掺有磷渣的水泥基材料研究现状与分析

简介了磷渣的组成、结构与活性,分析了影响磷渣活性的主要影响因素;综述了磷渣作为辅助性胶凝材料对水泥基材料凝结时间、水化热、结构变化、强度、干燥收缩和耐久性等的影响,分析了磷渣在水泥基材料中应用存在的主要问题,并提出了一些改善措施和解决思路。加强磷渣在水泥基材料中的应用基础研究,对提高磷渣在水基材料中的利用率和减少环境污染有着重要意义。     

锂渣粉的组成及在水泥浆体中的物理与化学反应特性

利用XRF、ICP、XRD、TG/DTG、FTIR、SEM-EDS和氮气吸附等手段,分析了典型锂渣粉的组成及锂渣粉在水泥浆体中的物理与化学反应特性。结果表明:锂渣中含有层块状锂辉石、棒状石膏、多孔状硅藻土、球形锂辉石与饼状碳酸钙等;锂渣属于多孔材料,其孔主要为2～50 nm的中孔,主要由锂辉石、炭黑、硅藻土等引起;锂渣的BET比表面积为P·II52.5水泥的5倍,总孔体积为水泥的4倍,但平均孔径小于水泥;锂辉石、石膏、硅藻土与炭黑等的存在是导致锂渣含水率较高的主要原因;此外,锂渣混凝土需水量大,还与石膏、硫酸钠、碳酸钠和碳酸锂等可与水泥中的铝酸盐矿物反应形成较多钙矾石等有关。锂渣属于酸性渣,掺加到水泥中会降低水泥浆体的碱度;锂渣中影响水泥水化的元素主要为S、Ca、Si、Al和K等,而Li的影响较小;锂渣具有较高活性,不仅与其中的石膏有关,还与硫酸钠、碳酸钠和碳酸锂有关。     

纳米SiO2粉在水泥基复合材料中的试验研究

研究了硅粉、纳米SiO2粉的活性,二者及复合粉体与C3S的二次水化反应产物成分,并研究了水泥基材料的力学性能和显微结构,探讨了纳米SiO2粉改善显微结构的机理,获得纳米SiO2粉应用于水泥基材料适合的方法.研究表明,纳米SiO2粉为非晶态,活性高于硅粉.粉体二次水化速率大小及水化程度高低依次为复合粉体、纳米SiO2粉、硅粉.复合粉体应用于水泥基材料中可增加致密性、提高均匀性,并提高强度.纳米SiO2粉与粉煤灰、硅粉复合应用于水泥基材料能够体现优异的使用性和经济性.     

蒸养条件下锂渣复合水泥的水化产物与力学性能

利用电感耦合等离子体发射光谱(ICP)、X射线衍射分析(XRD)、扫描电子显微镜与能谱分析(SEM-EDS)及同步热分析(TG-DTG)等手段研究了掺20%锂渣复合水泥在80℃蒸养7 h、7 d和标养28 d条件下的水化产物与力学性能。结果表明:锂渣中SiO_2和Al_2O_3大部分存在于锂辉石中,而少量存在于玻璃体中,且锂渣中存在少量的碳酸盐。与纯水泥不同,锂渣复合水泥在以上三种养护条件下形成的C-S-H凝胶均主要为网状;此外,蒸养7 d时还有水化硫铝酸钙(AFt)和立方体CaCO_3生成,但无水化石榴石形成;蒸养28 d时,还有球形等大颗粒状C-S-H凝胶和立方体CaCO_3生成。蒸养可以促进锂渣和水泥的反应,尤其是锂辉石与水泥水化产物氢氧化钙的反应。在蒸养7 h和7 d条件下,锂渣复合水泥胶砂的抗折强度、抗压强度均明显高于纯水泥胶砂的抗折强度、抗压强度。     

硅基材料和矿渣应用于水泥基材料的研究进展

水泥基材料是目前使用量最大的建筑材料,在实际应用过程中,水泥基材料会出现损坏,达不到预期的性能要求.水泥水化产物中存在大量结晶的Ca(OH)2,影响各种水泥水化产物之间的粘结性,造成水泥基材料性能的降低.如何增强水泥基材料的性能成了国内外研究的热点,需要找到能够有效改善水泥基材料性能的方法.查阅国内外相关文献发现,将粉煤灰、硅灰、纳米SiO2(因三种材料的主要组分为SiO2,以下统称为硅基材料)或矿渣掺入到水泥基材料中,因其具有火山灰反应,并能起到填充作用,可明显提高水泥基材料的性能.掺合料的加入可降低水泥基材料中Ca(OH)2含量,减小其晶粒尺寸,使C-S-H凝胶的数量增多,改善水泥基材料的孔隙率,提高其性能.粉煤灰和矿渣成分中有部分玻璃态物质,能减少水泥浆体用水量,增加和易性;具有较低的火山灰性,适量掺入能降低水泥浆体的水化速度;含有粉煤灰或矿渣的水泥基材料早期强度较低,后期强度较高.硅灰与纳米SiO2的火山灰活性较高,能促进水化,适量掺入能够使水泥基材料早期强度大幅提高,但后期强度发展较慢;同时也会增大水泥基材料早期收缩,增加其结构开裂的风险.不同掺合料复掺后能产生协同增强效应,可获得性能优异的复掺改性水泥基材料.本文主要介绍了硅基材料和矿渣在水泥基材料中的应用,从反应机理、水化热、强度、孔隙率等方面来阐述其在水泥基材料中的研究现状和相关成果.对目前研究中存在的相关问题进行了分析总结,以期为制备性能优异的水泥基材料提供一定的参考.     

聚合物改性水泥基材料性能和机理研究进展

论述了聚合物改性水泥基材料的性能和机理研究进展.性能研究进展方面主要从聚合物改性、聚合物和外加剂复合改性以及聚合物和其他填料复合改性水泥基材料3个方面进行了讨论.而聚合物改性机理则从聚合物改性水泥基材料的微观结构、聚合物对水泥水化的影响以及聚合物与无机胶凝相间的相互作用等方面进行了讨论.     

超细镁渣微粉-水泥复合胶凝材料的性能及水化机理

镁合金被誉为“21世纪绿色工程金属结构材料”,我国皮江法炼镁所得镁渣规模庞大、亟待解决，制备建筑材料是消纳镁渣的重要渠道，但国内外相关研究屈指可数，且普遍以镁渣耦合其他固废及水泥制备复合胶凝材料为主，鲜有针对镁渣-水泥简单体系的细致研究，故镁渣水化及其对水泥水化的影响机制尚未明确。本工作通过探究超细镁渣微粉-水泥复合胶凝材料(MS-C)新拌浆体和硬化浆体的性能、组成及结构演化规律，分析超细镁渣微粉对MS-C水化进程的影响机制，进一步揭示镁渣-水泥的协同水化机理。镁渣中的硅酸二钙以低活性γ-C₂S为主，超细粉磨是发挥其填充效应的关键途径，掺入30%的超细镁渣粉使水泥中1 000 nm以上孔含量由7.98%降低至6.83%。在减水剂作用下，MS-C浆体的流动性随超细镁渣微粉掺量的增大而增大，在无减水剂时其作用相反。低掺量超细镁渣微粉的水化及弱胶凝作用可增大其填充效应对强度的贡献，并促进Ca(OH)₂和C-S-H凝胶的生成，使得低超细镁渣微粉掺量的MS-C获得优于纯水泥的28 d力学性能。本研究获得了超细镁渣微粉-水泥水化特性的基础结论，为提高镁渣...     

超细粉体对水泥基材料力学性能的影响

为了研究超细粉体在水泥基材料中的应用,对掺加不同活性超细粉体的水泥基试件进行了抗压强度和抗折强度的测试,讨论了矿粉A掺量、硅粉掺量、复掺矿粉A和硅粉对水泥基材料力学性能的影响。结论表明:活性超细粉体对水泥基试件的抗折和抗压强度有较大影响,尤其是硅粉能够很好地提高试件的抗折强度和抗压强度。通过SEM形貌分析,说明掺加的超细粉体能够与水泥基材料内部的不利成分Ca(OH)2发生二次水化反应,生成有利的C-S-H凝胶,有效改善水泥基材料的微观结构。     

锂云母渣缓凝机理研究及改性效果验证

锂云母渣的综合利用对国家双碳政策的执行及锂电行业的健康发展具有重大意义。但是锂云母渣中含有一定的氟、磷等有害杂质限制了其作为混凝土矿物掺合料在混凝土中的大规模应用。因此，通过XRD、XRF等手段分析了锂云母渣的理化特性，并结合砂浆水化热及净浆凝结时间实验，确定了锂云母渣缓凝机理，同时研究了生石灰对锂云母渣的改性效果。结果表明，锂云母渣缓凝的主要原因是其中可溶性氟与磷与水泥水化产物中的Ca²⁺形成氟化钙、磷酸钙、氟羟基磷灰石吸附在水泥水化初期形成的半透水性水化薄膜上，导致薄膜致密性增加，从而阻碍了离子和水的通过，引起水化速度降低，进而导致缓凝；生石灰能够有效缩短锂云母渣净浆的缓凝时间，改性后锂云母渣净浆凝结时间缩短114 min。     

纳米材料优化水泥基材料性能的研究进展

近年来高铁、跨海大桥等大型工程建设对水泥基材料的性能提出了更高的要求。纳米科技与纳米材料是从微观角度提升水泥基材料性能的重要手段,近年来,以纳米二氧化硅、纳米碳酸钙、碳纳米管、石墨烯等为代表的纳米材料在水泥基材料性能优化方面的研究有了长足的进展。目前的研究进展表明,纳米材料可以从多方面提升水泥基材料的性能,包括加速水化,提升早期强度;改善水化产物的组成与形貌,增加水泥基材料微结构密实度,提升力学性能与耐久性。就性能优化程度而言纳米材料在本领域具有巨大的应用潜力。同时,分散性问题是目前纳米材料在水泥基材料中应用面临的主要问题,提供成熟可商业化的分散性解决方案是纳米材料应用中亟待解决的问题。此外,目前对于用于水泥混凝土的纳米材料的结构设计与改性方面的研究也有可以继续深化的空间。     

钢渣胶凝活性评价方法的研究进展

钢渣是炼钢时产生的工业废渣,因含有C2S、C3S等矿物相而表现出胶凝活性。钢渣利用其胶凝活性作为水泥混凝土的矿物掺合料,是其高效资源化利用的重要途径,同时也是绿色建材的发展方向。综述了钢渣胶凝活性评价方法的研究现状,包括碱度系数法、矿物相微观测试法、比强度法、活性因子法以及快速评定法,认为钢渣胶凝活性由钢渣中能够参与水化反应表现出水硬性的组分体现,并提出了钢渣胶凝活性评价的研究发展方向。     

A multi-phase kinetic model to simulate hydration of slag–cement blends

Ground granulated blast furnace slag, which shows cementitious behavior (latent hydraulic activity) and pozzolanic characteristics (reaction with lime), has been widely used as a mineral admixture in normal and high strength concretes. Hydration of slag–blended cement is much more complex than that of ordinary Portland cement because of the mutual interactions between the cement hydration and the slag reaction. This paper presents a kinetic hydration model for cement–slag blends. The proposed model analyzes the slag reaction separate from cement hydration by considering the production of calcium hydroxide in cement hydration and its consumption in slag reactions. The amount of free water and the amount of calcium hydroxide left in the system were adopted as the control indicators for determining the slag reaction. Using the proposed model, the reaction ratio of slag can be evaluated as a function of curing age, considering the influences of the water to binder ratio, the slag replacement ratio and the curing temperature. Furthermore, the amount of chemically-bound water (self-cementing properties), calcium hydroxide (pozzolanic capabilities), and the heat released from hydration are evaluated by determining the contributions from both the cement hydration and the slag reaction. The evaluated results show good accordance with the experimental results.     

Three-dimensional computer modeling of slag cement hydration

A newly developed version of a three-dimensional computer model for simulating the hydration and microstructure development of slag cement pastes is presented in this study. It is based on a 3-D computer model for Portland cement hydration (CEMHYD3D) which was originally developed at NIST, taken over in the authors’ group and further developed. Features like the digitized 3-D microstructure, the cellular automata (CA) algorithm for simulating the random walking, phase transformation for simulating the chemical reactions, are retained. But, the 3-D microstructure was reconstructed allowing for slag particles as binder in the system. Algorithms and rules are developed to account for the interaction between Portland cement hydration and slag reaction in the paste, of which the mechanisms were revealed in the studies by Chen and Brouwers [(2007) J Mater Sci 42(2):428; (2007) J Mater Sci 42(2):444] Methods for considering the various factors on the reactivity of slag in hydrating slag cement pastes are proposed, mainly for the oxide composition of slag and the alkalinity in the pore solution composition. A comparison between the model predictions and the experimental results in literature shows that the presented computer model can successfully predict the hydration process and the microstructure development of hydrating slag cement paste.     

矿渣对道路混凝土表面透气和吸水性影响

研究不同掺量的矿渣对硅酸盐水泥混凝土表面透气和吸水性能的影响规律,并对其作用机理进行探讨。利用X射线衍射(XRD)、扫描电镜(SEM)和孔隙分析(MIP),对水化生成物、混凝土微观结构和孔结构及其孔分布进行分析。结果表明:添加矿渣可以改善混凝土的表面透气和吸水性能。掺加15%矿渣对改善混凝土表面透气和吸水效果较显著,其透气和吸水系数分别为0.035和0.8,均小于基准混凝土。这是由于矿渣具有微集料效应和潜在水化活性造成的。随着矿渣掺量的增加,混凝土表面的透气和吸水性能随之降低。     

The hydration of slag,part 2: reaction models for blended cement

The hydration of slag-blended cement is studied by considering the interaction between the hydrations of slag and Portland cement clinker. Three reaction models for the slag-blended cement are developed based on stoichiometric calculations. These models correlate the compositions of the unhydrated slag-blended cement with the quantities and compositions of the hydration products. The model predictions are further used to calculate some properties of hydrating slag cement pastes, including the molar fractions of products, the water retention, chemical shrinkage and porosities of pastes. The models are validated by comparing the model predictions with the measurements and proven to be successful in quantifying the hydration products, predicting the composition of the main hydration product (C-S-H) and calculating the properties of the hydration process. The model predictions show that as the slag proportions in the blended cement changes, water retention in the hydration products changes only slightly if compared to that of Portland cement, but the chemical shrinkage can vary in a wide range, depending on the slag hydration degree in the cement.     

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.     

A discussion on improving hydration activity of steel slag by altering its mineral compositions

This study aims to investigate the ways to improve the cementitious properties of steel slag. The results show that the cementitious phase of steel slag is composed of silicate and aluminate, but the large particles of these phases make a very small contribution to the cementitious properties of steel slag. RO phase (CaO-FeO-MnO-MgO solid solution), Fe(3)O(4), C(2)F and f-CaO make no contribution to the cementitious properties of steel slag. A new kind of steel slag with more cementitious phase and less RO phase can be obtained by removing some large particles. This new steel slag possesses better cementitious properties than the original steel slag. The large particles can be used as fine aggregates for concrete. Adding regulating agent high in CaO and SiO(2) during manufacturing process of steel slag to increase the cementitious phase to inert phase ratio is another way to improve its cementitious properties. The regulating agent should be selected to adapt to the specific steel slag and the alkalinity should be increased as high as possible on the premise that the f-CaO content does not increase. The cooling rate should be enhanced to improve the hydration activity of the cementitious phase at the early ages and the grindability of steel slag.     

Thermal activation on calcium silicate slag from high-alumina fly ash: a technical report

The fly ash with alumina composition from 45 to 55 % has been found in China in last 10 years, which attracts great attention from Chinese government and related alumina industry. Chinese government and its state-owned enterprises have successfully extracted the Al as alloy product from the high-alumina fly ash. However, to recycle the calcium silicate slag as residue from the Al industry is still undetermined. In this report, an innovative process is introduced to achieve the regional sustainability for the high-alumina fly ash industry, and it is found that the cementitious material composed of calcium silicate slag met with the mechanical requirements of 32.5 cement for road pavement. The chemical and mineral analysis show that the calcium silicate slag has high CaO content, which reaches up to 48.64 %. C₂S and C₃A are the dominant mineral phases by XRD analysis indicating its potential pozzolanic activity during the hydration process. Thermal activation from 200 to 900 °C was applied to enhance its pozzolanic activity for the calcium silicate slag and it proved that 600 °C is the optimal calcination temperature due to the decomposition of calcite and clay minerals. Also the mineral phase amorphization was also observed during the XRD analysis, which might also contribute to the enhanced pozzolanic properties at 600 °C. Although the designed cementitious material contains a large quantity of solid waste, none of the hazardous heavy metals exceed the EPA limits. This short article originally reported a promising direction for managing solid waste for Al industry and enhancing utilization efficiency for the enterprise internal solid wastes.     

多技术联用鉴别含铅固体废物

采用X射线荧光光谱、X射线衍射等技术,结合超景深显微镜、扫描电镜等设备,对某含铅样品进行化学成分、物相组成和微观形貌分析,判断是否为固体废物.结果表明:样品主成分为Pb3(CO3)2(OH)2,PbSO4和Na2SO4等,并且含有大量玻璃态的钠钙铝硅酸盐和呈球状、椭球状、串珠状的金属铅和铅铁氧化物.样品中的硫酸铅呈疏松...