The hydration characteristics and expansion machanism of expansive cement at low<Emphasis Type="Italic">W/B</Emphasis> ratio

The hydration characteristics and expansion impetus of three kinds of cement paste under free-and confined-curing conditions were investigated, which were respectively mixed with three different kinds of expansive agent at low W/B ratio. The results show that the hydration products of pure cement paste and paste mixed with expansive agent are same, but the amount of hydration products, un-hydrated C₃S and C₂S are obviously different at the same hydration age. At 3 d age, the amount of CH in pure cement paste is less than that of paste mixed with expansive agent, but it is reverse when at 28 d age. The amount of AFt at 3d and 28d age in pure cement paste is less than those of paste mixed with expansive agent. Regardless of under free- or confined-curing condition, the amount of ettringite produced varies little since 3d age. The joint effect of the tumefaction of gel-ettringite due to water absorption and the expansive pressure on the pore caused by the crystalloid ettringite is the cause of the volume expansion of cement paste, and the former effect is much greater than the latter. LU Lin-nu : Born in 1972 Funded by 973 High-tech Project of China (No. 2001CB610704-2) and the Natural Science Foundation of Hubei Province(No. 2002AB075)     

The Hydration of Blended Cement at Low W/B Ratio

1　IntroductionThehydrationandhardeningprocessesofordinarycementhavebeenstudiedintensively[1-3 ] .Partlyreplac ingcementwithflyash ,slag ,orotheractivemineralad mixturecannotonlymodifythecementstrengthgrade ,re ducethehydrationheatofcement ,butalsomelioratethestructureofhardencementpaste[4] .Applyingexpansiveagentinordinaryconcretecancombinethebearingandwaterprooffunctionsofabuilding ,anditcanalsoreducetheshrinkageandpreventthecrackingofconcrete[5,6] .However ,thehydrationprocessofcementmixedw…     

The hydration of blended cement at low<Emphasis Type="Italic">W/B</Emphasis> ratio

The hydration process, hydration product and hydration heat of blended cement paste mixed with mineral admixture and expansive agent at low W/B ratio are studied by XRD, thermo analysis, and calorimetry instrument, and they were compared with those of pure cement paste. The results show that pure cement and blended cement at low W/B ratio have the same types of hydration products, but their respective amounts of hydration products of various blended cements at same ages and the variation law of the amount of same hydration products with ages are different; The joint effect of tumefaction of gel-ettringite due to water absorption and the expansive pressure on the pore and rift caused by the crystalloid ettringite is the impetus of the volume expansion of cement paste, and the former effect is much greater than the latter one. HU Shu-guang: Born in 1957 Funded by 973 High-tech Project of China (No. 2001CB610704-2) and the Natural Science Foundation of Hubei Province(No. 2002AB075)     

低碱低掺混凝土膨胀剂的试验研究

利用不同的原料配制了多组低碱低掺型混凝土膨胀剂．测定了各膨胀剂的膨胀性能及其对水泥物理力学性能的影响．利用SEM分析了掺膨胀剂水泥的水化产物、结构和形貌．研究结果表明,利用SA熟料、无水石膏、煤矸石和硅铝质矿物原料配制的膨胀剂具有良好的膨胀性能,并对水泥的物理力学性能无不良影响;掺膨胀剂水泥在一定时期内会持续形成大量的呈交又生长的针状钙矾石,它们填充在孔隙内,使水泥石结构致密．     

利用固硫灰制备混凝土膨胀剂试验

探讨了利用固硫灰、锂渣、硬石膏为原料制备混凝土膨胀剂。通过正交试验研究了原料掺量和细度对其膨胀性能的影响。结果表明：固硫灰、锂渣和硬石膏按照质量比25：15：60能制备出满足GB23439—2009的I型膨胀剂;各原料掺量和细度对混凝土膨胀剂的7d和28d膨胀性能的影响不尽相同。运用SEM电镜扫描、x—ray衍射分析研究了混凝土膨胀剂掺入水泥的水化反应,表明随着水化龄期延长钙矾石含量增多。制备的膨胀剂是以钙矾石为主要膨胀源的混凝土膨胀剂。     

Effects of clinker contents of different C3A and C4AF on the performance of PSC cement

Phosphogypsum-slag-clink (PSC) cement were prepared by original phosphogypsum(PG), which was grinded after dried at 60 °C combined with different contents of phosphogypsum (15%, 20%, 30%), and a small amount of different C₃A, C₄AF contents of finely ground cement clinker, and ground granulated blast furnace slag (GGBFS). Physical mechanical and sugaring properties were studied. The results show that compressive strength of PSC cement with 20% phosphogypsum at 3 d ages would be higher than 17 MPa and even 50 MPa at 28 days. Compressive strength at longer curing stage and sugaring properties of PSC with lower content of C₃A higher C₄AF clinker were improved. pH value of PSC cement system at early stage was relatively low, and pH gradually increased with the addition of clinker. pH increased firstly and then decreased with the hydration stage. SEM analyses showed that the amount of ettringite, which was influenced by pH and content of Al, must be controlled in PSC cement system, which may cause damage to microstructure or even expansive cracks if large amount of ettringite formed in hardened paste.     

煅烧温度对新型生态膨胀剂膨胀性能的影响

以菱镁矿和白云石尾矿为原料,通过调整煅烧温度制备了新型生态膨胀剂,用以补偿大体积混凝土由于温度应力引起的收缩。通过差热-热重、X射线衍射、扫描电镜和液相电导率法等手段对不同温度煅烧所得的产物进行表征分析,并研究它在水泥浆体中的膨胀性能。结果表明：随着煅烧温度的升高颗粒尺寸变大,晶体趋于完整,结构越来越致密,活性越来越差。水化早期,膨胀率随着煅烧温度的升高而减小;水化后期,膨胀率随着煅烧温度的升高而增大。掺量增大,膨胀率越大。提高养护温度,膨胀率增加比较明显,膨胀加速期缩短,膨胀稳定所需时间减少。     

低水胶比掺膨胀剂的水泥水化特性

应用XRD、TG-DTA和温度测量等方法，研究了低水胶比条件下普硅水泥和膨胀水泥的水化特点。结果发现，膨胀水泥水化各龄期中AFt的含量和CH的早期含量明显增加，水化后期CH量则与普硅水泥石基本相当。膨胀水泥硬化浆体的后期膨胀主要依靠凝胶状AFt吸水肿胀而形成驱动力。膨胀刑的组分对膨胀水泥的水化热有明显影响，如果膨胀剂含有硫铝酸盐类矿物，则可能造成体系水化热的升高。     

硅灰对水泥净浆抗硫酸盐侵蚀性能的改善作用

将水泥净浆试件在5%Na2SO4溶液中长期浸泡,用试件强度随浸泡时间的变化和试件中物相的XRD分析,研究了硅灰对水泥净浆抗硫酸盐侵蚀性能的影响.在Na2SO4溶液侵蚀下,普通硅酸盐水泥净浆试件强度随浸泡时间先增长,然后急剧降低;外观和XRD相分析表明,其原因是由于形成了膨胀性钙矾石,造成试件开裂破坏;加入硅灰的水泥净浆试件强度损失明显减小,尤其是抗折强度没有降低,其抵抗强度下降系数还略有增加;原因是由于硅灰的稀释作用和火山灰效应减少了水泥净浆中Ca(OH)2的量,从而降低了水泥净浆试件在硫酸盐溶液侵蚀下形成的膨胀性钙矾石的量.因而,硅灰对水泥混凝土抗硫酸盐侵蚀性能有改善作用.     

Study on activity evaluation of activated coal-gangue and the hydration process

Chemical compositions,mineral compositions and the activated mechanism of the coal-gangue were analyzed. And pozzolana activities of the coal-gangue were evaluated after activated. Moreover,hydration heat and hydration compositions of activated coal-gangue-calcium oxide system,as well as hydration degree and hardened paste microstructures of activated coal-gangue-cement system were studied. Results show that pozzolana activities of the activated coal-gangue root in amorphous SiO2 and activated Al2O3. With the exciting of gypsum,the reaction of activated coal-gangue and Ca(OH)2 would produce hydration products as ettringite,calcium silicate hydrate,and calcium aluminate. The relationship between the curing age and the content of Ca(OH)2 in coal-gangue-cement system was ascertained. Unhydrated particles in the coal-gangue-cement paste were more than that in the neat cement paste at the same hydration periods,and even existed at the later stage of hydration. Furthermore,the activated coal-gangue could inhibit growth and gathering of the calcium oxide crystal,and improve the structure of hardened cement paste.     

Properties of supersulphated phosphogysumslag cement (SSC) concrete

Supersulphated phosphogysum-slag cement （SSC） is a newly developed non-burned cementitious material mainly composed of phosphogysum （PG） and ground granulated blast furnace slag （GGBFS）, with small amount of steel slag （SS） and clinker （CL）. SSC is a kind of environmentally-friendly cementitious material due to its energy-saving, low-carbon emission, and waste-utilization. We prepared concretes with supersulphated phosphogysum-slag cement, and studied the mechanical properties, micro- properties and resistance to chloride penetration of concrete in comparison with those of portland slag cement （PSC） and ordinary portland cement （OPC） concrete. The test results show that the compressive strength of SSC concrete can reach 38.6 MPa after 28 d, close to PSC concrete and OPC concrete. Microanalyses indicate that large quantities of ettringite and C-S-H, and little amount of Ca（OH）2 are generated during the hydration of SSC. The dense cement paste structure of SSC is formed by ettringite and C-S-H, surrounded unreacted phosphogysum. The property of resistance to chloride penetration of SSC concrete is better than PSC and OPC concrete due to the fact that SSC can form much more ettringite to solidify more Cl^-.     

Hydration mechanism of sulphoaluminate cement

The feasibility of sulphoaluminate cement (SAC) utilization in support mortar was studied. Setting time and strength of as-received sulphoaluminate cement (SAC) paste were examined, hydration kinetics behavior was determined through Isothermal Calorimeter, and hydration mechanism was investigated by X-Ray diffraction analysis (XRD) and field emission scanning electron microscopy analysis(FSEM). Results showed that as-received SAC contained 61% of anhydrous calcium sulfate (3CA·CaSO4) and dicalcium silicate (C2S). The strength after 1 day or 3 days grew to 68.6% or 85.7% of that after 28 days respectively, while most of hydration heat was released within 1 day. The emergency of three exothermic peaks at acceleration stage was found and hydration kinetics model was established choosing the terminal time of the first exothermic peak at accelerating stage as the beginning of accelerating stage. XRD analysis suggested that large amount of ettringite (AFt) was produced at early age and FSEM observation revealed that ettringite (AFt) formed in sulphoaluminate cement (SAC) paste was characterized of different morphology which was proved to be caused by different ion concentrations.     

Properties and Acceleration Mechanism of Cement Mortar Added with Low Alkaline Liquid State Setting Accelerator

Low alkaline liquid state setting accelerator(LSA) for Portland cement was prepared in laboratory from aqueous solution of several inorganic sulfate salts and some organic chemical substances. Properties of cement with addition of LSA relating to its setting time and strength development as well as its resistance to sulfate attack for short and long term exposure were experimentally examined. The experimental results showed that 5%-7% addition of LSA significantly accelerated the initial and final setting of Portland cement in the presence or absence of the blending of mineral admixtures, the initial and final setting time being less than 3 min and 6 min respectively. Meanwhile, the early 1 day curing age compressive strength increased remarkably by 20%, while the late 28 th day curing age compressive strength remained almost unchanged as compared with that of the reference accelerator free cement mortar specimen. Furthermore, mortar specimens of cement added with LSA and exposed to 5% Na2SO4 solution showed their excellent resistance to sulfate attack, with their short and long term curing age resistance coefficient to sulfate attack being around 1.04 to 1.17, all larger than 1.0. XRD analysis on hardened cement paste specimens at very early curing ages of several minutes disclosed the existence of more ettringite in specimens added with LSA than that of the reference specimens, meanwhile SEM observation also revealed the existence of well crystallized ettringite at very early hydration stage, suggesting that the accelerated setting of Portland cement can be attributed to the early and rapid formation of ettringite over the whole cement paste matrix due to the introduction of LSA. MIP measurement revealed that hardened cement paste specimens with the addition of LSA presented less medium diameter pores, more proportion of small pores and less proportion of large capillary pores, which is in a very good coincidence with the improvement of strength development of cement mortars added with LSA.     

不同CO2养护压力下硫铝酸盐和硅酸盐水泥浆体早期微观结构

研究硫铝酸盐和硅酸盐水泥（CSA-OPC）浆体在不同碳养护压力下的早期碳化过程,通过X射线衍射、红外光谱、热重、压汞和扫描电镜等测试方法,表征碳化前后水泥浆体的物相组成和微观结构. 实验结果表明,CSA-OPC浆体的水化产物主要为钙矾石,碳化作用使钙矾石转变为碳酸钙和硫酸钙晶体;水泥中碳酸钙以3种晶型存在,其中方解石为主要存在形式. 碳化使半碳型的水化硫铝酸钙（Hc-AFm相）逐渐转化为单碳型的水化硫铝酸钙（Mc-AFm相）,碳化程度和碳化深度随着碳化压力的增加而递增. 碳化后CSA-OPC水化产物体积减小,样品总孔隙率增大、孔隙结构变疏松. 研究结果阐明了CSA-OPC浆体在早期碳化养护条件下的微结构变化过程,为制备基于硫铝酸盐水泥的高效碳汇材料提供了技术支撑.     

Influence of cellulose ethers on hydration products of portland cement

Cellulose ethers are widely used to mortar formulations,and it is significant to understand the interaction between cellulose ethers and cement pastes.FT-IR spectra,thermal analysis and SEM are used to investigate hydration products in the cement pastes modified by HEMC and HPMC in this article.The results show that the hydration products in modified cement pastes were finally identical with those in the unmodified cement paste,but the major hydration products,such as CH(calcium hydroxide),ettringite and C-...     

Long-term Performance of Moderate Heat Portland Cement with Double-expansive Sources

The long-term performance of moderate heat Portland cement with double-expansive sources （DE cement） in the system of high MgO clinker and gypsum was studied by XRD, SEM/EDAX and test methods for strength and expansion of cement. Results indicate that the periclase particle, whose size was 5-7.5μm in DE cement clinker containing 4.8 % MgO, existed individually. The periclase hydration in hardened DE cement paste started at about 60 days and completed up to 2 000 days, and ettringite in the paste was stable from 3 days to 2 000 days. Under the conditions of 4.5%-5.0 % MgO in clinker and 2.8%-3.4 %SO3 in cement, ettringite expansion and brucite expansion in DE cement paste had a continuity, entirety and stability. At the ages of 90, 365,730 and 2 000 days the expansion of the paste reached 0.07%-0.11%, 0.16%-0.21%, 0.21%-0.27 %, and 0.29%-0.38%, respectively. The results suggest that by using this cement in mass concrete it may compensate its temperature shrinkage and autogenous shrinkage to some extent.     

硅酸盐-硫铝酸盐水泥混合体系的试验研究

研究了不同比例的硅酸盐、硫铝酸盐水泥混合体系的凝结时间、水泥砂浆的强度性能,并对一定混合比例的OPC-SAC水泥进行了XRD、SEM和水化量热测试。结果表明,硅酸盐水泥与硫铝酸盐水泥混合,SAC中的C4A3-S矿物与OPC中的C3S矿物在共同水化过程中有相互促进的作用,会使混合水泥水化和凝结加速;混合水泥的强度性能与两种水泥的混合比例有关。本研究可对硅酸盐-硫铝酸盐水泥混合体系的应用提供借鉴。     

Effect of curing conditions on the hydration and performance of CFBC ash cementitious system

Circulating fluidized bed combustion （CFBC） ash can be used as supplementary cementitious material for concrete production for its high pozzolanic activity. We investigated the effect of curing conditions on the hydration and performance of CFBC ash-Portland cement system （30： 70, by mass） including hydration products, paste microstructure, linear expansion ratio, chemically combined water content and compressive strength. The results show that tobermorite rather than ettringite is generated under the condition of autoclaved curing. The expansion and mortar strength of the system cured in water is higher than those cured in air at a given age, and the strength and bulk volume may retract under the condition of air curing. In addition, autoclaved curing facilitates the increase of strength gain at early curing ages （the increase rate lowers down in the following ages） and the improvement of system volume stability. It is suggested that sufficient water is necessary for the curing of CFBC ash cementitious system, and autoclaved curing may be considered where volume stability is a primary concern.     

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.     

新型CSA膨胀剂的水泥基材料性能

针对水泥工业排放出的CO₂过量问题,研究了一种采用工业副产品(流化床锅炉灰)为原料的绿色CSA膨胀剂,并对新型CSA膨胀剂的基本性能和力学性能进行了研究.根据XRD衍射图谱进行分析,探讨了新型膨胀剂的作用机理.结果表明:随着流化床锅炉灰煅烧温度的升高,CSA膨胀剂转换率也升高;水化温度与CSA膨胀剂的掺入量成正比;在干燥收缩试验中,CSA膨胀剂砂浆试件在标准养护35 d后,长度的膨胀效果可达到700×10^-6 m;CSA膨胀剂的掺入量越高,砂浆试件的抗压强度越大.