间,拓展了后期水化效应,使得反应后期水化进程得以延续,硬化体更加密实,孔隙率降低,抗压强度增加50%;同时反应放热峰值显著降低40%,水化过程总放热量基本不变,有利于骨水泥在临床应用。