Research Progress of Additives to Improve Hydration Resistance of Magnesia-calcium Materials

Magnesia-calcium materials have stable hot performance,good resistance to the erosion and corrosion of liquid steel and steel slag,and a special role in purifying liquid steel,so they are widely used in iron and steel industry.However,hydration of magnesia-calcium materials seriously restricts their use,so researches have been done to improve their hydration resistance,obtaining a series of achievements.In this paper,the improvements on the hydration resistance of magnesia-calcium materials by additives in recent 20 years were presented,and their mechanisms were summarized.

Effects of Water-cement Ratio and Hydration Heat Regulating Materials on Hydration Process of Early-age Cementitious Materials

By means of low-field nuclear magnetic resonance(LF-NMR),the transverse relaxation time(T_(2))signals of physically bound water in cement paste were monitored to indicate water content change and characterize the early-age hydration process.With the curves of the T_(2)signals and hydration time obtained,the hydration process could be divided into four typical periods using the null points of the second derivative curve,and the influences of water-cement ratio(w/c)and hydration heat regulating materials(HHRM)on hydration process were analyzed.The experimental results showed that the hydration rate of pure cement paste in accelerated period presented a positive correlation with w/c.Compared to pure cement paste,the addition of HHRM extended all four periods,and led to a much faster hydration rate in initial period as well as a slower rate in accelerated period.Finally,according to the LFNMR test results,the early-age hydration model of cementitious materials was proposed considering w/c and HHRM content.

Properties and Hydration Mechanism on High-strength Anchorage Grouting Material for Highway Slope

The rheological and mechanical properties of high-strength anchorage grouting materials for highway slope were investigated to optimize the mix proportion. The experimental results showed that the optimized mix proportion of high-strength anchorage grouting material （HAGM） was C3 （FA：SP-SF= 1：2：2; AGI：AG2=3：7 and 0.03% FC）, which is agreement with the limitation of JCT 986-2005. Moreover, the XRD and FTIR results showed the addition of expansive components was in favor of the formation of ettringite. The intensity of AFt oeak of the samnles increased with the increasing of hydration time.

Hydration kinetics of cementitious materials composed of red mud and coal gangue

To elucidate the intrinsic reaction mechanism of cementitious materials composed of red mud and coal gangue（RGC）, the hydration kinetics of these cementitious materials at 20°C was investigated on the basis of the Krstulovi？-Dabi？ model. An isothermal calorimeter was used to characterize the hydration heat evolution. The results show that the hydration of RGC is controlled by the processes of nucleation and crystal growth（NG）, interaction at phase boundaries（I）, and diffusion（D） in order, and the pozzolanic reactions of slag and compound-activated red mud-coal gangue are mainly controlled by the I process. Slag accelerates the clinker hydration during NG process, whereas the compound-activated red mud-coal gangue retards the hydration of RGC and the time required for I process increases with increasing dosage of red mud-coal gangue in RGC.

Effect of Curing Temperature on the Morphology and Hydration of MgO Expansive Material in Paste

The morphologies and hydration properties of MgO expansive material at different curing temperatures were investigated.When the curing temperature varies from 25℃to 50℃,the conductivity of MgO rises from 40 to 80μs/cm,the hydration product of MgO expansive material curing in water for 28 days is from 1.5—2 mm to 2—2.5μm in length through SEM observation,and the expansion of pastes with 5%of the magnesium oxide is from 0.36%up to 1.01%,it is increased by 2.78 times.When the content of cement paste increases to 95%and cured in water for 90 days,the brucite forms as hexaflaggy?shaped crystal,which is less than 0.1μm and tends to aggregates.The effect of curing temperature on the hydration of MgO expansive material is obvious.

Analysis of Hydration Mechanism and Microstructure of Composite Cementitious Materials for Filling Mining

To obtain the compositions and microstructure of hydration products of cementitious material in different hydration ages and its growth law of filling strength, the optimal proportion of composite cementitious material was determined according to the chemical composition of cement clinker which was composed of the Portland cement 32.5R, CSA 42.5 sulphoaluminate cement and two gypsum（CS）. The characterization of composite cementitious materials in different hydration ages was conducted by NMR, XRD and SEM techniques. The mechanism of hydration was explored. It is shown that the compressive strength of the test block increases gradually with the increase of hydration age. The microstructure of composite cementitious material can be changed from Al-O octahedron into Al-O tetrahedron in the hydration process. The hydrated alkali alumi niumsilicate formed with Si-O tetrahedron and Al-O tetrahedron. The degree of polymerization of Si-O tetrahedron gradually increased, and the structural strength of cementitious materials continued to increase. The diffraction peak of clinker minerals gradually decreased with the extension of hydration age. The CaSO4 completely hydrated to produce Aft during hydration which resulted in high early strength of cementitious material. The early hydration product of composite cementitious materials was Aft with a needle bar structure. The main middle and last hydration products were CSH gel and CH gel with dense prismatic shape. The microscopic pore of composite cementitious material gradually decreased and improved the later strength of filling block. The strong support was provided for mined-out area.

Hydration mechanism of low quality fly ash in cement-based materials

The hydration mechanism of low quality fly ash in cement-based materials was investigated. The hydration heat of the composite cementitious materials was determined by isothermal calorimetry, and the hydration products, quantity, pore structure and morphology were measured by X-ray diffraction(XRD), thermalgravity-differential thermal analysis(TG-DTA), mercury intrusion porosimetry(MIP) and scanning electron microscopy(SEM), respectively. The results indicate that grinding could not only improve the physical properties of the low quality fly ash on particle effect, but also improve hydration properties of the cementitious system from various aspects compared with raw low quality fly ash(RLFA). At the early stage of hydration, the low quanlity fly ash acts as almost inert material; but then at the later stage, high chemical activity, especially for ground low quality fly ash(GLFA), could be observed. It can accelerate the formation of hydration products containing more chemical bonded water, resulting in higher degree of cement hydration, thus denser microstructure and more reasonable pore size distribution, but the hydration heat in total is reduced. It can also delay the induction period, but the accelerating period is shortened and there is little influence on the second exothermic peak.

The NMR core analyzing tomograph:a multi-functional tool for non-destructive testing of building materials

NMR is becoming increasingly popular for the investigation of building materials as it is a non-invasive technology that does not require any sample preparation nor causes damage to the material.Depending on the specific application it can offer insights into properties like porosity and spatial saturation degree as well as pore structure.Moreover it enables the determination of moisture transport properties and the(re-)distribution of internal moisture into different reservoirs or chemical phases upon damage and curing.However,as yet most investigations were carried out using devices originally either designed for geophysical applications or the analysis of rather homogeneous small scale(<10 mL)samples.This paper describes the capabilities of an NMR tomograph,which has been specifically optimized for the investigation of larger,heterogeneous building material samples(diameters of up to 72 mm,length of up to 700 mm)with a high flexibility due to interchangeable coils allowing for a high SNR and short echo times(50-80 ms).

Dielectric Permittivity of Various Cement-Based Materials during the First 24 Hours Hydration

The dielectric permittivity of cementitious materials during 24 hours hydration period at a frequency of 2.45 GHz using a network analyzer with open-ended probe technique was measured. Influences of water-to-cementitious ratios, cement types, pozzolans and aggregate types are taken into consideration. The results show that dielectric permittivity is strongly affected by initial water-to-cementitious ratio and the rate of hydration reaction which can be changed by fineness of cement (Types 1 and 3), pozzolan materials and aggregates (river sand with/without crushed limestone rock). Dielectric permittivity is relatively high and remains constant during the dormant period, after that it decreases rapidly when the hydration reaction resumes and continues to decrease during the acceleratory period.

Preliminary Study of Agricultural Waste as Biochar Incorporated into Cementitious Materials

Incorporating small amounts of biochar into cementitious materials has partial effects on the environment.In this present study,rice husk was collected as agricultural biomass from a local area of Roorkee Uttarakhand,which contains siliceous material to a significant extent.Biochar was prepared from agricultural waste in a muffle furnace at a temperature of 500℃for 90 min and ground to a fineness of less than 10μm.Prior to incorporation into building envelopes such as mortar and concrete,a basic study on cement pastes is essentially required.For this purpose,different dosages of biochar such as 0,3%,5%and 10%wt.were replaced with cement in cementitious materials.Physical properties such as water absorption,density and porosity were investigated.Furthermore,mechanical and thermal properties such as compressive strength and thermal conductivity were studied.Advanced tools like field emission scanning electron microscopy(FESEM),X-ray diffraction(XRD)and thermogravimetric analyzer(TGA)were used to identify the hydration products.As the dosages increased in the cement matrix,the physical properties of sample were increased and porosity decreased.The compressive strength of biochar incorporated cement paste improved according to 0,3%,5%and 10%wt.It further reveals that as the dosage increased,the thermal conductivity of the samples decreased significantly.Moreover,the sustainable assessment showed that biochar could reduce embodied carbon,embodied energy and strength efficiency substantially over the control sample.A satisfactory result was obtained at 5%wt.and 10%wt.of biochar.The overall result revealed that biochar up to 10%wt.can be incorporated into mortar and concrete due to better results than the control mix.

Hydration Process of Cement-Based Materials by AC Impedance Method

AC impedance is a new method to study the changes of pore structure and the hydration degree during the hydration and hardening process of cement paste by the change of the electrochemical parameters. Employing AC impedance method, we studied the hydration and hardening process of cement paste with fly ash and slag, and analyzed the influence of different hydration age, water-binder ratio and mineral admixture on the impedance parameters. Moreover, we compared the results with those by the conventional porosity testing method and X-ray diffraction method. The results showed that AC impedance could be taken as a new technology in cement and concrete research.

Adding Hydrated Lime in a Material Made of Clayey Soil and Fibres: Formulation and Effects on Thermo-Mechanical Properties

In this study, we have focused our investigations on effect of adding hydrated lime on a locally made composite material, based on clayey earth (soil) and Hibiscus sabdariffa fibres, for envelope (walls) in the building. Prior to sample’s formulation, we selected an appropriate mineral (soil) material based on criteria as: plasticizer power for good workability, dense coarse particles to withstand loads and finally porous structure to take advantage of air insulating character. We then formulated, following a mixing process by shearing and compaction by vibration that we recommend, two composite materials (A), (B) which contain respectively 1% Fibres plus 1% lime, 1% Fibres plus 3% lime. We determined thermal properties by the mean of KD2 Pro thermal analyzer, compression strength accordingly to the standard NF P 18-406, porosity following volumetric and gravimetric methods and pH of soil-hydrated lime solution. As results, up to 5% of hydrated lime, the measured pH is inferior to 12: mineralization of vegetal fibres is highly unlikely. Moreover, we observe that the addition of hydrated lime resulted in a reduction in the number of cracks and their depths;Samples (A) and (B) have a rather compact appearance than the case 1% Fibres without lime (material (C)). Furthermore, with lime stabilization, the insulating potential is improved while the thermal inertia has been deteriorated compared to material (C). However, compressive strength decreases with lime, which could be due to the presence of fibres that would inhibit the hardening of the lime. At last, with 3.39% ± 3.07% MPa, 2.27% ± 11.30% MPa for samples (A), (B) respectively, the minimum required by CRATerre-EAG (guide of CDI, 1996) for construction of envelope (walls) of single storey (ground floor) buildings is met.

Effect of distortion degree on the hydration of red mud base cementitious material

The interaction of Si anions with AI sites during the hydration process was observed by NMR, IR and SEM to understand the reaction mechanism of the hydrates formation mixed with oil shale calcined at different temperatures. As the reaction progressed,the coordination of AI (IV, V, and VI) changed almost completely to IV, when mixed with oilshale calcined at 700^(。)C. However, when mixed with oil shale calcined at 400^(。)C, some6-coordination of AI still remained in the hydrates. Under the function of alkaline solutions,which were produced with the hydration of clinker, a certain amount of Si and AI atomsdissolved or hydrolyzed from aluminosilicate, formed geomonomers in solutions, and thenpolycondensed to form networks.

Preparation and Performance Research of Cement-based Grouting Materials with High Early Strength and Expansion

Main performance of the cement grouting materials made up by Portland cement（PC） and sulphoaluminate cement（SAC） was investigated in this program, a kind of expanding agent（EA） which was mainly constituted by metakaolin and alunite was utilized for the compensation of the shrinkage, the hydration products and micro structure of the grouting materials were researched by X-ray diffraction（XRD） and scanning electron microscopy（SEM）. The results showed that a high expansion rate of the grouting materials could be reached as the expanding agent mixed in 6% of PC mass; the addition of SAC in the S2（PC：SAC：EA=34：6：2.25） brought a further improvement of the expansion rate of the grouting materials, the analysis of XRD and SEM showed that due to the reaction of expanding agent and SAC in the grouting materials, more ettringite crystal was generated, which resulted in a higher early strength, the addition of SAC played an expansion and strength reinforcement role in the grouting materials.

Graphene Oxide Application in Cement-Bound Materials-State of the Art

In recent years,the incorporation of nanoparticles in the cementitious matrix has been regarded as a prominent strategy in the research effort.This paper reviews the influences of the nanomaterial GO(graphene oxide)in cement bound materials,as GO has become one of the most well-known inclusion nanoparticles in the cementitious matrix in the last few years.This study describes(i)the influences of the GO on enhancing hydration mechanism in the cementitious materials;and(ii)the improved performance of the cementitious materials,which are highly dependent on the functionalizing behavior of the GO.All this improves the properties of the matrix.The paper reports the influences of GO on the workability of the mixtures and the durability enhancement of the cementitious composites.Therefore,it demonstrates promising results of employing GO in the fabrication of novel building materials.However,tremendous progress in utilizing GO in scientific domains like materials technology has achieved a significant level.Remarkable progress has been achieved by applying the GO in different fields such as solar cells and super capacitors.Hence,more intensive research is required to achieve comparable improvement in building materials which constitutes a significant future challenge.

基于水合物层骨架重构的低温早强胶凝材料

针对于天然气水合物能源试采过程中出砂导致试采作业被迫终止的问题,在水合物第2次试采工作经验和层内加固、防砂理论的基础上,进行了水合物层骨架重构的低温早强胶凝材料体系构建研究。该研究对比了嘉华G级、超细水泥和早强水泥的低温早期强度和长期长度、粒径分布,基于满足层内加固骨架重构孔隙尺寸,进行了低温早强胶凝材料组分设计,以水泥浆流动度、早强性及成本为目标,尽可能提高固结体的早期强度,为后续增渗提供更多强度下降空间。通过研究超细油井水泥与嘉华G级水泥的配比、早强剂优选及加量优化,构建出了低温早强胶凝材料体系,该体系在15℃水浴下24 h抗压强度可达到12.86 MPa,具有良好的流动性、稠化时间和失水可控性,相较于文献的低温早强水泥浆体系具有更好的增渗高强特性。该研究为后续研究水合物层内骨架重构高渗透、高强度的工作液体系奠定了材料基础。

钢渣-矿渣基胶凝材料的协同水化机理

通过胶砂强度试验及X射线衍射仪(XRD)、热失重分析(TG-DTG)、扫描电镜-能谱仪(SEM-EDS)等微观测试技术,对不同配合比钢渣-矿渣基胶凝材料的力学性能、水化产物及其水化硬化过程进行了研究.结果表明:当胶凝材料的n(CaO+MgO)/n(SiO2+Al2O3)=0.90时,其水化后期有较多的水化硅酸钙、水化铝酸钙凝胶生成,微观结构更加致密,力学性能表现最优,28 d抗压强度和抗折强度分别达到20.20、7.25 MPa;pH值的变化反映出协同水化效应的关键在于钢渣活性矿物的溶解和矿渣的二次火山灰反应,钢渣和矿渣的最佳配合比可以保证水化程度有较高的水平.

铅冶炼渣基生态胶凝材料的研发及重金属固化

铅冶炼渣(LSS)是一种含有重金属(Cr、Ni、Cu、Zn、As和Pb)的危险废物,其不当处置会对生态系统造成不可挽回的危害。本工作采用化灰渣(LAS)、水氯镁石(BF)、矿粉(SP)及适量水泥(CM)协同激发铅冶炼渣制备生态胶凝材料。通过正交试验得到胶凝材料的最优配比,阐述了不同因素对生态胶凝材料抗压强度的影响;采用XRD、SEM、FTIR、硫酸和硝酸法等方法分析了胶凝材料水化产物的特性及重金属浸出规律。研究结果表明:当铅冶炼渣和水泥的质量比为3∶1,化灰渣、水氯镁石、矿粉的外掺量分别为铅冶炼渣和水泥质量总量的20%、10%、10%时,制备出的生态胶凝材料抗压强度最优,28 d抗压强度达到40.9 MPa,且矿粉掺量为影响其抗压强度的第一要素。微观分析表明,胶凝材料的水化产物主要为弗里德尔盐、方解石、C-S-H和C-A-S-H,它们相互连接形成致密的空间网络结构,这不但有助于提高胶凝材料的力学性能,还能实现对重金属元素的物理固封和离子交换吸附固化。胶凝材料对主要重金属的胶结固化率大于83%,重金属浸出液浓度符合生活饮用水卫生标准(GB5749-2006)的要求。

干湿循环下复合激发膏体充填材料宏-细-微观强化与损伤特性

为探明盐-碱复合激发膏体充填材料的性能变化规律及干湿循环作用下充填体结构多尺度损伤机制,对以脱硫石膏和水泥熟料为复合激发剂的膏体充填材料进行多目标优化,并对最优配比下的充填体试块进行0~25次干湿循环,开展抗压强度、X射线衍射(XRD)、低场核磁共振(NMR)、扫描电镜(SEM)试验,揭示充填体宏观力学行为和微细观结构演化规律。研究结果表明:充填材料最优配比是矿渣掺量为50%,脱硫石膏与水泥熟料质量比为3:7,硅灰掺量为2.5%。随着干湿循环次数的增加,充填体宏观表现为抗压强度的折减及累积电导率升高,干湿循环10次时出现拐点,质量损失率和强度损失率分别达极小值-1.91%和-8.36%;在细观尺度上,T2谱反演良好,干湿循环作用10次后,横向弛豫时间逐渐右移且谱面积增大,表明膏体充填材料孔隙尺寸及数量随着干湿循环次数增加而增大;微观尺度上,钙矾石、石膏和方解石等侵蚀产物的膨胀结晶应力加速了微观孔隙结构的发育,反复干湿循环作用削减了C-S-H凝胶的黏聚力,由最初的堆叠蜂窝状劣化为小块状。综合宏、细、微观结构演变规律可知,孔隙结构的损伤演化与力学性能的劣化特征具有较好的同步性。

灌浆料流变性能的时变特性与屈服应力演化模型

为研究灌浆料流变性能的时变特性,厘清流变性能随时间变化的机理,通过流变试验研究灌浆料的流变模型和流变参数随时间的变化规律。结合灌浆料的冷冻扫描电镜微观结构随时间的变化过程和流体力学理论,研究屈服应力的时变机理,并建立考虑絮凝效应、水化反应和骨料颗粒-水泥浆体相互作用三者共同影响的新屈服应力演化模型。结果表明:灌浆料的流变模型符合Herschel-Bulkley模型,屈服应力随时间增加而增加。水化产物在网状絮凝结构上不断堆积,网状絮凝结构逐渐变大,这不仅增强了水泥浆体的抗剪切能力,也导致浆体表现更高的黏度,使得骨料颗粒-水泥浆体的相互作用力增大。因此,灌浆料的屈服应力增大。提出的新屈服应力演化模型能更好地描述含骨料颗粒水泥基材料的屈服应力随时间的变化规律。研究结果可为灌浆料的流动扩散研究和深入理解水泥基材料流变性能的时变性提供理论基础。