粉煤灰水泥基材料的水化产物

用热重仪-差示扫描量热仪、扫描电子显微镜、透射电子显微镜、X射线能量散射、高分辩电子显微镜、压汞仪,测定了粉煤灰水泥基材料水化产物的形貌特征、微观结构、化学组成及水泥石的孔结构,讨论了水化产物性质及水泥石孔结构随粉煤灰掺量的变化规律。结果表明：粉煤灰的大量掺加,可以改善凝胶的化学组成。水化后期,粉煤灰与Ca(OH)2及由熟料水化生成的高n(Ca)／n(Si)的水化硅酸钙(C—S—H)凝胶发生二次水化反应,生成低n(Ca)／n(Si)的C—S—H凝胶,此种凝胶的固碱能力强,可减少碱-集料反应的危害性。同时,二次水化产物能够填充那些对水泥石强度和耐久性极为不利的孔隙空洞,使水泥石的结构更加致密,优化水泥石的孔结构,对提高水泥基材料的耐久性作用极大,为进一步提高工业废渣利用的技术水平奠定了基础。     

粉煤灰-水泥浆体的孔体积分形维数及其与孔结构和强度的关系

采用压汞法对不同龄期粉煤灰-水泥浆体的孔分形结构进行了实验研究，测定了复合浆体孔体积分形维数，探讨了孔体积分形维数与孔隙率，孔表面积、平均孔径、孔分布及宏观力学性能的关系。实验结果表明：粉煤灰-水泥浆体的孔结构具有明显的分形特征，孔体积分形维数在3．3～3．5之间；孔体积分形维数越大，浆体的孔径越小、孔隙率越低，孔表面积越大，小于20nm的微孔越多，大于100nm的大孔越少，而且复合体系的抗压及抗折强度也越高。     

The influence of water removal techniques on the composition and microstructure of hardened cement pastes

The removal of water from hardened cement paste for analysis or to arrest ongoing hydration has been reported to affect the composition of hydrated phases and microstructure. The effect that arresting the hydration of hardened cement paste by replacing the pore water with acetone before drying, and by removing the water by freeze, vacuum and oven drying has on the hardened cement paste has been investigated. Two pastes were studied, a cemented iron hydroxide floc where a high proportion of ordinary Portland cement (OPC) had been replaced by pulverised fuel ash, and a pure hydrated OPC. The results showed that none of the water removal techniques caused any major deterioration in the composition and microstructure of the hardened cement pastes studied, but the pores appeared better preserved after arresting hydration using acetone quenching. Freeze drying appeared to cause more cracking of the microstructure than the other water removal techniques.     

Activation of fly ash cementitious systems in the presence of quicklime: Part I. Compressive strength and pozzolanic reaction rate

In the first part of this study, the effect of industrially produced quicklime on the strength development and pozzolanic reaction rates of different fly ash/cement (FC) systems was investigated. Two high calcium fly ashes, diversified on their active silica and calcium oxide contents, and one with moderate calcium content were used. Strength development, hydration evolution, and pozzolanic reaction rates of the quicklime-fly ash-cement (QFC) systems were monitored and presented. Moreover, new efficiency factors were calculated for the activated systems in an attempt to optimize the quicklime addition in each case, whilst correlations were attempted between the nonevaporable water contents (W_n) and the cementitious efficiency factor (k values) of the activated systems. The addition of quicklime increased both the early and later strengths of the high-calcium fly ash specimens. For the two high-lime ashes tested, a 3% addition of quicklime was found to be the optimum dosage both for short and longer curing periods. It is possible that such an offer of lime fully employed the available silica from the ashes to form additional cementitious compounds, principally pozzolanic C-S-H. In the case of lower-lime fly ash, a small quantity of added lime (5%) was found to be effective only during the initial stages of the hardening process. When quicklime additions increased, no accelerating effect was detected, as a result of the diminished proportion of soluble silica in the pore solution. Identification of the generated hydration products, porosity of the activated mixtures and examination of their microstructure will be presented in Part II of the study.     

掺合料对硫铝酸盐水泥抗Cl-渗透性能的影响

研究了矿渣、粉煤灰和沸石粉单掺及复掺时对硫铝酸盐水泥砂浆Cl-渗透性的影响,采用SEM、孔结构等方法分析了不同龄期的净浆水化产物.结果表明,在硫铝酸盐水泥浆体中,加入掺合料可以改善结构致密性,提高抗Cl渗透能力,3种掺合料作用效果为:矿渣＞粉煤灰＞沸石粉;复掺时效果更好,矿渣与粉煤灰复掺＞矿渣与沸石粉复掺＞沸石粉与粉煤灰复掺.     

粉煤灰的微观形态及其在水泥水化中的特性

研究粉煤灰的形貌、微观结构、形成机理及水化界面特性。水化后期,粉煤灰颗粒表面层已完全与水泥水化产物发生二次反应,填充水泥石的孔隙空洞,使孔结构高度细化,强度逐渐提高。     

不同pH值碱性电解水对砂浆工作性能和强度的影响

碱性电解水具有强碱性、高活性、离子性和吸附性等优点,本文利用不同pH值(9.5、10.5、11.5)的碱性电解水制备粉煤灰砂浆,并在粉煤灰取代率为0%、15%及30%(质量分数)的条件下,系统研究了不同pH值碱性电解水对粉煤灰砂浆的工作性能、力学性能以及Ca(OH)₂等水泥水化产物含量的影响规律,并利用XRD、SEM等微观试验对比分析了不同pH值的粉煤灰净浆的结构组成和微观形貌特征。试验结果表明:随着pH值的提高,相较于普通自来水粉煤灰砂浆,碱性电解水粉煤灰砂浆的流动度、抗压强度和抗折强度逐渐提高,水化产物Ca(OH)₂含量逐渐降低。当碱性电解水pH值为10.5,粉煤灰取代率为15%时,碱性电解水粉煤灰砂浆的早期强度和流动度的改善效果达到最佳,28 d的抗压强度和抗折强度较普通水砂浆分别提高了8.4%和12.5%。同时,相较于普通自来水净浆,不同pH值的碱性电解水净浆的团簇化和颗粒化均表现得更加明显,这对于促进水泥水化进程,提高砂浆流动性,激发粉煤灰早期活性起到了积极作用,除了生成更多的C-S-H凝胶体和Ca(OH)₂等水化产物以外,还生成了钾长石等其他水化产物。     

Mechanism for performance of energetically modified cement versus corresponding blended cement

The microstructure of cement paste of 50/50 mixes of cement/quartz and cement/fly ash, both ground in a special mill [energetically modified cement (EMC) process] and simply blended, have been studied under sealed curing conditions. The grinding process reduced the size of both cement grains and quartz/fly ash markedly and created flaky agglomerates of high inner surface for the finer particles. EMCs had much higher degree of hydration at 1 day, but similar as blends at 28 days. The pores were much finer for EMC paste due to smaller particles as also reflected in the strength. The morphology of calcium hydroxide in EMC paste appeared more mass like. Pozzolanic reaction was insignificant for quartz in EMC, but increased for fly ash. Thus, improved performance of EMC versus OPC can be explained by increased early hydration and extensive pore size refinement of the hardened binder resulting in reduced permeability and diffusivity for concrete.     

Influence of a fine glass powder on cement hydration: Comparison to fly ash and modeling the degree of hydration

This paper reports the results of an investigation carried out to understand the influence of a fine glass powder on cement hydration. The pozzolanicity of the glass powder and a Class F fly ash for comparison was evaluated using strength activity index over a period of time, and a rapid electrical conductivity based method. Flame emission spectroscopy and electrical conductivity tests were used to quantify the alkali release from glass powder, and gain information on the rate of alkali release. It was found that the glass powder releases only a very small fraction of sodium ions into the solution. It was observed that the glass powder modified pastes show higher non-evaporable water contents than the plain paste and fly ash modified pastes, indicating that glass powder facilitates enhancement in cement hydration. An expression has been developed for the change in non-evaporable water content as a result of enhancement in cement hydration and the hydration of the cement replacement material. The efficiency of any cement replacement material with age in the paste system can be quantified using this parameter. Based on this parameter, a 5% cement replacement with glass powder was found to be effective at the chosen water-to-cementing materials ratio (w/cm), whereas at higher replacement levels, the dilution effect dominates. A model to predict the combined degree of hydration of cement pastes incorporating more than one cementing material is outlined. The measured and predicted combined degrees of hydration agree well.     

垃圾焚烧飞灰胶凝活性和水泥对其固化效果的研究

垃圾焚烧飞灰是生活垃圾焚烧后烟气除尘器收下的物质,其主要成分属CaO-SiO_2-Al_2O_3-Fe_2O体系,与目前常用的高炉矿渣、粉煤灰等辅助性胶凝材料非常接近,因其中含有能被水浸出的重金属物质而被认为是危险废物,必须对之进行稳定及固化处理。通过试验研究了掺入垃圾焚烧飞灰的硬化水泥浆体的力学性能和水化机理,考察了水泥固化垃圾焚烧飞灰的效果,探讨了垃圾焚烧飞灰作为辅助性胶凝材料利用的可行性。研究表明:垃圾焚烧飞灰的水化反应活性较低,它的掺入在一定程度上延缓了水泥的水化过程,虽然其水化过程可以形成适量的钙矾石,对强度发展有利,但掺量较大时会显著降低水泥强度;采用水泥稳定及固化垃圾焚烧飞灰的效果良好,垃圾焚烧飞灰中重金属可以通过包容、替代或吸收等形式固化进水化产物结构中。     

煤矸石对硅酸盐水泥水化历程的影响

从强度、反应程度、孔溶液碱度和SEM等方面,研究了煤矸石作为水泥辅助胶凝材料的水化情况,并与Ⅱ级粉煤灰进行比较。试验结果表明:煤矸石发生火山灰反应时间比粉煤灰早,且发生火山灰反应所需的碱度值比粉煤灰低;掺煤矸石水泥水化样的早期抗压强度比粉煤灰水泥水化样低,但7d到28d强度增长速率明显大于相同掺量的粉煤灰水泥,相同28d抗压强度的条件下,煤矸石掺量比粉煤灰的掺量高10%。     

Sulphate resistance of OPC, OPC/fly ash and SRPC pastes: pore structure and permeability

Fly ash is a slow acting pozzolana and requires substantial curing to achieve its potential strength and durability properties. Results are presented of the sulphate resistance, permeability and pore size distribution of OPC, OPC/fly ash andSRPC pastes variously cured before immersion in 0.7M Na₂SO₄. A range of pores is identified which are particularly susceptible to sulphate attack and a qualitative relationship established between the variation, with curing, of the entry size of these pores, the permeability of the paste and sulphate resistance.     

矿物掺合料对水泥耐酸性的影响及配比设计

以硅粉、粉煤灰和矿渣为矿物掺和料,采用XRD和SEM研究了矿物掺和料对水泥水化产物、水泥石结构和形貌的影响,探讨了酸溶液对水泥的腐蚀机理,并对矿物掺和料配比进行优化设计,以提高水泥的耐酸性.研究结果表明:掺加矿物掺和料有利于改善水泥石孔结构,降低水泥碱度,当硅粉、粉煤灰和矿渣以占水泥质量5%,10%和15%的配比掺入时,水泥的耐酸性最好.     

Improving the performance of ternary blended cements by mixing different types of fly ashes

For overcoming certain drawbacks characterizing both basic types of fly ashes (of high and low calcium content), different ash intermixtures consisting of two types of fly ashes were prepared. The principal idea lying beneath the effort presented herein is that beneficial assets of the one type of ash could compensate for the shortcomings of the other. Compressive strength development, pozzolanic activity potential and nature of hydration products of all ternary cements were closely monitored and presented in comparison to the respective properties of the initial binary blends. Moreover, efficiency factors were calculated for all new systems and were further used to validate previously reported expressions describing Binary Fly ash-Cement (BFC) systems. In accordance with previous works, ternary fly ash systems examined here outperformed the respective binary systems almost throughout the curing period. Synergy between the different types of fly ashes was considered the main reason for the excellent performance of the ternary mixtures. Results obtained indicate that previously developed analytical expressions, correlating active silica of SCMs and k-values, can be applied in the case of multicomponent ash systems as well.     

矿物掺合料对蒸养水泥净浆性能的影响

研究了蒸养条件下粉煤灰、矿渣的掺量对水泥净浆化学结合水量和抗压强度的影响,揭示了矿物掺合料对蒸养水泥净浆水化性能和力学性能的影响。试验结果表明,与标准养护相比,蒸汽养护更有利于激发粉煤灰和矿渣的火山灰活性,促进水泥的早期水化,提高水泥浆体的早期强度;但无论是蒸汽养护还是标准养护,随着矿物掺合料掺量的增加,复合胶凝材料的水化性能和力学性能明显减弱,因此矿物掺合料掺量不宜太大。     

粉煤灰掺量对氯氧镁水泥混凝土物理力学性能的影响

为了拓展氯氧镁水泥(MOC)材料的应用领域,以盐湖提钾肥副产物水氯镁石、轻烧氧化镁和粉煤灰为胶凝材料,制备了不同粉煤灰掺量的氯氧镁水泥混凝土(MOCC)。研究了粉煤灰掺量对MOCC抗压强度、物相组成、微观形貌和孔结构的影响。结果表明:随着粉煤灰掺量的增加,MOCC的抗压强度逐渐降低,当粉煤灰掺量为40%(质量分数)时,其300 d抗压强度降低至39.99 MPa,降低了22.52%。MOCC的主要水化产物为5Mg(OH)₂·MgCl₂·8H₂O(5·1·8)和Mg(OH)₂,掺加粉煤灰并没有产生新的晶相。掺入粉煤灰增加了MOCC的孔隙率和有害孔体积,从而降低了其抗压强度。采用相同水灰比制备了普通硅酸盐水泥混凝土,抗压强度对比测试结果表明:掺40%的粉煤灰MOCC的抗压强度虽然比未掺粉煤灰MOCC抗压强度低,但仍比普通硅酸盐水泥混凝土300 d龄期的抗压强度(33.42 MPa)高出19.66%,说明MOCC比普通硅酸盐水泥混凝土具有较高的抗压强度。     

蒸汽养护条件下甲酸钙/纳米C-S-H复合对粉煤灰-水泥体系早期水化的影响

本文研究了蒸汽养护条件下,甲酸钙/纳米C-S-H(NC)复合对粉煤灰-水泥体系早期抗压强度的影响,并结合XRD、DSC-TG、MIP、SEM及FTIR等手段分析了其影响机理。结果表明:蒸汽养护条件下掺入甲酸钙能显著提高粉煤灰-水泥体系的早期抗压强度,且掺量为1.5%(质量分数)时效果最佳;甲酸钙能促进水泥和粉煤灰水化,提高水化产物的生成速率,降低粉煤灰-水泥体系的孔隙率和总孔容;在掺入甲酸钙的基础上掺入NC可进一步提高体系抗压强度,且随着NC掺量的增加而提高;NC能促进水化产物生成,提升水化程度,细化孔结构,提高体系致密度。     

海水环境下矿物掺合料对硫铝酸盐水泥的水化影响

研究了海水环境下掺入硅灰、粉煤灰、矿渣对硫铝酸盐水泥抗压强度、化学收缩和水化产物的影响规律.结果表明:当硅灰的掺量为2.5%时,水泥浆体的抗压强度比空白组高.矿渣掺量为10%的水泥浆体28 d抗压强度明显超过掺入硅灰和粉煤灰时的强度,60 d强度高于空白组.掺入2.5%硅灰后,水泥浆体的化学收缩增大;在水化早期,粉煤灰和矿渣的火山灰活性很低,导致水泥浆体的化学收缩降低.掺入10%硅灰加快了硫铝酸盐水泥3 d水化反应,钙矾石生成量增多,水泥浆体早期强度比掺其它掺合料有所提高,但体积过快膨胀会破坏其内部结构,对水泥浆体的强度发展不利.     

Hydration mechanisms of ternary Portland cements containing limestone powder and fly ash

The effect of minor additions of limestone powder on the properties of fly ash blended cements was investigated in this study using isothermal calorimetry, thermogravimetry (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM) techniques, and pore solution analysis. The presence of limestone powder led to the formation of hemi- and monocarbonate and to a stabilisation of ettringite compared to the limestone-free cements, where a part of the ettringite converted to monosulphate. Thus, the presence of 5% of limestone led to an increase of the volume of the hydrates, as visible in the increase in chemical shrinkage, and an increase in compressive strength. This effect was amplified for the fly ash/limestone blended cements due to the additional alumina provided by the fly ash reaction.     

低水胶比下超细粉煤灰对不同细度硅酸盐水泥水化历程的影响

从强度、结合水、粉煤灰反应程度、SEM分析及孔隙溶液碱度等方面,研究了低水胶比下超细Ⅱ级粉煤灰对不同细度硅酸盐水泥水化历程的影响。研究结果表明,水泥细度从4500cm2/g提高到5500cm2/g,对纯水泥水化过程影响不大。但当该高细度水泥与超细II级粉煤灰复合时,则对水泥及粉煤灰的水化程度、水化产物特性、孔隙溶液碱度以及力学性能均影响较大;随粉煤灰掺量的增加,其影响程度呈由小变大再变小的趋势,粉煤灰掺量存在阈值,本试验中,阈值为30%。