硫铝酸盐水泥基复合体系的胶凝膨胀性能

研究了硫铝酸盐水泥熟料、二水石膏和氢氧化钙的不同复合胶凝体系水化产物与其膨胀性能及抗压强度的关系，利用XRD及Rietveld全谱拟合法和TG/DTG技术，对水化产物进行定性定量分析，得出硫铝酸盐水泥熟料-二水石膏体系（简称CG体系）和硫铝酸盐水泥熟料-二水石膏-氢氧化钙体系（简称CGL体系）水化产物中钙矾石（AFt）、单硫型水化硫铝酸钙（AFm）、铝凝胶（AH3）等物相含量的变化规律，并进行比较。结果表明，CGL体系水化产物中AH3和AFm生成量多于CG体系，而AFt生成量在二水石膏与硫铝酸钙摩尔比为0.5和1.0时少于CG体系，达到1.5摩尔比时两个体系相差不大；CGL体系中，掺加氢氧化钙会降低试件早期抗压强度，后期其抗压强度赶上甚至超过未掺加氢氧化钙的试件；随着二水石膏掺量增加，CG体系中AFt早期生成速率和试件膨胀率均呈增大趋势，而CGL体系中AFt早期生成速率和试件膨胀率均呈减小趋势。     

Na2SO4对煅烧煤矸石的激发效应

利用TG-DSC、XRD、等温量热计、SEM、Ca(OH)2含量测定等方法,比较研究了掺与不掺Na2SO4时煅烧煤矸石水泥早期水化过程中的Ca(OH)2含量、水化放热速率、水化产物及其形貌、浆体力学强度的差别,分析了Na2SO4对水泥早期水化过程中煅烧煤矸石的激发作用.结果表明,掺入Na2SO4后,水泥试样在水化减速期早期阶段的水化放热速率高,二次水化产物形成的时间早.这反映出Na2SO4对水泥中煅烧煤矸石有明显的激发效应.其外,水泥浆体试样中Ca(OH)2含量明显降低,水泥水化加速期延续的时间短,水化放热速率高;结果还表明,在水化早期,掺Na2SO4的煅烧煤矸石水泥有较多的CSH凝胶和AFt,较少的Ca(OH)2.     

添加不同温度煅烧煤矸石水泥的早期水化及浆体的显微结构

用X射线衍射仪,热重-差热仪,扫锚电镜。压汞法测定孔隙率和Ca(OH)2生成量分析等。研究分别掺加500～1100℃7个温度点煅烧煤矸石水泥的早期水化过程及其浆体的显微结构。结果表明：在7种试样中,掺700℃煅烧煤矸石水泥的早期水化最快。力学强度高,凝胶孔多,总孔隙率低,其早期水化产物为C-S-H凝胶、Ca(OH)2和钙矾石,在1～28d的水化试样中均存在钙矾石。研究表明：煅烧煤矸石能促进水泥熟料的水化。该促进作用随煤矸石的煅烧温度而异,以700℃煅烧煤矸石的促进作用为最好。     

石膏对贝利特-硫铝酸钡钙水泥强度和硬化浆体结构的影响

研究了石膏对贝利特-硫铝酸钡钙水泥强度和硬化浆体结构的影响.结果表明:贝利特-硫铝酸钡钙水泥熟料的矿物组成主要有C3S、C2S、C,A、C4AF和C2.7B1.25A3S;当水泥中石膏掺量为10%时,贝利特-硫铝酸钡钙水泥的3d、7 d、28 d和90 d抗压强度分别达到了45.0、61.9、82.1和85.6 MPa;贝利特.硫铝酸钡钙水泥的水化产物主要有AFt、Ca(OH)2、C-S-H凝胶等,随石膏掺量的增加,AFt的数量逐渐增加,水化后期的Ca(OH)2数量逐渐减少.用XRD和SEM来分析硬化水泥浆体组成和结构.     

垃圾焚烧飞灰煅烧阿利尼特水泥熟料的形成过程及其水化性能研究

以城市垃圾焚烧飞灰(以下简称焚烧飞灰)为主要原料,在实验室电炉里成功研制了阿利尼特水泥熟料。本文主要研究水泥熟料煅烧形成过程及其水化性能,分析了阿利尼特水泥的适宜石膏掺量、水化放热特征、水化产物及其显微结构。研究结果表明:利用垃圾焚烧飞灰为主要原料可以成功烧制阿利尼特水泥熟料,煅烧过程中首先出现C2S、C12A7和C2S·CaCl2,随后与MgO和CaCl2反应生成阿利尼特;掺加5%二水石膏可以促进阿利尼特水泥水化,较普通硅酸盐水泥更快,阿利尼特水泥可以作为一种早强快硬型水泥使用;阿利尼特水泥主要水化产物除含有硅酸盐水泥中常见的CSH凝胶、棒状AFt和Ca(OH)2晶体外,还含有C3A·CaCl·210H2O晶体。     

卤水侵蚀对水泥粉煤灰浆体微结构影响

采用XRD、29Si和27Al MAS NMR测试技术,研究了粉煤灰掺量和侵蚀龄期对卤水侵蚀下水泥-粉煤灰浆体水化产物相组成、含铝相产物迁移与转变、C-S-H凝胶微结构变化的影响规律.研究结果表明:卤水侵蚀导致浆体Ca (OH)2含量降低,AFm和TAH向AFt转变,同时生成大量Friedel盐,C-S-H凝胶中Al[4]脱出;随粉煤灰掺量增加,浆体中AFt、AFm和TAH生成量降低,C-S-H的MCL和Al[4]/Si增大,Friedel盐生成量先增后减;侵蚀早期,水泥-粉煤灰浆体结构疏松,AFt生成量较纯水泥高,后期浆体致密性提高,抑制卤水侵蚀,AFt生成量较少,C-A-S-H脱铝作用减弱.     

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.     

铝酸盐水泥-半水石膏二元体系饰面砂浆泛白原因分析

采用碱浸出率法测试了铝酸盐水泥及两种铝酸盐水泥-半水石膏二元体系饰面砂浆浸水后水中物相的质量,并用XRD分析了水化产物及浸水后水中物相成分,得出(1)引起铝酸盐水泥饰面砂浆泛白的主要物相为CaCO3和Al(OH)3,而CaCO3和Al(OH)3是由铝酸盐水泥的水化产物水化铝酸钙碳化分解而生成;(2)铝酸盐水泥-半水石膏二元体系在石膏量为5％时水化产物主要为CAH10和AFm,在石膏量为25％时水化产物主要为AFt,铝酸盐水泥-半水石膏二元体系出现泛白的原因是AFm的碳化,推测主要水化产物为AFt时砂浆未出现泛白的原因是生成AFt的同时有足够的AH3生成并包裹AFt,保护其不被碳化.     

不同石灰石粉掺量对硅酸盐水泥水化的影响

采用外掺的方式,在石灰石粉占水泥质量比例的0％、3％、6％、9％、12％时,对比研究了石灰石粉对硅酸盐水泥水化的影响规律.通过分析XRD、拉曼光谱、XRD定量分析的试验结果,得出在7d时,随着石灰石粉掺量的增加,AFm相逐渐减少,石粉掺量大于9％时,AFm相已不再生成,在28 d时,掺有石粉的水泥水化产物中,AFm相均消失.在28 d时,在掺有石粉的水泥水化产物中,随着石粉掺量的增加,水化产物中Ca(OH)2的生成量逐渐增加,但石粉掺量不大于6％时,Ca(OH)2生成量低于空白样的.在180 d时,随着石粉掺量增加,水化产物中Ca(OH)2的生成量,则是随着石粉掺量的增加而增加,且其生成量均大于空白样的.     

复合使用高效减水剂与缓凝剂对水泥水化历程的影响

用直接测温法及X射线衍射技术,系统研究了萘系、氨基磺酸盐系及聚羧酸盐系3种高效减水剂,三聚磷酸钠及糖钙2种缓凝剂及复合使用高效减水剂与缓凝剂对水泥水化热、水化温峰、温峰出现时间及不同水化龄期Ca(OH)2和钙矾石(ettringaite,AFt)生成量等方面的影响.结果表明:单掺高效减水剂使水化温峰升高,温峰出现时间延迟,水化热及温峰时的Ca(OH)2生成量增加.单掺缓凝剂使水化温峰降低,温峰出现时间大幅度延迟,水化热及温峰时的Ca(OH)2生成量明显减少.复合使用高效减水剂与缓凝剂时,由于协同效应,使高效减水剂的分散作用及缓凝剂的缓凝作用同时得到加强.与单掺缓凝剂相比,复掺后水泥水化温峰出现的时间进一步延迟,水化温峰进一步降低,水化热及水化温峰时Ca(OH)2生成量进一步减少;但是,外加剂对AFt生成量影响不大.     

热活化煤矸石—水泥复合体系水化性能分析

采用比强度法对活化煤矸石的火山灰效应进行评定,通过Ca(OH)2剩余量和化学结合水量的测定,分析活化煤矸石-水泥体系的水化程度,并采用X射线衍射分析,差热分析对其水化过程进行研究。结果表明:煅烧温度为750℃,保温时间为4h的热活化煤矸石对水泥体系的火山灰贡献率较高;该体系Ca(OH)2剩余量较少,化学结合水量较多,其水化产物主要以C-S-H凝胶,Ca(OH)2和钙矾石为主。     

Influence of the availability of calcium on the hydration of tricalcium aluminate (C3A) in seawater-mixed C3A–gypsum system

This work examined the effects of seawater (SW) on the hydration of tricalcium aluminate (C₃A) in C₃A–gypsum and C₃A–gypsum–Ca(OH)₂ systems through the characterization of hydration heat release, the evolution of aqueous phase composition and hydration products with the hydration time. It was found that SW increased the dissolution driving force of C₃A and solubility of gypsum, which accelerated the early hydration of C₃A and the formation of ettringite (AFt), leading to a higher hydration degree of C₃A at an early age compared with the deionized (DI) water–mixed pastes. After gypsum depletion to form AFt, and in the absence of Ca(OH)₂, the formation of chloroaluminate hydrates was slower due to the insufficient Ca resulted in an accumulation of Al in solution. This would delay the subsequent transformation of AFt to monosulfate (SO₄–AFm) and the formation of hydrogarnet (C₃AH₆), which would further reduce the hydration degree of the C₃A at the later ages. However, in the presence of Ca(OH)₂, the hydration degree of C₃A–gypsum–Ca(OH)₂ at later ages was increased, which was similar to that of the corresponding DI pastes. This can be inferred that the amount of Ca available in SW-mixed cement concrete can affect the hydration degree of C₃A in cement.     

玻璃粉水泥浆的初期水化产物和浆体结构

采用SEM、XRD研究了玻璃粉水泥浆的初期水化产物、浆体结构.并用化学结合水量和有效结合水法来定性和定量分析玻璃粉对水化初期复合体系及水泥的促进或抑制作用以及作用程度.研究表明:在水化反应初期(1d内),因为玻璃粉的掺入既由此而产生的稀释作用使有效水灰比增加而产生的对水泥熟料水化的促进作用,因此,硅酸盐水泥熟料的水化程度较高,但从整体来看,大掺量(50%)的玻璃粉延缓了复合胶凝材料总水化程度;水化开始(6 h~1 d)时,水化反应开始加速进行,水化产物的数量迅速增加,主要为纤维状CSH凝胶、针棒状钙矾石晶体和Ca(OH)2,这些水化产物彼此间相互搭接、交错生长,部分未水化的水泥颗粒镶嵌其中,并将玻璃粉粘结成整体,构成体系骨架.     

Solubility behavior of Ca-, S-, Al-, and Si-bearing solid phases in Portland cement pore solutions as a function of hydration time

The concentrations of Ca, S, Al, Si, Na, and K in the pore solutions of ordinary Portland cement (OPC) and white Portland cement (WPC) pastes were measured during the first 28 days of hydration at room temperature. Saturation indices (SI) with respect to various solid phases known to occur in cement pastes were calculated from a thermodynamic analysis of the elemental concentrations, resulting in good agreement between the two pastes. In agreement with other published work, gypsum was saturated during the first several hours of hydration and then undersaturated thereafter, while portlandite was modestly supersaturated after the first few hours. High levels of supersaturation with respect to ettringite and calcium monosulfoaluminate were calculated, particularly prior to the consumption of gypsum at around 10 h. Results are consistent with published thermodynamic studies that show calcium monosulfoaluminate is metastable with respect to ettringite under normal hydration conditions. Three different ion activity product (IAP) equations for C-S-H were applied to the data. From 10 h onward, each of the IAP values declined gradually over time and the values for the OPC and WPC pastes were in close agreement. The same IAP equations were applied to experimental data from the pure CaO-SiO₂-H₂O system, resulting in good agreement between the cement paste pore solutions and the equilibrium between portlandite and the upper, or metastable, C-S-H solubility curve.     

煅烧磷石膏对蒸压硅酸盐制品水化过程的影响

磷石膏经高温煅烧改性后与粉煤灰、砂粉、石灰及水泥熟料等制备蒸压硅酸盐制品,研究了不同温度煅烧的磷石膏对蒸压硅酸盐制品水化过程的影响,用蒸压制品中未反应的Ca(OH)₂量及结合水量分析它们的反应速率,用XRD测定蒸压硅酸盐制品的水化产物,并结合SEM分析,结果表明,经煅烧的磷石膏对蒸压硅酸盐制品的水化有明显的促进作用,托勃莫来石与C-S-H(1)等水化产物的迅速生长而形成密实的水化产物结构是其增强蒸压硅酸盐制品的根本原因。     

Hydration Kinetics and Phase Stability of Dicalcium Silicate Synthesized by the Pechini Process

Reactive dicalcium silicate (Ca₂SiO₄) has been synthesized by the Pechini process, and hydration kinetics studied. With increasing calcination temperature, the amorphous product first crystallizes to α'_L-phase and subsequently to the ß- and γ-phases. The specific surface area, ranging from 40 to 1 m²/g, strongly depends on the calcination temperature of 700°-1200°C for 1 h. Samples with a high surface area have a high water demand; a water/cement ratio >2.0 is required to produce formable pastes in some instances. Hydration kinetics are determined by XRD, ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR), and differential scanning calorimetry/thermogravimetry (DSG/TG). The hydration rate depends only on the surface area, not on the polymorph. Complete hydration occurs in as early as 7 d. Very little calcium hydroxide (Ca(OH)₂) is formed in the most reactive specimens (calcined at 700° and 800°C), which indicates the Ca/Si ratio in C-S-H gels is ∼2.0, but more Ca(OH)₂ forms from samples calcined at higher temperature. The silicate structure of the hydrated Ca₂SiO₄ pastes is investigated using ²⁹Si MAS NMR spectroscopy and trimethylsilylation analysis.     

减缩剂对水泥基材料水化和孔结构的影响(英文)

通过对水泥净浆水化放热量、Ca(OH)2的含量和化学结合水量及水泥砂浆的孔结构的测定,研究减缩剂对水泥基材料水化和孔结构的影响.结果表明:减缩剂会延缓水泥的水化,且随着龄期的发展,延缓作用渐弱.具体表现为减缩剂会降低水泥水化放热的峰值,延迟峰值出现的时间,减小水化放热量;减缩剂能够减小水泥净浆的化学结合水量;龄期为3d时,掺减缩剂的净浆中Ca(OH)2的含量明显低于空白样的,28d时与空白样的相当;减缩剂能够减小水泥砂浆中多害孔和有害孔的孔体积,增加无害孔的孔体积.另外还对减缩剂在水泥基材料中存在的形态提出设想.     

Influence of polymer on cement hydration in SBR-modified cement pastes

The influence of styrene-butadiene rubber (SBR) latex on cement hydrates Ca(OH)₂, ettringite, C₄AH₁₃ and C-S-H gel and the degree of cement hydration is studied by means of several measure methods. The results of DSC and XRD show that the Ca(OH)₂ content in wet-cured SBR-modified cement pastes increases with polymer-cement ratio (P/C) and reaches a maximum when P/C is 5%, 10% and 10% for the pastes hydrated for 3 d, 7 d and 28 d, respectively. With wet cure, appropriate addition of SBR promotes the hydration of cement, while the effect of SBR on the content of Ca(OH)₂ and the degree of cement hydration is not remarkable in mixed-cured SBR-modified cement pastes. XRD results illustrate that SBR accelerates the reaction of calcium aluminate with gypsum, and thus enhances the formation and stability of the ettringite and inhibits the formation of C₄AH₁₃. The structure of aluminum-oxide and silicon-oxide polyhedron is characterized by ²⁷Al and ²⁹Si solid state NMR spectrum method, which shows that tetrahedron and octahedron are the main forms of aluminum-oxide polyhedrons in SBR-modified cement pastes. There are only [SiO₄]⁴⁻ tetrahedron monomer and dimer in the modified pastes hydrated for 3 d, but there appears three-tetrahedron polymer in the modified pastes hydrated for 28 d. The effect of low SBR dosage on the structure of aluminum-oxide and silicon-oxide polyhedron is slight. However, the combination of Al³⁺ with [SiO₄]⁴⁻ is restrained when P/C is above 15%, and the structure of Al³⁺ is changed obviously. Meantime, the polymerization of the [SiO₄]⁴⁻ tetrahedron in C-S-H gel is controlled.     

Hydration of fly ash-portland cements

Hydration products of fly ash-portland cements were studied with x-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM) as part of a continuing research effort to understand the pozzolanic activity of fly ashes. It was found that the amount of calcium hydroxide crystals in the cement pastes is diminished due to the addition of fly ash to the cement. Ettringite was produced in the early age, and the consumption of sulfate by the formation of ettringite was accelerated by the addition of fly ash. A partial conversion of ettringite to monosulfate within the first 7 days of hydration in the fly ash-portland cement pastes, but the formation of ettringite continued to form up to at least 28 days of hydration in the pastes without fly ash. Examination of the fly ash bearing pastes showed, in all cases, varying amounts of calcium hydroxide and unreacted portland cement, with minor quartz and gehlenite hydrate. It appears that hydration reactions actually occur in the fly ash cement pastes more or less on a particle-by-particle basis.     

MgO膨胀剂对水泥浆体收缩的影响

研究了掺轻烧MgO膨胀剂的水泥浆体在不同养护条件下的变形性能,并采用X射线衍射仪、同步热分析以及背散射扫描电镜分析了掺MgO膨胀剂的水泥浆体中MgO的水化性能.结果表明:水泥浆体在不同的养护条件下养护,其相对湿度越大,收缩越小.在相同养护湿度条件下,水中预养护时间越长,其收缩越小.掺入MgO膨胀剂可以有效地降低低湿度条件下水泥浆体的收缩,其主要原因是轻烧MgO膨胀剂在缺水养护的低湿度条件下也能进行水化反应生成Mg(OH)2,从而降低了水泥浆体的收缩.