BaSO4对C2S结构及性能的影响

通过XRD，EDM/EDAM及化学分析等手段测定了Ba^2 和S^6 2种离子对C2S结构的影响，得出Ba^2 、S^6 在C2S中的固溶形式和极限固溶量，以及固溶引起的结构变化，并对固溶2种离子的C2S水化活性进行了研究，结果表明：固溶Ba^2 ，S^6 离子的C2S水化活性大大提高。     

BaSO_4对C_2S结构及性能的影响

通过XRD ,EDM /EDAM及化学分析等手段测定了Ba2 + 和S6 + 2种离子对C2 S结构的影响 ,得出Ba2 + 、S6 + 在C2 S中的固溶形式和极限固溶量 ,以及固溶引起的结构变化 .并对固溶 2种离子的C2 S水化活性进行了研究 .结果表明 :固溶Ba2 + ,S6 + 离子的C2 S水化活性大大提高 .     

Cr3+离子在硅酸三钙中的固溶行为

通过制备纯C3S和掺杂Cr2O3的C3S样品,采用ICP、XRD、IR、SEM等测试方法研究了掺杂Cr3+离子对C3S晶体结构及性能的影响,Cr3+离子在C3S矿物中的最大固溶量.结果表明:原料中掺杂2％ Cr3+离子,使得C3S的晶型发生改变;掺量超过4％时,将造成C3S矿物分解.Cr3+离子的掺杂将提高C3S晶体结构对称性,加速早期水化速率.     

碱金属掺杂对硫硅酸钙水化性能的影响机理

碱金属离子作为水泥原料中常见的杂质离子，其存在会影响熟料矿物结构与性能。采用分析纯试剂合成碱金属掺杂的硫硅酸钙单矿物，借助等温量热仪、综合热分析、扫描电镜和²⁹Si核磁共振等手段，研究了碱金属离子对硫硅酸钙水化活性及力学性能的影响。结果表明：碱金属离子在硫硅酸钙晶体结构中的固溶，能够降低晶体结晶度，形成晶体缺陷，有效提升硫硅酸钙早期水化活性，促进其早期力学性能快速发展。同时，碱金属的掺杂能够改变水化硅酸钙(C–S–H)凝胶等产物的微观形貌及结构。其中，Li₂O掺杂能够稳定絮状形态的C–S–H凝胶，而Na₂O和K₂O掺杂能够诱导C–S–H凝胶纤维状生长。经碱金属掺杂影响，C–S–H凝胶聚合度有所增加，平均硅链长增长。     

公路粉煤灰水泥水化产物及机理的研究

本文采用了X-ray衍射、扫描电镜、孔结构分析等多种测试方法对公路粉煤灰水泥的水化产物及水化机理进行了研究。实验结果表明,公路粉煤灰水泥的主要水化产物为C－S－H凝胶、钙矾石及少量的Ca(OH)2。C－S－H凝胶的Ca／Si比较低,并固溶了大量的Al3＋、Fe3＋、K＋、Na＋等。Ca(OH)2含量较低,并在水化7天后呈降低的趋势,而化学结合水则逐渐增加。水泥石的总空隙率随着水化龄期的延长而逐渐降低,大于1000的大孔体积率较低,而小于500的微孔及凝胶孔体积率较高。大量的针棒状AFt晶体与C－S－H凝胶相互连接,使得结构致密,具有较好的物理性能。     

杂质缺陷诱导阿利特晶胞常数的改变及多晶转变

阿利特或硅酸三钙,(C3S)固溶体是水泥熟料中最重要的矿物,某些杂质离子可以稳定其多晶型中的三方R型,具有较高的水化活性.杂质离子固溶进入C3S晶格,形成杂质缺陷,这些缺陷引起C3S晶格常数的变化.研究显示:C3S晶格常数的变化与其对称性有关,从而提出了-种由杂质缺陷引起晶格常数相对变化的计算方法,用于预测C3S固溶体和阿利特可能的稳定晶型.在实验室合成了不同掺杂的C3S固溶体单矿物,并从实验熟料中萃取了阿利特.对样品晶型进行X射线衍射(X-ray diffraction,XRD)测定及晶格常数相对变化计算的预测.计算预测结果和XRD分析结果之间较好相符.XRD分析表明:纯C3S的对称性最差,属于三斜晶系.当C3S中P2O5固溶量在0.4%(质量分数,下同)时,C3S固溶体为单斜M1型.当CaF2掺量在1.0%时,C3S固溶体也为M1型.当CaF2掺量提高到2.0%时,C3S固溶体是R型.复合掺加氟磷对改变C3S固溶体对称性有显著作用,只要掺杂0.4%的P2O5和0.7%的CaF2即可使R型C3S固溶体在室温下稳定.对熟料中萃取阿利特的分析表明:普通熟料中萃取阿利特的稳定晶型属于Mi型;含氟磷的熟料中阿利特是以R型为主的R型和M3型的混合体.分析结果验证了计算预测结果.     

转炉钢渣中物相易磨性及胶凝性的差异

将钢渣粉磨后分级,得到7种不同粒径的试样,用x射线衍射仪分析了它们的矿物成分,研究了粗粒子试样在硅酸钠作用下的胶凝性,并以矿渣为参比样,比较研究了钢渣细粉与矿渣易磨性及胶凝性的差异,用扫描电子显微镜及X射线能谱仪分析了钢渣中硅酸盐矿物硅酸二钙(C3S)和硅酸二钙(C2S)的固溶组分.结果表明:钢渣中难磨组分为铁铝酸钙[Ca2(Al,Fe)205] 和镁铁相同溶体(MgO·2FeO),且它的水化反应活性很低;钢渣中C3S和C2S具有较好的易磨性,其易磨性比矿渣的略好,但其水化反应活性明显比矿渣的差,钢渣中的C3S和C2S固溶了较多的异离子;钢渣水化活性低是由于它所含的矿物Ca2(Al,Fe)2O5,MgO·2FeO无水硬性,C2S呈γ型,水硬性低,而C3S是在长时间高温下形成的,它具有较稳定的结构,其水化活性亦相对较低.     

烧成温度对低热水泥性能的影响及其机理研究

检测了不同烧成温度制成的低热水泥的物理性能及水化速率，并采用岩相分析、XRD、EDS﹑化学分析方法研究了不同烧成温度对低热水泥熟料岩相结构﹑矿物组成、矿物晶型及矿物固溶组分的影响。结果表明，低温烧制的熟料中C4A3S的生成及C3A、C4AF含量相对较多是低温烧制的低热水泥早期强度较高的主要原因;而高温烧成的熟料中高温晶型C2S含量高，B矿中固溶SO3、Al2O3、Fe2O3多，B矿的Ca/Si增高，水化活性增大，这是高温烧成的低热水泥后期强度较高的主要原因。     

氧化铁掺杂对阿利特结构及活性的影响（英文）

用X射线衍射结合Rietveld方法、热释光及微量热分析等,研究了Fe2O3掺杂对同时固溶有Na、K等多种杂质的典型组成阿利特的结构及性能的影响。结果表明:阿利特晶型未发生改变,晶格常数随Fe2O3掺量呈线性变化,并在Fe固溶类型改变处(0.6%Fe2O3)发生突变,符合Vegard固溶体定律。阿利特水化活性和原始热释光性均显著降低,并呈现正相关性,且相关性主要体现在结晶成核与晶体生长控制过程。这一现象可以归因于储存在阿利特中的介稳能量,据此提出了Fe影响阿利特水化的新机制。     

Al3+掺杂对硅酸三钙结构及水化活性的影响

利用X射线衍射仪、差示扫描量热-热重分析仪、红外光谱及微量热分析等,研究了Al3+掺杂对硅酸三钙C3S结构及活性的影响.结果表明:Al3+在C3S中固溶同时取代Ca和Si,并伴随少量Ca空位的形成保持电荷平衡.当Al2O3掺量高于0.5％(质量百分数,下同)时,Al取代Si比例增加.Al2O3掺量≤0.5％时仅使C3S晶胞参数改变,当掺量达1％时,可稳定T3晶型,符合离子稳定C3S多晶态规律.Al3+在C3S中固溶形成大量非本征缺陷,显著提高C3S早期水化反应活性.     

The Effect of Magnesium and Zinc Ions on the Hydration Kinetics of C3S

Impure tricalcium silicate (C₃S) in portland cement may contain various foreign ions. These ions can stabilize different polymorphs of C₃S at room temperature and may affect its reactivity. In this paper, the effects of magnesium and zinc on the polymorph type, hydration kinetics, and the hydrate morphology of C₃S were investigated. The pure C₃S has the T1 structure while magnesium and zinc stabilize polymorphs M3 and T2/T3, respectively. The two elements have distinct effects on the hydration kinetics. Zinc increases the maximum heat released. Magnesium increases the hydration peak width. The C–S–H morphology is modified, leading to longer needles in the presence of zinc and thicker needles in the presence of magnesium. Zinc is incorporated into C–S–H, while magnesium is only incorporated slightly, if at all, but rather seems to inhibit nucleation. Implementing experimentally measured parameters for C–S–H nucleation and growth in the μic hydration model captured well the observed changes in hydration kinetics. This supports C–S–H nucleation and growth to be rate controlling in the hydration of C₃S.     

稀土离子掺杂Co2O3-ZnO-NiO-Fe2O3陶瓷在特定波段的红外辐射性能

用常规固相合成法成功地制备出La3 ,Ce3 ,Pr3 及Nd3 掺杂的Co2O3-ZnO-NiO-Fe2O3陶瓷材料.用x射线衍射分析、红外吸收光谱和IRE-2双波段红外发射率测量仪对材料的结构特征与红外辐射性能进行研究.稀土离子主要以八面体配位形式进入Co2O3-ZnO-NiO-Fe2O3类尖晶石型体系中取代Ni2 ,形成有限置换型固溶体结构,导致体系晶胞参数从0.8383nm缩小为0.8373nm.样品的红外辐射性能随La3 ,Ce3 ,Pr3 及Nd3 离子半径的降低呈现极值的变化,掺杂质量分数为0.5%的Ce3 在8～14μm波段的平均辐射率最高,可达0.92.     

The effect of gyrolite additive on the hydration properties of Portland cement

The influence of gyrolite additive on the hydration properties of ordinary Portland cement was examined. It was found that the additive of synthetic gyrolite accelerates the early stage of hydration of OPC. This compound binds alkaline ions and serves as a nucleation site for the formation of hydration products (stage I). Later on, the crystal lattice of gyrolite becomes unstable and turns into C–S–H, with higher basicity (C/S ~ 0.8). This recrystallization process is associated with the consumption of energy (the heat of reaction) and with a decrease in the rate of heat evolution of the second exothermic reaction (stage II). The experimental data and theoretical hypothesis were also confirmed by thermodynamic and the apparent kinetic parameters of the reaction rate of C₃S hydration calculations. The changes occur in the early stage of hydration of OPC samples and do not have a significant effect on the properties of cement stone.     

The Effect of Alkali Ions on the Incorporation of Aluminum in the Calcium Silicate Hydrate (C–S–H) Phase Resulting from Portland Cement Hydration Studied by 29Si MAS NMR

The incorporation of aluminum in the calcium–silicate–hydrate (C–S–H) phases formed by hydration of three different white Portland cements has been investigated by ²⁹Si MAS NMR. The principal difference between the three cements is their bulk Al₂O₃ contents and quantities of alkali (Na⁺ and K⁺) ions. ²⁹Si MAS NMR allows indirect detection of tetrahedral Al incorporated in the silicate chains of the C–S–H structure by the resonance from Q²(1Al) sites. Analysis of the relative ²⁹Si NMR intensities for this site, following the hydration for the three cements from 0.5 d to 30 weeks, clearly reveals that the alkali ions promote the incorporation of Al in the bridging sites of the dreierketten structure of SiO₄ tetrahedra in the C–S–H phase. The increased incorporation of Al in the C–S–H phase with increasing alkali content in the anhydrous cement is in accord with a proposed substitution mechanism where the charge deficit, obtained by the replacement of Si⁴⁺ by Al³⁺ ions in the bridging sites, is balanced by adsorption/binding of alkali ions in the interlayer region most likely in the near vicinity of the AlO₄ tetrahedra. This result is further supported by similar ²⁹Si MAS NMR experiments performed for the white Portland cements hydrated in 0.30M NaOH and NaAlO₂ solutions.     

Aluminum Incorporation in the C–S–H Phase of White Portland Cement–Metakaolin Blends Studied by 27Al and 29Si MAS NMR Spectroscopy

The composition and structure of the calcium‐silicate‐hydrate (C–S–H) phases formed by hydration of white portland cement–metakaolin (MK) blends have been investigated using ²⁷Al and ²⁹Si MAS NMR. This includes blends with 0, 5, 10, 15, 20, 25, 30 wt% MK, following their hydration from 1 d to 1 yr. ²⁹Si MAS NMR reveals that the average Al/Si ratio for the C–S–H phases, formed by hydration of the portland cement–MK blends, increases almost linearly with the MK content but is invariant with the hydration time for a given MK content. Correspondingly, the average aluminosilicate chain lengths of the C–S–H increase with increasing MK content, reflecting the formation of a C–S–H with a lower Ca/Si ratio. The increase in Al/Si ratio with increasing MK content is supported by ²⁷Al MAS NMR which also allows detection of strätlingite and fivefold coordinated aluminum, assigned to AlO₅ sites in the interlayer of the C–S–H structure. Strätlingite is observed after prolonged hydration for MK substitution levels above 10 wt% MK. This is at a somewhat lower replacement level than expected from thermodynamic considerations which predict the formation of strätlingite for MK contents above 15 wt% after prolonged hydration for the actual portland cement–MK blends. The increase in fivefold coordinated Al with increasing MK content suggests that these sites may contribute to the charge balance of the charge deficit associated with the incorporation of Al³⁺ ions in the silicate chains of the C–S–H structure.     

Impact of Annealing on the Early Hydration of Tricalcium Silicate

It was recently proposed that the induction period observed during the hydration of tricalcium silicate could be explained by the build‐up of ions in solution. Due to the importance of defects in this mechanism, this work describes the effect of different annealing effects on the defect structure and hydration behavior of C₃S. The impact of annealing on the crystal structure was checked by X‐ray diffraction and the defect structure studied by transmission electron microscopy. The hydration kinetics were followed by isothermal calorimetry of pastes. Scanning electron microscopy was used to look at the microstructure formation. It was observed that grinding created a highly deformed layer on the surface of the grains, which disappeared after annealing. The defect structure was closely related to the length of the induction period observed in pastes by calorimetry. There was no observable effect on the morphology of C–S–H during hydration, but the number of calcium hydroxide nuclei was less in pastes from annealed material.     

镁渣晶体结构对脱硫活性影响实验

研究了激冷水合过程中镁渣晶体结构的变化,结合钙转化率研究了晶体结构对镁渣脱硫活性的影响。借助X射线衍射和透射电镜分析了镁渣的晶体结构和形貌特征。结果表明：β-C₂S中的Ca²⁺配位不规则是其水合活性高于γ-C₂S的原因。随着镁渣激冷温度升高,β-C₂S增加,促进了具有发达孔隙结构的C－S－H生成,提高了物理吸附能力;晶粒细化程度增大,晶胞参数变化引起的晶格缺陷增多,增强了化学吸附能力。950℃激冷温度下镁渣脱硫活性最高,钙转化率达到24.6%。     

The filler effect: The influence of filler content and type on the hydration rate of tricalcium silicate

The partial replacement of ordinary portland cement (OPC) by fine mineral fillers accelerates the rate of hydration reactions. This acceleration, known as the filler effect, has been attributed to enhanced heterogeneous nucleation of C‐S‐H on the extra surface provided by fillers. This study isolates the cause of the filler effect by examining how the composition and replacement levels of two filler agents influence the hydration of tricalcium silicate (T1‐Ca₃SiO₅; C₃S), a polymorph of the major phase in ordinary portland cement (OPC). For a unit increase in surface area of the filler, C₃S reaction rates increase far less than expected. This is because the agglomeration of fine filler particles can render up to 65% of their surface area unavailable for C‐S‐H nucleation. By analysis of mixtures with equal surface areas, it is hypothesized that limestone is a superior filler as compared to quartz due to the sorption of its aqueous CO₃^2? ions by the C‐S‐H—which in turn releases OH^? species to increase the driving force for C‐S‐H growth. This hypothesis is supported by kinetic data of C₃S hydration occurring in the presence of CO₃^2? and SO₄^2? ions provisioned by readily soluble salts. Contrary to prior investigations, these results suggest that differences in heterogeneous nucleation of the C‐S‐H on filler particle surfaces, caused due to differences in their interfacial properties, have little if any effect on C₃S hydration kinetics.