考虑界面过渡区及集料因素的水泥基材料碳化模型

集料和界面过渡区对水泥基材料抗碳化性能有显著影响。基于Fick第二定律,提出一种考虑集料和界面过渡区影响的CO₂扩散模型,模型中首次引入界面过渡区的扩散系数并给出相应参数的计算方法,并基于质量守恒定律给出CO₂反应模型,利用该模型研究荷载作用下C30和C50混凝土中CO₂的浓度分布。结果表明,考虑集料和界面过渡区影响能更准确地计算CO₂在水泥基材料中的扩散系数及碳化深度值。通过与文献中的试验数据进行比较,进一步验证了理论模型的可靠性。模型将集料和界面过渡区作为评价混凝土耐久性的重要因素,为钢筋混凝土结构的设计和寿命预测提供依据。     

具有可见光响应的改性纳米TiO2研究进展

通过改性可以改变TiO₂只有在紫外光激发下才显示出较高光催化效率的特点,使其在可见光范围也显示出较高的活性。本文综述了纳米TiO₂改性方面的研究进展,指出通过元素掺杂、贵金属修饰、聚合物修饰、半导体复合、染料敏化等手段对TiO₂进行改性,可以减小纳米TiO₂禁带,提高纳米TiO₂对可见光的响应性和量子效率。分析认为,实验室制备的改性纳米TiO₂可见光光催化效果已经比较理想,解决回收难、工程易操作性等问题是未来的发展方向。     

纳米SiO2超高强高流态混凝土及改性机理

通过正交试验提出纳米超高强高流态混凝土的胶凝材料配合比设计参数,并研究了纳米SiO₂的掺入对传统掺硅灰、粉煤灰超高强水泥基胶凝材料强度及工作性能的影响。在保证水胶比不变的条件下,开展了混凝土配合比试验,并研究了纳米SiO₂对混凝土抗压强度的影响及其微观机理。结果表明：超高强高流态混凝土中胶凝材料最优比例为：纳米SiO₂：硅灰：粉煤灰：水泥=1：8：20：71;在胶凝材料用量为600~1 000 kg/m³范围内,随着其掺量的增加,混凝土流动度不断增加,抗压强度先增大后减小,当其掺量为800 kg/m³时,抗压强度最大。分析认为,纳米SiO₂、硅灰与粉煤灰形成的三元多尺度堆积体系能优化粉体材料在混凝土中的微集料密实填充效应,纳米SiO₂的二次水化反应也有效改善了硬化水泥石的微观结构,并优化其形态分布,进一步增大其强度。     

沸石负载Mn,N共掺杂TiO2及光催化性能

为提高传统TiO₂光催化剂的可见光催化活性,本文采用溶胶-凝胶法合成了Mn,N共掺杂TiO₂光催化剂,改善了传统TiO₂光生载流子易复合的问题;进一步采用沸石作为载体对改性后的TiO₂样品进行负载,解决了传统光催化剂存在的难分离回收问题,以达到光催化剂可重复使用的目的.借助X-射线衍射仪、扫描电子显微镜、紫外分光光度计、傅立叶变换红外光谱仪等测试手段对Mn,N共掺杂TiO₂光催化剂的结构、元素组成、微观形貌和光催化降解性能进行系统分析与研究.研究结果表明,沸石负载Mn,N共掺杂TiO₂的样品较未改性的TiO₂样品具有更高的光催化降解活性,在可见光照射下,在最优掺杂条件下获得的TiO₂光催化剂在60 min内对孔雀石绿的降解率可达到97%,这主要归因于锰离子掺杂能够对TiO₂光生载流子的复合产生抑制作用,促进光生电荷分离,与此同时氮元素掺杂可有效拓宽TiO₂半导体光催化剂光响应范围.此外,经过5次循环使用后,对孔雀石绿的降解率没有较大程度的减弱,依然能够维持在88%以上,表明沸石负载Mn,N共掺杂TiO₂的样品具有较好的光催化循环稳定性.     

Pd纳米晶修饰TiO2纳米管阵列光电极的制备及性能

为提高TiO₂的可见光催化性能,采用阳极氧化法在Ti箔上原位生成TiO₂纳米管阵列,再利用阴极电沉积法制备了贵金属Pd纳米晶修饰的TiO₂纳米管阵列光电极,并利用扫描电子显微镜（SEM）、X-射线光电子能谱（XPS）及紫外-可见漫反射光谱（UV-vis DRS）对其表观形貌、表面形态及光吸收性能进行表征．结果表明:Pd纳米晶有效地修饰在TiO₂纳米管阵列的表面,且以Pd⁰形式存在．此外,Pd纳米晶修饰明显拓展了TiO₂纳米管阵列的可见光响应范围．以甲基蓝为模型污染物,重点考察阴极沉积电压及沉积时间对其光催化性能的影响．结果表明:阴极沉积电压为-0.8 V、沉积时间为10 min对甲基蓝的光催化降解效果最佳,且符合拟一级反应动力学模型．模拟太阳光下光照120 min对甲基蓝的降解率可达71.4％,是纯TiO₂纳米管阵列光电极的1.5 倍．     

水环境中不同浓度TiO2纳米颗粒混凝工艺去除效果

为了探究水环境中不同质量浓度TiO₂ 纳米颗粒(NPs)混凝工艺去除影响因素及与浊度去除规律的区别,研究了在超声预处理后投加表面活性剂(LAS)对TiO₂ NPs分散稳定性的影响,通过烧杯实验分别考察了混凝剂(聚合氯化铝,PAC)投加量及pH对不同质量浓度TiO₂ NPs和浊度去除的影响,及pH对TiO₂ NPs表面Zeta电位的影响机制．结果表明,在250 W超声处理10 min后加入20 mg／L的LAS获得的纳米悬浮液稳定性最好;不同混凝剂投加量下,TiO₂ NPs和浊度的去除规律呈相近趋势,TiO₂ NPs初始质量浓度为0.5,1和2 mg／L时,PAC最优投加量为3 mg／L,对应TiO₂ NPs和浊度最大去除率分别为46.2％、60.2％、68.8％和23.2％、43.6％、47.6％．TiO₂ NPs初始质量浓度为5 mg／L时,PAC最优投量为4 mg／L,TiO₂ NPs和浊度最大去除率分别为77.64％和54.08％．pH对TiO₂ NPs表面Zeta电位有明显影响,进而影响TiO₂ NPs的去除效果．     

超低离子渗透性水泥基材料的性能与微观结构

采用显微硬度、MIP、SEM—EDXA研究了超低离子渗透性水泥基材料（Ultra Low Ion Permeability Cementitious Materials,简称ULIPCM）的微观结构,同时研究了UI。IPCM的宏观性能。结果表明：ULIPCM的28d抗压强度≥80MPa,抗折强度≥11．0MPa,弹性模量在38．0～42．0GPa之间;Cl^-扩散系数≤0．8×10^-13m^2·s^-1,6h导电量≤300C;抗硫酸盐侵蚀性能较好;28d收缩值可控制在400×10“以内。UI．IPCM的集料与水泥石界面过渡区的微观结构和性能得到了显著改善,有利于提高其力学性能和抗渗性能。ULIPCM的集料与水泥石界面过渡区由普通混凝土的60～100μm细化为30μm以下,有效阻断了侵蚀性介质的渗入通道;ULIPCM的孔隙率、最可几孔径等孔结构参数均得到了优化,显著改善了其孔结构;ULIPCM的集料与水泥石界面过渡区中的CH晶体较少,且CH晶体的取向性差。     

TiO2/石墨烯复合材料的水热法合成与光催化性能

为了提高TiO₂的光催化性能,采用水热法一步制备了TiO₂/石墨烯(TiO₂/RGO)复合物．采用XRD、FT-IR、RS、UV-Vis DRS、TEM等测试方法对其进行了表征,并研究了不同质量比的复合物在可见光下对甲基橙(MO)的光催化降解．结果表明:在TiO₂/RGO复合物中,TiO₂以10 nm左右的颗粒均匀地分散在石墨烯层上;与在同等条件下制备的TiO₂相比,TiO₂/RGO复合物在可见光区吸收明显增强,吸收边缘红移了20 nm;质量比为1∶0.005的TiO₂/RGO复合物,2 h内的降解率达到74.79％．可见将石墨烯与TiO₂复合,能够有效地提高TiO₂的可见光催化性能．     

活性矿物掺合料对超高性能水泥基材料的影响

通过复掺粉煤灰和硅灰,制备一种抗压强度超过200 MPa的超高性能水泥基复合材料(UHPCC),采用扫描电镜、微区能谱分析、X射线衍射、汞压入法和差示扫描量热分析等现代测试手段,研究了活性矿物掺合料对UHPCC微观结构及性能的影响.实验结果表明,UHPCC水泥石主要以低mCa/mSi、结构致密的C-S-H凝胶和许多未水化颗粒组成;活性矿物掺合料的火山灰效应使水泥浆体与集料间界面过渡区得以改善;矿物掺合料的微集料效应使体系颗粒级配优化,致使基体内部结构致密,总孔隙率减小,孔尺寸得到细化,孔结构得以优化,材料性能得以提高.     

混凝-超滤工艺去除水中复合污染物试验研究

研究分析腐殖酸对水溶液中纳米TiO₂稳定性的影响,探究混凝剂投加量、pH值、钙离子对混凝-超滤工艺去除水中腐殖酸-纳米TiO₂复合污染物的影响。结果表明,纳米TiO₂与腐殖酸在水溶液中发生静电吸附以及配位反应,使纳米TiO₂有效粒径减小,静电斥力增强,胶体分散更均匀,体系稳定性增加,易于迁移,从而给饮用水安全带来威胁。在单因素影响实验中,实验结果显示,混凝剂浓度为0.46 mmol/L、pH值在7~8之间（即弱碱性）时,能有效去除复合污染物,此时,膜通量较高,膜污染较轻,而水中钙离子的存在会加重膜污染。     

Multi-scale modeling of the effective chloride ion diffusion coefficient in cement-based composite materials

N-layered spherical inclusions model was used to calculate the effective diffusion coefficient of chloride ion in cement-based materials by using multi-scale method and then to investigate the relationship between the diffusivity and the microstructure of cement-basted materials where the microstructure included the interfacial transition zone（ITZ）between the aggregates and the bulk cement pastes as well as the microstructure of the bulk cement paste itself.For the convenience of applications,the mortar and concrete were considered as a four-phase spherical model,consisting of cement continuous phase,dispersed aggregates phase,interface transition zone and their homogenized effective medium phase.A general effective medium equation was established to calculate the diffusion coefficient of the hardened cement paste by considering the microstructure.During calculation,the tortuosity（n）and constrictivity factors（D_s/D₀）of pore in the hardened pastes are n≈3.2,D_s/D₀=1.0×10^-4respectively from the test data.The calculated results using the n-layered spherical inclusions model are in good agreement with the experimental results;The effective diffusion coefficient of ITZ is 12 times that of the bulk cement for mortar and 17 times for concrete due to the difference between particle size distribution and the volume fraction of aggregates in mortar and concrete.     

再生细骨料及其混凝土的微观结构特征

采用扫描电镜、能谱分析、X射线衍射、显微硬度和氮吸附等微观测试方法研究了再生细骨料及其混凝土的微观结构特征.研究结果表明:再生细骨料是一种组成复杂的、具有一定水化活性的和高渗透性的人造骨料,其主要矿物相为SiO2、CaCO3以及少量的C2S.再生细骨料混凝土内部水泥石孔隙较多,结构密实性较差,同时其与再生细骨料间存在较为明显的界面过渡区,该界面过渡区宽度较大,且界面过渡区两侧的骨料和水泥石的显微硬度均较低.再生细骨料的多孔结构,以及再生细骨料混凝土内部水泥石和界面过渡区微观结构缺陷是导致其大孔增多的主要原因,大孔的增多会对混凝土抗渗性产生不利影响.     

水泥基复合材料界面过渡区体积分数的定量计算

为了计算水泥基复合材料的界面过渡区体积分数,采用最邻近表面分布函数和骨料比表面积2种方法,结合实际骨料的筛分曲线,给出了界面过渡区体积分数定量关系式．结果表明：单位体积水泥基复合材料中,当骨料的体积分数〈0．5,界面厚度〈50μm时,2种方法计算的误差约为10％;界面区厚度越小,2种方法计算的误差也越小．     

Influence of Thermally Treated Flue Gas Desulfurization （FGD） Gypsum on Performance of the Slag Powder Concrete

The feasibility of flue gas desulphurization （FGD） as concrete admixture was studied. A combined concrete admixture of the thermally-treated FGD gypsum and slag powder was explored. The FGD gypsum was roasted at 200℃ for 60 min and then mixed with the slag powder to form FGD gypsum-slag powder combined admixture in which the SO3 content was 3.5wt%. Cement was partially and equivalently replaced by slag powder alone or FGD gypsum-slag powder, at concentration of 25wt%, 40wt%, and 50wt%, respectively. The setting times, hydration products, total porosity and pore size distributions of the paste were determined. The compressive strength and drying shrinkage of cement mortar and concrete were also tested. The experimental results show that, in the presence of FGD gypsum, the setting times are much slower than those of pastes in the absence of FGD gypsum. The combination of FGD gypsum and slag powder provides synergistic benefits above that of slag powder alone. The addition of FGD gypsum provides benefit by promoting ettringite formation and forms a compact microstructure, increasing the compressive strength and reduces the drying shrinkage of cement mortar and concrete.     

矿物掺合料对机制砂水泥基自流平砂浆性能的影响

试验选用普通硅酸盐水泥、硫铝酸盐水泥与半水石膏的三元胶凝体系,选用机制砂作为细集料,制备全机制砂水泥基自流平砂浆.选用粉煤灰、石粉与硅灰作为矿物掺合料,并研究矿物掺合料对全机制砂制水泥基自流平砂浆流动度、抗压抗折强度与尺寸变化率的影响.研究结果表明:矿物掺合料的火山灰效应对自流平砂浆力学性能的发展产生积极影响,自流平砂...     

Comparison of hydration properties between cement-GGBS-fly ash blended binder and cement-GGBS-steel slag blended binder

The hydration properties of cement-GGBS-fly ash blended binder and cement-GGBS-steel slag blended binder were compared. The experimental results show that the hydration rate of cement-GGBS- steel slag blended binder is higher than that of cement-GGBS-fly ash blended binder within 28 days, but lower than the latter after 28 days. The hydration of cement-GGBS-steel slag blended binder tends to produce more Ca（OH）2 than the hydration of cement-GGBS-fly ash blended binder, especially at late ages. Cement-GGBS- steel slag mortar exhibits higher strength than cement-GGBS-fly ash mortar within 28 days, but at late ages, it exhibits similar compressive strength with eement-GGBS-fly ash mortar and even slightly lower bending strength than cement-GGBS-fly ash mortar. Cement-GGBS-steel slag paste has finer early pore structure but coarser late pore structure than cement-GGBS-fly ash paste. Cement-GGBS-steel slag paste can get satisfied late pore structure and cement-GGBS-steel slag mortar can get satisfied late strength as compared with pure cement paste and pure cement mortar, respectively.     

Influence of Superplasticizer Type and Dosage on Early-age Drying Shrinkage of Cement Paste with Consideration of Pore Size Distribution and Water Loss

We introduced a parameter r_s (the radius of the pores where the meniscus forms),which is composed of two factors,i e,water loss and cumulative pore size distribution (PSD),to provide a better explanation of the influence of superplasticizers(SPs) on early-age drying shrinkage.In our experiments,it is found that the addition of three types of SPs leads to a significant increase in the early-age drying shrinkage of cement paste,and drying shrinkage increases with the dosage of SPs.Based on the results above,we further studied the mechanism of the effects of SPs on the early-age drying shrinkage of cement paste by PSD and water loss,which are two components of r_s.The experimental results indicate that r_s can be a better index for the early-age drying shrinkage of cement-based materials with SPs than a single factor.In addition,the effects of SPs on other factors such as hydration degree and elastic modulus were also investigated and discussed.     

超临界碳化对水泥基材料性能和孔径结构的影响

为了考察超临界碳化技术在水泥基材料改性方面的应用,研究超临界碳化对水泥基材料微观和宏观性能的影响,基于此设计了超临界二氧化碳碳化试验研究水泥砂浆、水泥净浆和混凝土试件的碳化深度、强度、孔径分布以及二氧化碳吸收量的变化。试验分析表明,超临界碳化可以快速实现水泥基材料的碳化,大幅提高试件强度,改善材料的孔径分布,使材料的中细径孔大幅降低,提高材料的抗渗透能力,为改善重金属等危害废物的水泥基固化效果提供了依据。同时超临界碳化可以将大量二氧化碳转化在碳酸钙中沉淀吸收,具有重要的环境保护意义。     

水泥基材料早期水化特性与体积稳定性的关系

采用五路裂缝测定仪和非接触式电阻率测定仪，分别测试了水泥砂浆在干燥条件下约束收缩开裂的初裂时间与相应水泥浆体早期水化24h内的电阻率变化，分析研究了水泥浆体在非常早期水化中的电阻率极小值与相应砂浆的初裂时间的关系，结果发现二者之间具有较好的线性相关性（相关系数〉0．90）。机理研究表明在水泥类型和骨料确定的条件下，胶凝材料体系初始水化的液相特征是影响早期收缩开裂的关键；不同化学与矿物外加剂及微量组分（可溶碱）的添加将通过改变水化的液相特征而影响水化物的初始形成速率、形貌、分散性及其生长能力等，最终影响材料的体积稳定性。