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%。     

Utilization of fly ash coming from a CFBC boiler co-firing coal and petroleum coke in Portland cement

Fly ash coming from a circulating fluidized bed combustion (CFBC) boiler co-firing coal and petroleum coke (CFBC fly ash) is very different from coal ash from traditional pulverized fuel firing due to many differences in their combustion processes, and thus they have different effects on the properties of Portland cement. The influences of CFBC fly ash on the strength, setting time, volume stability, water requirement for normal consistency, and hydration products of Portland cement were investigated. The results showed that CFBC fly ash had a little effect on the strength of the Portland cement when its content was below 20%, but the strength decreased significantly if the ash content was over 20%. The water requirement for normal consistency of cement increased from 1.8% to 3.2% (absolute increment value) with an addition of 10% CFBC fly ash; and the free lime (f-CaO) content of CFBC fly ash affected the value of increasing. The setting time decreased with an increase of CFBC fly ash content. The volume stability of the cement was qualified even when the content of SO₃ and f-CaO reached 4.48% and 3.0% in cement, respectively. The main hydration productions of cement with CFBC fly ash were C-S-H (hydrated calcium silicate), AFt (ettringite), and portlandite.     

Studies on blended cement with a large amount of fly ash

The influence of the contents of the clinker, activators and fly ash on the properties of blended cement with high fly ash content was studied. Experimental data from X-ray diffraction and pore size distribution indicated that the main hydration product of the fly ash blended cement was C-S-H gel, ettringite and a small amount of Ca(OH)₂. The volume porosity of the pores with diameter bigger than 0.1 μm was lower than that of the micro pores and gel pores with diameter lower than 0.05 μm. The amount of chemical combined water has increased with the curing age duration, while the content of Ca(OH)₂ has reduced after 7 days.     

海水和矿物掺合料对硫铝酸盐水泥砂浆性能的影响

本文研究了不同拌和水以及海水拌和时粉煤灰和硅灰掺量对硫铝酸盐水泥(SAC)砂浆力学性能和表观孔隙率以及净浆凝结时间、化学收缩、孔溶液pH值和氯离子结合能力等的影响,并通过XRD、SEM和EDS分析水泥水化产物和微观结构。结果表明,海水能加快SAC早期水化并提高其早期强度,但后期强度和淡水拌和时无明显差别。粉煤灰和硅灰均会延长SAC凝结时间,对早期抗压强度不利,而掺加质量分数为5.0%和7.5%的硅灰能提高SAC砂浆28 d抗压强度。硅灰掺量增加时会提高用水量和表观孔隙率,降低流动性,使水泥化学收缩增大,降低净浆pH值且减少氯离子结合量;粉煤灰能够提高砂浆流动性,减少水泥化学收缩,但掺量越大对SAC砂浆抗压强度和抗折强度越不利,掺质量分数为10%的粉煤灰可小幅提高氯离子结合量且减小表观孔隙率。     

Properties of high-volume fly ash concrete incorporating nano-SiO2

This paper presents a laboratory study on the properties of high-volume fly ash high-strength concrete incorporating nano-SiO₂ (SHFAC). The results were compared with those of control Portland cement concrete (PCC) and of high-volume fly ash high-strength concrete (HFAC). Assessments of these concrete mixes were based on short- and long-term performance. These included compressive strength and pore size distribution. Significant strength increases of SHFAC compared to the high-volume fly ash high-strength were observed as early as after 3 days curing, and improvements in the pore size distribution of SHFAC were also observed. In this work, the hydration heat of nano-SiO₂ fly ash cement systems was also studied in comparison to the fly ash-cement systems and to the pure cement systems. In addition, the weight change of fly ash incorporating nano-SiO₂, fly ash, and nano-SiO₂ alone after immersed in saturated lime solution was also studied.     

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。     

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.     

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。     

水泥-硅灰/粉煤灰体系强度、收缩性能与微观结构研究

为研究硅灰及粉煤灰对不同养护龄期的水泥浆体强度及收缩性能的影响,以水胶比为0.29的水泥浆体为基体,设计制备了五种硅灰及粉煤灰掺量的复合水泥浆体,借助量热仪和压汞仪测试表征了不同复合水泥浆体的水化放热特性以及孔结构组成,分析了水化放热量、孔隙率等参数随硅灰和粉煤灰掺量增加的变化规律,建立了复合浆体抗压强度与孔结构以及水化特性与收缩应变之间的量化关系。结果表明,掺入粉煤灰会大幅降低水泥净浆早期抗压强度,但对减小自收缩应变和干缩应变极为有利。掺入硅灰能明显提高净浆3 d抗压强度,但当硅灰掺量超过10%(质量分数)后,净浆3 d自收缩应变及28 d干缩应变增加极为明显。掺入硅灰会使水泥水化诱导期开始和结束的时间提前,还会增加水化反应级数和各阶段的反应速率常数值,导致水泥-硅灰复合浆体的水化放热总量和放热速率相较于水泥-粉煤灰体系大幅增加。粉煤灰和硅灰的掺入均能有效细化水泥浆体内部孔结构,提高凝胶孔比例,大幅降低大孔比例。复合浆体的72 h水化放热总量和3 d自收缩应变呈现正相关关系,而孔隙率和抗压强度呈现明显的负相关关系。     

Early age strength enhancement of blended cement systems by CaCl2 and diethanol-isopropanolamine

The enhancement of the 1 day strength of cementitious systems by a combination of calcium chloride (CaCl₂) and diethanol-isopropanolamine (DEIPA) was studied, particularly in blended cement systems. A combination of quantitative X-ray diffraction with Rietveld refinement (QXRD), scanning electron microscopy (SEM)/backscattered electron image analysis, thermogravimetric analysis (TGA), and isothermal calorimetry were used to investigate the mechanism of strength enhancement by the additives. The additives were found to increase the early age mortar strength by enhancing the cement hydration, with the DEIPA enhancing primarily the aluminate hydration. DEIPA also affected the morphology of portlandite which was formed as thin plates. In parallel, the calcium-to-silica ratio of the C-S-H was found to increase with the use of DEIPA, possibly because of the inclusion of microcrystalline portlandite. After 48 h DEIPA was found to directly enhance the rate of reaction of granulated blast-furnace slag and fly ash.     

Effects of mineral and chemical admixtures on high-strength concrete in seawater

The effects of mineral and chemical admixtures namely fly ash, ground granulated blast furnace slag, silica fume and superplasticizers on the porosity, pore size distribution and compressive strength development of high-strength concrete in seawater curing condition exposed to tidal zone were investigated. In this study, three levels of cement replacement (0%, 30% and 70% by weight) were used. The total cementitious content used was 420 kg/m³. A water/binder ratio of 0.4 was used to produce concrete having a target compressive strength ranging between 54 and 63 MPa at the age of 28 days. At the age of 364 days, the compressive strength of the specimens produced ranged between 59 and 74 MPa. The pore size distribution of both high-strength concrete (MSS-0 and MSS-40) was significantly finer and the mean volume pore radii (MVPR) at the age of 6 months were reduced about three times compared to NPC concrete. Results of this study indicate that both concrete mixes (30% and 70%) exhibited better performance than the NPC concrete in seawater exposed to tidal zone. Hence, it is believed that both high-strength concrete produced would withstand severe seawater exposure without serious deterioration.     

Improvement of the durability of glass fiber reinforced cement using blended cement matrix

Blended cements prepared with two fly ashes were used as matrices in glass fiber reinforced cement (GRC) composites in an attempt to improve their durability. The hydrated matrices from the two blended cements investigated here had similar strength and composition. Both fly ashes reduced the Ca(OH)₂ content to the same extent but in both cases the pH level was only slightly reduced compared to the portland cement matrix. In spite of these similarities, the GRC prepared with one fly ash showed considerable improvement in durability while the other one had only a small positive effect. SEM observations indicated that the improved durability in one case was associated with modification in the microstructure of the hydration products deposited in between the glass filaments, resulting in a much more open structure compared to that of portland cement matrix or the other blended cement. It is therefore suggested that the potential of the blended cement matrix to improve the durability of GRC is associated with its ability to modify the microstructure of the paste at the glass interface. This characteristic is not necessarily related to the overall composition of the blended cement matrix and to the reactivity of fly ash with Ca(OH)₂.     

Effect of fly ash–gypsum blend on porosity and pore size distribution of cement pastes

Abstract

Abstract

This paper reports results on the porosity and pore size distribution (PSD) of cement paste containing simulated desulphurised waste (SDW). The SDW was chosen due to the variability in chemical composition of real desulphurised waste. The SDW is a combination of fly ash and gypsum. The content of fly ash in the SDW changed from 0 to 100% by weight. The water to binder ratio was 0·5. The binder consists of cement and SDW. Cement in the pastes was partially replaced with 25 wt-% SDW. The porosity and PSD of cement pastes at 28 days of curing is reported. Increasing amount of gypsum does not seem to greatly change the pore volume; however, there is tendency of obtaining coarser pore structure in the presence of gypsum. The compressive strength increases with increasing amounts of gypsum. Correlation between strength and PSD is conducted.     

低品位粉煤灰的改性及其对水泥浆体强度和自收缩的影响

采用石灰石粉对低品位粉煤灰进行煅烧改性,利用X射线衍射、扫描电镜和能谱分析等方法对改性粉煤灰的矿物组成和化学组成进行表征.同时测定了掺改性粉煤灰的水泥浆体的抗压强度和自收缩,并采用背散射扫描电镜和压汞测孔仪研究了掺改性粉煤灰水泥浆体的微观结构.结果表明,粉煤灰经煅烧改性生成了水硬性矿物β-C2S,水化可生成CSH凝胶,改善了等外粉煤灰颗粒与水泥基体的界面粘接,降低了复合水泥浆体的孔隙率和自收缩,提高了复合水泥浆体的强度.     

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。     

Hydration of fly ash cement

It is necessary to establish the material design system for the utilization of large amounts of fly ash as blended cement instead of disposing of it as a waste. Cement blended with fly ash is also required as a countermeasure to reduce the amount of CO₂ generation. In this study, the influences of the glass content and the basicity of glass phase on the hydration of fly ash cement were clarified and hydration over a long curing time was characterized. Two kinds of fly ash with different glass content, one with 38.2% and another with 76.6%, were used. The hydration ratio of fly ash was increased by increasing the glass content in fly ash in the specimens cured for 270 days. When the glass content of fly ash is low, the basicity of glass phase tends to decrease. Reactivity of fly ash is controlled by the basicity of the glass phase in fly ash during a period from 28 to 270 days. However, at an age of 360 days, the reaction ratios of fly ash show almost identical values with different glass contents. Fly ash also affected the hydration of cement clinker minerals in fly ash cement. While the hydration of alite was accelerated, that of belite was retarded at a late stage.     

粉煤灰对水泥浆体早期水化和孔结构的影响

通过硬化水泥浆体力学性能、交流阻抗和孔结构等性能的测试,以及扫描电镜分析,研究了不同掺量的粉煤灰对硬化水泥浆体早期水化和孔结构的影响。结果表明：随着粉煤灰掺量的增加,水泥的凝结时间增加,抗压强度降低,熟料矿物的水化速率提高,但水泥-粉煤灰体系的水化速率降低,水泥浆体中孔溶液电阻和阻抗相应降低,硬化水泥浆体中大孔数量减少,微孔数量增加。     

高钙粉煤灰-水泥体系细度匹配与胶砂强度关系的试验研究

将高钙粉煤灰与纯水泥分别粉磨至不同的细度 ,然后分别与纯水泥按 1∶1的比例配成高钙粉煤灰水泥 ,进行龄期抗压强度试验。运用origin软件 ,以水泥与高钙粉煤灰比表面积之差S 为x轴 ,以它们混合后的比表面积S为y轴 ,以高钙粉煤灰 -水泥试样的抗压强度为z轴 ,进行三维区域图分析 ,给出各项性能指标发展趋势与水泥、高钙粉煤灰的相对位置以及混合体系总体细度的相互关系 ,进而考察高钙粉煤灰与水泥的细度匹配 ,并用高钙粉煤灰早期化学结合水量方法测定各匹配的高钙粉煤灰水泥的早期水化速度 ,以证实其宏观结果     

磨细矿物掺合料对水泥硬化浆体孔结构及砂浆强度的影响

采用压汞法研究了钢渣、矿渣、粉煤灰单掺或复掺对水泥硬化浆体孔结构的影响.同时还研究了掺合料单掺或复掺对水泥砂浆抗压强度的影响.结果表明:掺合料单掺或复掺对早期水泥硬化浆体的孔结构有一定的劣化作用;水化后期,矿渣与钢渣均明显降低了水泥硬化浆体的孔隙率,矿渣与粉煤灰均明显降低了水泥硬化浆体的中值孔径并改善了水泥石的孔径分布,掺合料复掺对改善水泥硬化浆体的孔结构有积极作用,尤其是掺合料三元复合可取得最佳的效果.3种掺合料降低水泥硬化浆体孔隙率能力的大小顺序为:矿渣>钢渣>粉煤灰.3种掺合料降低水泥硬化浆体孔径并改善孔径分布能力的大小顺序为:矿渣>粉煤灰>钢渣.掺合料降低了水泥砂浆早期的抗压强度,却增加了水泥砂浆90 d的抗压强度.掺合料的活性大小顺序为:矿渣>钢渣>粉煤灰.