The Reaction Mechanism between MgO and Microsilica at Room Temperature

It was proved that MgO and MicroSilica can react at room temperature, giving a hardened product primarily comprised of Mg （ OH ）2 and Magnesium Silicate Hydrate （ M- S- H ）. The reaction ratio and process and the chemical composion of M- S- H were studied and analyzed by QXRD and DTA- TG. The experimental results indicate that much Mg（ OH）2 and less M-S-H were formed at early period. After 7 days there is no change in the quantity of Mg（ OH）2, while M-S-H was increased slowly. The chemical composion of M-S-H would vary with the mix proportion in the hydrution process , but M1.32 SH2.37 is finally the approximute form.

Effects of Molecular Structure of Polycarboxylate-type Superplasticizer on the Hydration Properties of C_3S

Effects of polycarboxylate-type superplasticizer（PC） molecular structure on the hydration heat of tricalcium silicate（C3S） paste and polymerization degree of hydration products（C-S-H gel） were researched by using TAM AIR isothermal microcalorimetry（TA） and 29Si nuclear magnetic resonance（NMR）.Methoxy polyethylene glycol-methacrylates-based polycarboxylate superplasticizers with different side chain lengths and main chain lengths were employed.PC molecules with shorter main chain or longer side chains caused stronger retardation of C3S early hydration and lesser increase of C3S 3 d hydration degree.NMR measurement indicated that the incorporation of PC increased the hydration degree of C3S paste and the polymerization degree of silicon-oxygen tetrahedron of C-S-H gel.The tendency for C3S 7 d hydration degree to improve was more pronounced while PC molecules with longer main chain or shorter side chain were added.Whereas,PC molecules with longer main chains or longer side chains increased the 7 d polymerization degree of C-S-H gel.

Effect of Magnesium on the C-S-H Nanostructure Evolution and Aluminate Phases Transition in Cement-Slag Blend

The microstructural study was conducted on cement and cement-slag pastes immersed in different concentrations of Mg（NO3）2 solutions utilizing ^29Si, ^27Al NMR spectroscopy and XRD techniques. The results show that the hydration of both the cement and cement-slag pastes is delayed when the pastes are cured in Mg（NO3）2 solutions as compared to the pastes cured in water. Moreover, Mg^2＋ ions also exhibit an decalcifying and dealuminizing effect on the C-A-S-H in cement and cement-slag pastes, and thereby decrease Ca/Si and Al[4]/Si ratios of the C-A-S-H. The dealuminization of C-A-S-H is mitigated for cement-slag paste as compared to pure cement paste. The depolymerized calcium and aluminum ions from C-A-S-H gel mainly enter the pore solution to maintain the pH value and form Al^[6] in TAH, respectively. On the other hand, Mg^2＋ ions exert an impact on the intra-transition between Al^[6] species, from AFm and hydrogarnet to hydrotalcite-like phase. NO3^-ions are interstratified in the layered Mg-Al structure and formed nitrated hydrotalcite-like phase（Mg1-xAlx（OH）2（NO3）x·nH2O）. Results from both ^27Al NMR and XRD data show that ettringite seems not to react with Mg^2＋ ions.

Chemical Composition and Microstructure of Hydration Products of Hardened White Portland Cement Pastes Containing Admixtures

This study investigated the nature of hydration products of white portland cement （WPC） containing 20 mM malic acid or 1 M calcium chloride hydrated for 11 years. The study identified the hydration products and characterized the chemical composition, morphology, micro/nano structure of C-S-H and the main binding phase in cementitious materials. Calcium hydroxide （CH）, ettringite and C-S-H were identified in WPC with 20 mM malic acid paste hydrated for 11 years. WPC with 1 M calcium chloride paste hydrated for 11 years contained the same phases, but with less CH, and the presence of Friedel＇s salt （Ca2AI（OH）6CI2H2O）. There were still small amount of anhydrous cement particles remaining in both pastes after 11 years hydration according to the SEM and 29Si MAS NMR results. The hydration products of paste containing malic acid had a lower porosity than those prepared with calcium chloride upon visual inspection under SEM. The morphology of the outer product （Op） C-S-H was coarse fibrillar and the inner product （Ip） C-S-H had a very fine microstructure in both pastes under TEM. Both Ip and Op C-S-H formed in paste containing malic acid had lower Ca/Si and higher A1/Si than those in paste containing calcium chloride. C-S-H in paste containing calcium chloride had longer MCL and less percentage of bridging tetrahedra occupied by aluminum in silicon/ aluminum chains due to relatively less Qp and more Q2. A new type of silicon tetrahedra, Q28, was introduced during deconvolution of 29Si MAS NMR results. Ip and Op C-S-H in both pastes had aluminum substituted tobermorite-type and jennite-type structure, and all the charges caused by aluminum substituting silicon bridging tetrahedra were balanced by Ca2＋.

MgO活性对MgO-SiO2-H2O胶凝体系的影响

通过在900℃保温煅烧不同时间来制备活性不同的MgO,研究了MgO与硅灰(SF)所制备胶凝材料(MgO-SF)的流动性、凝结时间、强度和pH值,采用X射线衍射(XRD)、同步热分析(DSC-TG-DTG)、傅里叶红外光谱(FTIR)等分析了MgO对MgO-SF水化产物和水化硅酸镁(MgO-SiO2-H2O,M-S-H)结构的影响.结果表明:随着保温时间的缩短,MgO衍射峰强度减弱,峰宽增大,晶粒尺寸减小,活性增强;高活性MgO制备的MgO-SF净浆和砂浆流动性较差,初凝和终凝时间较短,强度较高;采用保温时间为2.0h的MgO所制备的MgO-SF浆体流动性最好,凝结时间最长,力学性能最好;MgO-SF净浆试样养护3d时M-S-H中Mg(OH)2的含量达到最高,随后降低,在28d时Mg(OH)2含量小幅度增加并出现强度倒缩现象;随着养护龄期的增长,M-S-H含量逐渐增加且其硅酸盐网络结构聚合程度增加.

水化硅酸镁(M-S-H)凝胶的制备与影响因素研究

为深入了解水化硅酸镁凝胶(M-S-H)的性质,本研究以MgO、H2_O,硅灰和稻壳灰为原材料,制备MgO-SF、MgO-RHA浆体,在室内合成M-S-H凝胶产物。通过X射线衍射(XRD),热重(TG)分析,差示扫描量热(DSC)等方法,研究了MgO-SF、MgO-RHA浆体在不同的养护温度、养护周期和SiO_2掺量情况下,对水化生成M-S-H凝胶的影响。研究表明:随着养护温度和养护周期的增长,M-S-H凝胶的生成量逐渐增多。试验表明,养护温度为40℃,养护周期为28 d时,生成的M-S-H凝胶最多。硅灰和稻壳灰均可作为水泥基原材料制备M-S-H凝胶。当MgO与SiO_2掺量的摩尔比为1∶1.5时,两者可以完全反应,比两者摩尔比为1∶1时生成的M-S-H凝胶多。相同条件下,MgO-RHA浆体中的M-S-H凝胶含量比MgO-SF浆体中略少。

基于分子动力学模拟的聚合物纤维/C-S-H界面黏结性能研究

纤维增强混凝土(FRC)的宏观力学性能是由界面微观结构和水化产物与纤维之间的界面结合性能决定的。通过分子动力学模拟研究了PVA,PA和PP纤维在水化硅酸钙(C-S-H)基体中的拉拔过程,表征了聚合物纤维/C-S-H界面的黏结性能。研究结果表明,聚合物纤维类型与复合材料界面的黏结性能密切相关,CS-H黏结性能排序为PVA>PA>PP。界面中的Ca^(2+)通过形成O_(CSH)-Ca-O_(poly)连接,为界面键合的主要贡献者。此外PVA或PA纤维与C-S-H基体之间可以形成H键,起到辅助增强界面键合的作用。通过配位数的分析定量比较了界面处不同键合数目,并联合原子动力学行为差异的分析结果来综合解释键合差异的原因。纤维界面黏结性能在分子尺度的探明有助于指导水泥/纤维复合材料的设计与制备。

Reaction Products of MgO and Microsilica Cementitious Materials at Different Temperatures

The paste was prepared by mixing MgO, microsilica and H2O in the presence of water reducer at different reaction ratios and temperatures, and characterized by XRD, DTA, TGA, IR, and solid-state 29Si NMR. The experimental results showed that, besides Mg（OH）2, magnesium silicate hydrate （M-S-H） was formed at a low temperature such as 25 and 50 ℃. At a high temperature of 100 ℃, Mg（OH）2 can be further transformed into M-S-H completely, for instance, within ca. 1 month in an excess of microsilica. The average composition and structure of M-S-H was mainly related to the reaction mixture and curing temperature and was discussed in detail.

Nanoindentation Characteristics of Cement Paste and Interfacial Transition Zone in Mortar with Rice Husk Ash

The nanostructure of cementitious materials has important effects on concrete properties. The effects of rice husk ash（RHA） on cement hydration product phases and interfacial transition zone（ITZ） in mortar were investigated from the nano-scale structure perspective. The experimental results indicate that, with the increase of RHA dosages of samples, the volume fraction of high-density calcium-silicate-hydrate（HD C-S-H） in porosity and hydration product phases increases. The volume fractions of HD C-S-H in C-S-H of samples show an increasing trend with the increase of RHA dosages. RHA decreases the thickness of ITZ and increases the matrix elastic moduli of samples, however, the RHA dosoges hardly affect the thickness and elastic moduli.

C-S-H复合絮凝剂的制备及其对洗毛废水的处理

针对纺织洗毛废水使用单一絮凝剂处理困难的问题,以水化硅酸钙为原料,将其作为复合絮凝剂无机组分的絮凝性能效果,研究此类复合絮凝剂对絮凝效果的影响和作用。实验表明:改性后的水化硅酸钙、聚合氯化铝和PAM作复合絮凝剂投加,可得到较好的絮凝性能。通过正交实验、单因素实验等方法优化,复合絮凝剂对洗毛废水的污泥去除量超过96%。最佳絮凝工艺为:絮凝剂总投加量2.5 g/100 ml,废水pH值7,温度30℃,搅拌时间4 min。

A Method for Semi-quantitative Analysis of C-S-H Gel in a Blended Cement Paste

An amended method for accurate measuring the quantity of calcium silicate hydrate(C-S-H) in pure cement paste and blended cement paste by water adsorption was made, which based on R.A.Olson’s method. Two improvements to this method, such as using C-S-H gel by hydro-thermal synthesis as standard sample and the stoichiometry of C-S-H gel is partitioned based on hydration time and the amount of mineral admixture. The result of C-S-H gel content in pure cement paste and blended cement paste is higher than by R.A.Olson’s method.

纳米C-S-H-PCE对沿海地铁管片用C50免蒸养混凝土性能的影响

针对蒸汽养护造成的混凝土热损伤问题,利用纳米C-S-H-PCE制备了沿海地铁管片用C50免蒸养混凝土,并采用电导仪、傅里叶红外光谱仪等研究了纳米C-S-H-PCE对水泥净浆水化、混凝土抗压强度、耐久性性能和自收缩性能的影响.结果表明,纳米C-S-H-PCE能够为水化硅酸钙凝胶的形成提供晶核,降低水化硅酸钙凝胶成核的离子临界浓度,促进水化硅酸钙凝胶的形成和Ca^(2+)、SiO_(4)^(2-)的继续溶出,进而缩短水泥水化的诱导期;促进水泥浆体中水化硅酸钙凝胶的聚合,从而提高混凝土的早期抗压强度,提升程度可达312%,但对后期抗压强度影响不大.掺入纳米C-S-H-PCE后,混凝土抗氯离子能力提高了2%~28%,抗碳化能力提高了10%~40%,自收缩变形降低,抗冻性变化不大.

养护温度对MgO/SiO_2体系水化产物微观结构的影响

采用X射线衍射(XRD)和固体魔角核磁共振硅谱(^(29)Si MAS NMR)技术,研究了不同养护温度下MgO/SiO_2体系水化产物的结构特征.结果表明:死烧MgO比轻烧MgO衍射峰强度更大;水化硅酸镁(M-S-H)凝胶呈结晶性较差、短程有序的层状硅酸盐结构;M-S-H含量随着养护温度的升高而增多,相同养护温度下M-S-H的含量随着龄期的延长而增多,50℃下养护28d的试样M-S-H含量最多;养护温度过高会抑制M-S-H的生成;高温养护有利于Q^1向Q^2、Q^2向Q^3转化,使得M-S-H硅氧四面体聚合度提高.

碳化过程中C-S-H平均链长演变规律

为了研究碳化过程中水化硅酸钙凝胶(C-S-H)平均链长的演变规律,采用29Si NMR技术对不同水灰比、不同碳化时间的水泥净浆试样进行了分析.同时,对碳化后试样的氢氧化钙(CH)和CaCO3质量进行了热重分析.结果表明:加速碳化条件下试样的C-S-H平均链长增加,相同水灰比试样的碳化时间越长,其C-S-H平均链长越长;相同碳化时间的试样,水灰比越大,其C-S-H平均链长越长;碳化28d之后,0.53水灰比(质量比,下同)试样的C-S-H已基本完全碳化,0.35水灰比试样的C-S-H结构在一定程度上发生了变化,而0.23水灰比试样的C-S-H结构基本没有变化.另外,0.53水灰比试样的C-S-H碳化不是在CH完全反应后才开始的,碳化至7d时CH和C-S-H都发生了碳化反应且都没有完全碳化.

水泥水化产物——水化硅酸钙(C-S-H)的研究进展

水化硅酸钙(C-S-H)作为水泥基材料的主要水化产物,决定着水泥基材料的强度发展、收缩、徐变和结构的服役寿命,被称为水泥基材料的"基因"。对C-S-H组成、结构和性能的充分认识有助于理解水泥基材料微结构的形成机理,进而对其性能进行自下而上的设计和调控。近年来先进测试和分析技术的发展为C-S-H基本性能的研究提供了新思路。C-S-H的成核生长理论、力学性能提升以及形貌调控等逐渐成为当前研究热点,已取得重要进展。学者们大多采用合成的方法制备体系纯净且具有一定结晶度的C-S-H,并以此研究水泥体系中无定形C-S-H凝胶的基本性能。研究发现,双分解合成C-S-H的成核生长过程中存在球形中间体,其最终转化为箔片状形貌的产物,遵循非经典的成核生长方式。在亚粒子尺度,越来越多的结构信息表明,与尖乃石相比,C-S-H的结构与托贝莫来石更为接近;在粒子尺度上,CM凝胶系列模型被广泛应用于解释C-S-H比表面积等物理参数以及水泥基材料收缩徐变的机理。C-S-H的Ca/Si、含水量、硅链聚合程度以及形貌等微纳结构的广泛研究为建立C-S-H微纳结构与宏观性能之间的联系提供了丰富的数据支撑。对C-S-H进行本征结构调控有望从根本上改善水泥基材料韧性差的力学特征,许多学者试图从孔结构调控、有机和无机复合材料构建以及纳米材料改性等方面提升C-S-H的力学性能,取得了一定突破。本文系统总结了C-S-H的合成方法、成核生长理论、结构模型;主要从Ca/Si、含水量、硅链聚合程度以及形貌四个方面综述了C-S-H的微纳结构;围绕形貌和力学性能介绍了C-S-H的调控和设计方法;分析了目前存在的研究不足并提出了未来的发展方向,以期为全面认识C-S-H以及水泥基材料的性能调控提供借鉴。

Properties of Alkali-activated Yellow River Sediment-slag Composite Material

In order to consume the Yellow River sediment as much as possible and improve the longterm stability of the Yellow River, Yellow River sediment was utilized as the main raw material to produce a composite material. Ca(OH)_2 was used as alkali-activator to activate the active SiO_2 and Al_2O_3 compositions in Yellow River sediment. 10 wt% slag was added into the mixture to further improve the strength of the composites. The effect of activity rate of the Yellow River sediment and dosage of Ca(OH) _2 on the compressive strength of the Yellow River sediment-slag composite material at different curing ages was researched. XRD, SEM/EDS, light microscope and FTIR were used to further explore the products and the microstructure of the composite material. Results showed that the active ratio of sediment had a great influence on the compressive strength of specimen. In addition, the compressive strength of specimen increased with the increase of Ca(OH)_2dosage and curing age. When the dosage of Ca(OH)_2 was more than 5 wt% as well as the curing age reached 90 days, the compressive strength of the composite material could meet the engineering requirement. In the alkali-activated process, the main product was hydrated calcium silicate(C-S-H) gel, which filled up the gaps among the sediment particles and decreased the porosity of the specimen. Moreover, the CaCO_3 produced by the carbonization of the C-S-H gel and excess Ca(OH)_2 also played a role on the strength.

MgO活性对新型水化硅酸镁水泥性能的影响

通过对原料轻烧氧化镁粉在不同温度下进行二次恒温煅烧1.5 h制备不同活性MgO,研究了不同活性MgO与硅灰(SF)和磷酸氢二钾(K 2HPO 4)所制备的新型水化硅酸镁水泥胶凝材料(又称水化磷硅酸镁水泥,MSPHC)的凝结时间、流动度、抗压强度、反应溶液pH值。结合X射线衍射(XRD)、热重分析(TG-DTG)和扫描电子显微镜(SEM)测试手段,分析其影响机理。结果表明:随着煅烧温度的升高,MgO衍射峰强度增大,MgO活性降低;活性越高的MgO制备的MSPHC净浆凝结时间越短且流动性越差,而活性适中MgO制备的MSPHC具有较好的力学性能。MSPHC最主要的水化产物是水化硅酸镁(M-S-H)凝胶,另外还有Mg(OH)2和MgKPO 4·6H 2O(MKP)生成,原料轻烧氧化镁粉中的MgCO 3成分不参与体系反应。活性适中的MgO制备的MSPHC在28 d龄期内的水化产物M-S-H凝胶生成量最多,因此硬化体抗压强度最高。活性越高的MgO在MSPHC反应体系中溶解的速度越快,体系水化反应进程速度也越快。

Quantification of hydration products in cementitious materials incorporating silica nanoparticles

In the present work, silica nanoparticles （30-70nm） were supplemented into cement paste to study their influence on degree of hydration, porosity and formation of different type of calcium-silicate-hydrate （C-S-H） gel. As the hydration time proceeds, the degree of hydration reach to 76% in nano-modified cement paste whereas plain cement achieve up to 63% at 28 days. An influence of degree of hydration on the porosity was also determined. In plain cement paste, the capillary porosity at lhr is ~48%, whereas in silica nanoparticles added cement is -35 % only, it revealed that silica nanoparticles refines the pore structure due to accelerated hydration mechanism leading to denser microstructure. Similarly, increasing gel porosity reveals the formation of more C-S-H gel. Furthermore, C-S-H gel of different CaJSi ratio in hydrated cement paste was quantified using X-ray diffractometer and thermogravimetry. The results show that in presence of silica nanoparticles, -24% C-S-H （Ca/Si 〈 1.0） forms, leading to the formation ofpolymerised and compact C-S-H. In case of plain cement this type of C-S-H was completely absent at 28 days. These studies reveal that the hydration mechanism of the cement can be tuned with the incorporation of silica nanoparticles and thus, producing more durable cementitious materials.

水化硅酸钙的形貌调控及其在水泥水化中的作用

采用化学沉淀法制备无定形、球状、针状、层状等不同形貌的水化硅酸钙(C-S-H),探究了表面活性剂十二烷基苯磺酸钠(SDBS)和十六烷基三甲基溴化铵(CTAB)与C-S-H形貌和结构之间的变化规律,研究了不同形貌的C-S-H对水泥性能的影响。发现当表面活性剂浓度大于临界胶束浓度(CMC)时,水泥水化热与水泥强度之间存在显著相关性。通过C-S-H形貌设计得到不同微观形貌的水泥制品,其增强效果由高到低依次是无定形、球状、针状、层状。该实验结果对于普通水泥的性能改善具有一定的指导意义。

合成钙矾石-水化硅酸钙复合晶种的水泥早强效应

【目的】解析钙矾石-水化硅酸钙晶种的协同效应,改善普通硅酸盐水泥的早期力学强度。【方法】以溶液法合成的超细钙矾石和纳米水化硅酸钙为复合晶种,在微观结构表征基础上,探究钙矾石和水化硅酸钙的掺量以及水灰比对水泥净浆试块1、3 d抗压强度的影响与作用机制。【结果】溶液法合成的超细钙矾石和纳米水化硅酸钙的纯度高,结晶完整,在水中可长时间保持稳定悬浮状态,适合作为复合晶种使用。当纳米水化硅酸钙质量分数固定为5%情况下,随着超细钙矾石掺量的增大,水泥净浆试块的早期抗压强度先升高后降低,在钙矾石掺量(质量分数,下同)为0.6%时,试块的1 d抗压强度提高125%;当钙矾石掺量为0.4%时,水泥净浆试块的3 d抗压强度提高57%。在超细钙矾石掺量一定情况下,水泥净浆试块早期强度随水化硅酸钙掺量的提高而明显增长,但掺量高于5%会导致泌水现象的发生。【结论】超细钙矾石与纳米水化硅酸钙作为复合晶种具有明显的协同效应,可有效提高普通硅酸盐水泥的早期力学强度,早强效果明显优于单独使用的钙矾石或水化硅酸钙晶种。