高贝利特硫铝酸盐水泥活化研究进展

基于我国提出的“双碳”战略目标,水泥行业应针对其高碳排放问题制定脱碳计划,因此,低碳水泥的研发和应用迫在眉睫。高贝利特硫铝酸盐水泥是一种在节能减排的同时能够资源化利用含铝工业废弃物的新型低碳水泥,未来也将会是一种具有高强度的低成本水泥。因此,高贝利特硫铝酸盐水泥的研发促进了水泥行业的绿色化发展。然而,水泥矿物组成中高活性无水硫铝酸钙含量较低,导致水泥石早期强度较低。对水泥早期活性进行研究可提升水泥强度,进而扩大其应用范围。本文通过简述高贝利特硫铝酸盐水泥的组成、特点和研究现状,从水泥主要矿物硅酸二钙、无水硫铝酸钙的活化和水泥矿物组成设计优化三个方面总结了影响高贝利特硫铝酸盐水泥活性的因素,旨在为高性能水泥的研制提供理论指导。     

水硬性活化贝利特水泥

活化贝利特水泥是以贝利特代替阿利特作为主要熟料矿物的一种水泥。通过热力活化和化学活化,贝利特在强度和其它结构性能方面与普通波特兰水泥相当。生产石灰标准KSt I=80～82的活化贝利特熟料节能10～14％,煅烧温度至少降低100K。此外,生产活化贝利特水泥所用的石灰石或灰质泥灰岩的     

贝利特的活化途径及高贝利特水泥

文章论述了贝利特水泥活化的结晶化学基础又提高贝利特活性、生产高贝利特水泥的主要技术途径。认为熟料急冷、化学活化和水热合成可大幅度提高贝利特的水化反应活性，结合对水泥熟料矿物组成的合理设计，利用含有各种微量元素的工业废渣尾矿，技之以能激发贝利特水化活性的外加剂的使用，有可能生产高性能的高贝利特水泥。从保护资源、保护生态环境，提高泥凝土工程的耐久性的观点看，生产高贝利特水泥具有广阔前景。     

贝利特-硫铝酸钡钙水泥的微观结构和力学性能

贝利特-硫铝酸钡钙水泥是一种新型的水泥材料,通过在贝利特熟料矿物体系中引入硫铝酸钡钙矿物,达到提高贝利特水泥早期强度的目的.研究了过量掺加SO3和BaO对贝利特-硫铝酸钡钙水泥性能的影响.研究结果表明:熟料中SO3和BaO最佳过掺量(质量分数)分别为50%和80%,制得的贝利特-硫铝酸钡钙水泥的3 d和28 d抗压强度分别达到27.0MPa和85.6MPa,展现了良好的力学性能.SO3和BaO的掺入促进了硫铝酸钡钙矿物的形成,同时对阿利特在低温下形成及对贝利特矿物的活化起到了重要作用.     

高贝利特水泥活化技术的研究

在生料中掺入微量元素及矿化剂来活化β—C2S，经试验确定，BasSO4对高贝利特活化的最佳掺钡量为0．8％，并可将高贝利特水泥的3d强度提高18％，28d强度提高到近120MPa；在掺入氟硫复合矿化剂后，高贝利特水泥的活性更高，更加贴近实际生产，也能达到节约能源、提高早期强度的试验目的。     

CaF2 对贝利特-硫铝酸钡钙水泥性能的影响

采用化学纯试剂为原料,将硫铝酸钡钙矿物引入到贝利特熟料矿物体系中,合成了贝利特-硫铝酸钡钙水泥.本文主要研究了 CaF2 对熟料矿物组成和水泥性能的影响.研究结果表明,CaF2 能够加快熟料中f-CaO的吸收,促进C2.75B1.25A3(S)矿物形成,提高水泥的早期强度.当CaF2 在熟料中的掺人量为0.6%时,贝利特.硫铝酸钡钙水泥的 3d 和 28d 抗压强度分别达到 26.8 MPa和 83.4 MPa,展现了良好的力学性能.利用 XRD,SEM-EDS 和岩相分析等测试手段分析了水泥熟料的组成和结构.     

低钙水泥熟料矿物水化活性、性能及其制备熟料的发展

与硅酸三钙相比,硫铝酸钙、硅酸二钙和硫硅酸钙等具有钙含量低、烧成温度低和CO₂排放量少的特点,属于低钙水泥熟料矿物。发展以低钙矿物为主要组成的水泥熟料是水泥低碳发展的重要方向。本文在分析硫铝酸钙、硅酸二钙和硫硅酸钙3种低钙矿物的活性、水化和性能发展的基础上,分别对以低钙矿物为主要矿物的硫铝酸盐水泥熟料、高贝利特硫铝酸盐水泥熟料的水化和性能发展,硅酸二钙–硫铝酸钙–硫硅酸钙水泥熟料的制备、水化和性能优化进行了综合评述。同时,鉴于石膏在低钙水泥熟料水化方面具有重要影响,综述了石膏在几种低钙水泥中的作用。文章以期为运用硫铝酸钙、硅酸二钙和硫硅酸钙等矿物制备低钙水泥熟料提供参考。     

高贝利特硫铝酸盐熟料矿物的活化及其混凝土性能

研究了Ba2+、P5+、Zn2+和B3+四种外掺离子对高贝利特硫铝酸盐 (HBCSA)熟料中贝利特和C4A3S　矿物的影响机制以及活化效果最佳试样的混凝土性能。利用X射线衍射（XRD）、扫描电子显微镜（SEM）和红外光谱（IR）表征了熟料矿物结构及形貌，试验表明， Ba2+、P5+和Zn2+在高温煅烧条件下，进入β-C2S和C4A3S　矿物晶格，引起晶体结构的不对称性，造成晶格畸变，从而稳定晶型、提高矿物的水硬性；B3+对C4A3S　矿物影响不显著，而对贝利特矿物有显著负面影响。综合得出：外掺离子对β-C2S的稳定及活化效果顺序为：Ba2+＞P5+＞空白＞Zn2+＞B3+, 对C4A3S　的活性提高作用次序则为：P5+＞Ba2+＞Zn2+＞空白＞B3+，对水泥强度的提高作用依次为：Ba2+＞P5+＞Zn2+＞空白＞B3+。经Ba2+活化后的强度等级为C30 的HBCSA混凝土的抗压强度、轴心抗压强度、弹性模量等力学性能以及抗硫酸侵蚀性能、抗碳化性能和干缩等耐久性能均优于PC混凝土。     

钡掺杂对高阿利特硅酸盐水泥熟料组成与性能的影响

采用正交试验方法研究了掺杂氧化钡及形成的新矿物硫铝酸钡钙(C_(2.75)B_(1.25)A_3(S))对高阿利特水泥熟料组成与性能的影响.借助于X射线衍射和扫描电镜-能谱仪及岩相等分析方法,研究了水泥熟料的组成、结构及性能.结果表明:阿利特和硫铝酸钡钙矿物可以在同一熟料体系中共存;氧化钡的掺入促进了硫铝酸钡钙矿物的形成,同时对在低温下形成阿利特及对贝利特矿物的活化起到了重要作用.从早期强度角度分析,BaO的适宜掺量为1.8%(质量分数,下同),硫铝酸钡钙矿物的最佳设计含量为4.0%.所制备的高阿利特硅酸盐水泥的3,7,28d抗压强度分别为52.3,78.4,102.5MPa,展现了良好的早期力学性能;从后期强度分析,BaO的适宜掺量为1.3%,硫铝酸钡钙矿物的最佳设计含量为2.0%,所制备的高阿利特硅酸盐水泥的3,7,28d抗压强度分别为42.9,77.8,108.8MPa,显示了较高的后期强度.     

活化煤矸石水泥水化机理与性能研究

近些年来,水泥的低碳化成为国内外的研究热点,利用活性矿物掺和料取代水泥是一种有效降低CO₂排放量的方法。为验证活化煤矸石作为水泥矿物掺和料的可行性,研究了活化煤矸石对水泥流变性能、力学性能、水化产物及水化程度的影响,揭示了水胶比、龄期及活化煤矸石掺量等对水泥胶砂试件抗压和抗折强度的影响,并利用XRD、SEM和TG/DTG等表征活化煤矸石对水泥水化产物和微观结构的影响。结果表明,活化煤矸石水泥的流变性能对水胶比的变化更加敏感。将活化煤矸石掺入水泥中,能够有效降低水泥早期的水化速率。活化煤矸石含有大量的活性SiO₂和Al₂O₃,具有很强的二次水化反应活性。二次水化产物水化硅酸钙和水化铝酸钙凝胶能够填充水泥机体的孔隙,提升水泥基体的强度。与掺30%(质量分数)石英粉的试件相比,掺30%(质量分数)活化煤矸石试件的28 d抗折和抗压强度分别提升了11.69%和11.82%。     

Quality design of belite–melilite clinker

We have developed a new cement clinker, consisting mainly of belite and melilite, which is capable of increasing the amount of recycled waste as a part of its raw materials. We analyzed clinkers with a wide range of compositions, and clarified the quantitative relationship between the chemical and mineral compositions. Clinkers consisting mostly of belite and melilite were successfully obtained at the CaO/SiO₂ mass ratio of 1.7 to 1.9. Test cements were prepared using these clinkers and mixed with OPC for the evaluation of fluidity and strength. The belite–melilite cement was found to have good fluidity, and the belite–melilite cement mixed with OPC at up to 30% exhibited a satisfactory long term strength equivalent to the OPC, demonstrating the potential as an alternative to OPC. Electron probe microanalysis revealed the relatively high concentration of diphosphorus pentaoxide in belite, suggesting this component might contribute to the strength enhancement of the cement.     

Phase development in conventional and active belite cement pastes by Rietveld analysis and chemical constraints

High belite cements may be an alternative to reduce CO₂ emissions. Although CO₂ emissions may be depleted up to 10%, unfortunately, the hydration reactivity of belite phases is slow which leads to low mechanical strengths at early ages. In order to enhance their hydraulic reactivity, the activation of these cements by doping with alkaline oxides has been proposed. Here, we have synthesised a laboratory belite clinker without activation (47 wt.% of β-C₂S and 19 wt.% of α_H′-C₂S) and two alkaline oxide activated clinkers (one with 13 wt.% of β-C₂S, 24 wt.% of α_H′-C₂S and 19 wt.% of α-C₂S; and the second with 12 wt.% of β-C₂S, 42 wt.% of α_H′-C₂S and 5 wt.% of α-C₂S). We have also developed a methodology to analyse quantitatively the phase evolution of cement pastes and we have applied it to these high belite cements. Rietveld quantitative phase analysis of synchrotron X-ray powder diffraction data, together with chemical constraints, is used to determine the phase development up to 1 year of hydration in the belite cement pastes. β-C₂S almost does not react during the first 3 months, meanwhile α_H′-C₂S reacts on average more than 50% in the same period. Moreover, the degree of reaction of α-C₂S is slightly larger (on average about 70% after three months) than that of α_H′-C₂S. Full phase analyses are reported and discussed including the time evolution of amorphous phases and free water.     

Structure and Properties of Portland Cement Clinker Doped with Zinc Oxide

ZnO added to the raw meal accelerates the rate of portland clinker formation. Due to ZnO doping, the amount of alite and C₂(AF) formed increases at the expense of belite and C₃A. The ZnO is preferentially taken up by the interstitial phase. The initial rate of tricalcium silicate hydration is retarded and the formation of ettringite is moderately accelerated in cements made from ZnO-doped clinkers. The set time of these cements is gradually prolonged and their strength development retarded with increasing degrees of ZnO doping.     

有替代硅酸盐水泥熟料的生产的选择吗?(英文)

人们一直在寻找CO2排放量低的水硬性胶凝材料,用它替代传统的以硅酸盐水泥熟料(Portland clinker,PC)为主的水泥。介绍了几种处于不同发展时期的新型非PC基的胶凝材料体系。目前大多数水泥生产商都尽可能多地用辅助性胶凝材料替代硅酸盐水泥熟料。火山灰材料具有低的水硬活性,它可使用高浓度碱金属溶液来激发,得到介于"地聚合物"和石灰激发火山灰胶凝材料间的复合胶凝材料。较远期可以期待基于贝利特、硫铝酸钙和铁铝酸钙矿物组成的水泥熟料,如拉法基公司的AetherTM已投入生产。更远的将来,不产生CO2的原材料,如硅酸镁等,可能使得水泥生产中实现CO2零排放,然而,这些胶凝材料的耐久性有待验证,用其配制的混凝土中钢筋锈蚀的防护是实际应用中的关键问题。     

Hydration products in sulfoaluminate cements: Evaluation of amorphous phases by XRD/solid-state NMR

The hydration of four sulfoaluminate cements have been studied: three sulfoaluminate systems, having different content of sulfate and silicate, and one blend Portland-CSA-calcium sulfate binder. Hydration was followed up to 90 days by means of a combination of X-ray diffraction and solid state MAS-NMR; Differential scanning calorimetry and Scanning electron microscopy were also performed in order to help the interpretation of experimental data. High amount of amorphous phases were found in all the four systems: in low-sulfate cements, amorphous part is mainly ascribed to monosulfate and aluminium hydroxide, while strätlingite is observed if belite is present in the cement; in the blend system, C-S-H contributes to the amorphous phase beyond monosulfate.     

Aluminum-rich belite sulfoaluminate cements: Clinkering and early age hydration

Belite sulfoaluminate (BSA) cements have been proposed as environmentally friendly building materials, as their production may release up to 35% less CO₂ into the atmosphere when compared to ordinary Portland cements. Here, we discuss the laboratory production of three aluminum-rich BSA clinkers with nominal mineralogical compositions in the range C₂S (50-60%), C₄A₃$ (20-30%), CA (10%) and C₁₂A₇ (10%). Using thermogravimetry, differential thermal analysis, high temperature microscopy, and X-ray powder diffraction with Rietveld quantitative phase analysis, we found that burning for 15 min at 1350 ºC was the optimal procedure, in these experimental conditions, for obtaining the highest amount of C₄A₃$, i.e. a value as close as possible to the nominal composition. Under these experimental conditions, three different BSA clinkers, nominally with 20, 30 and 30 wt.% of C₄A₃$, had 19.6, 27.1 and 27.7 wt.%, C₄A₃$ respectively, as determined by Rietveld analysis. We also studied the complex hydration process of BSA cements prepared by mixing BSA clinkers and gypsum. We present a methodology to establish the phase assemblage evolution of BSA cement pastes with time, including amorphous phases and free water. The methodology is based on Rietveld quantitative phase analysis of synchrotron and laboratory X-ray powder diffraction data coupled with chemical constraints. A parallel calorimetric study is also reported. It is shown that the β-C₂S phase is more reactive in aluminum-rich BSA cements than in standard belite cements. On the other hand, C₄A₃$ reacts faster than the belite phases. The gypsum ratio in the cement is also shown to be an important factor in the phase evolution.     

Influence of the clinker SO3 on the cement characteristics

This paper aims to clarify the influence of the clinker SO₃ on the cement characteristics. The impact on the strength development rate and the level of sulfate resistance were studied .The results show that increasing the amount of clinker SO₃ at low alkali level reduces the percentages of the tricalcium aluminate (C₃A) and alite as well as the alite/belite ratio, leading to a modification in the cement quality.For these reasons cements produced from a clinker containing high sulfate and low alkali, have slower strength development and higher sulfate resisting level than that produced with low sulfate clinker.     

Technical calcium nitrate as set accelerator for cement at low temperatures

The objective was to test the efficiency of technical calcium nitrate (CN) as a set accelerator for different cements at low temperatures (5–7 °C). The applied dosages were 0.00, 1.55, 2.32, 3.10, 3.86 and 7.73 % CN of the cement weight, corresponding to 0.00, 1.00, 1.50, 2.00, 2.50 and 5.00 % NO₃, respectively. Five different portland cements were chosen covering a wide range in C₃A contents, since it was initially believed that the set regulating mechanism involved C₃A (i.e. the efficiency depend on the C₃A content). The setting characteristics of the cement pastes with w/c = 0.40 were determined by an automatic Vicat-needle apparatus in a room with an ambient temperature of 5–7 dgC. The results revealed that the set accelerating efficiency of CN depended very much on the cement type. However, no correlation with the C₃A content was found. On the other hand, the set accelerator efficiency of CN seems to increase with increasing belite content according to the Bogue analyses of the cements, or other cement characteristica promoting belite formation in the clinker process.     

硫硅酸钙-硫铝酸盐水泥研究进展

硫铝酸盐水泥具有煅烧温度低、CO₂排放少、快硬早强以及抗冻抗渗等优良特性,在建材、固废领域具有广阔的应用前景,并衍生出贝利特-硫铝酸钙、贝利特-硫铝酸钡钙等一系列硫铝酸盐水泥。然而,硫铝酸盐水泥主要矿物成分贝利特(β-C₂S)具有水化活性低、水化速度慢的缺点,易导致水泥后期强度增长缓慢。硫硅酸钙(C₅S₂$\bar{\text{S}}$)曾被认为是一种“惰性”矿物,但在硫铝酸盐体系下可表现出比β-C₂S更强的水化活性,因此硫硅酸钙-硫铝酸盐水泥(TSAC)的研究具有重要意义。本文从C₅S₂$\bar{\text{S}}$矿物的形成和水化、TSAC的制备和性能等方面,综述了C₅S₂$\bar{\text{S}}$和TSAC的研究现状,并提出了TSAC需进一步研究和解决的问题,如固废原料探寻、TSAC性能调控以及TSAC熟料矿物组成优化等,以期为新型低碳水泥的研究和应用提供积极有利的参考和支持。