均相催化水合法合成乙二醇动力学研究

在反应温度为45～75℃,NY 健化剂浓度为0.093mol/L,水比为6～10的反应条件下,对均相催化水合法合成乙二醇动力学进行了研究。测定了反应速率常数及反应过程中溶液 pH 值的变化。依据实验结果,提出了反应机理,建立了反应动力学方程,并利用 Levenberg-Marquardt 方法回归了动力学参数。研究结果表明:在 NY 催化剂存在下,均相催化水合法合成乙二醇反应对环氧乙烷浓度是一级反应,其表观活化能为71113.8 J/mol 和指前因子3.05×10~9 min~(-1)。相对直接水合法而言,NY 催化剂降低了反应的活化能,大大提高了反应速度。     

浆料体系中异丁烯水合反应的实验研究

以高纯异丁烯气体、去离子水为原料,阳离子交换树脂NKC-9颗粒为催化剂,在搅拌高压釜中进行半连续的水合反应,实验考察了温度、压力、催化剂质量含量、叔丁醇初始浓度、搅拌速度及催化剂颗粒粒径对反应的影响。结果表明．过高的温度对反应产生不利影响;增加异丁烯气体压力、提高搅拌速度及叔丁醇初始浓度能提高反应速率;减小催化剂颗粒粒径能提高反应速率,而且超细催化剂颗粒能增强异丁烯气体在水中的传质速率。     

机械激活矿渣水泥

用于式高能振动磨机械激活矿渣（炉渣和／或硅灰）水泥。研究表明：经机械激活后．矿渣水泥的颗粒粒度降低，颗粒的比表面积增大。在掺合了矿渣的水泥中硅微粒聚团经机械激活后可有效地分散并作用于水泥中．使矿渣水泥的水化反应括性增强，促进水泥水化反应，降低水泥制品的孔隙度．从而可以提高水泥制品的力学性能。通过Fourier变换红外光谱和核磁共振等方法分析了机械激活作用的机理。     

矿渣掺量对高水胶比水泥净浆水化产物及孔结构的影响

测定了水胶比为0．5、矿渣质量分数为30％～80％的硬化水泥浆体中Ca(OH)2和非蒸发水量、孔径分布及孔隙率,以确定矿渣在高水胶比条件下的合理掺量。结果表明：即使在矿渣为大掺量情况下也能够改善浆体孔结构,而非蒸发水量、孔隙率随矿渣掺量的变化而变化,并存在使水化产物含量最多、浆体孔隙率最低的矿渣最佳掺量。在矿渣为大掺量情况下,Ca(OH)2含量可降低到极低。在比较纯水泥浆体和掺矿渣浆体的非蒸发水量和孔隙率的基础上提出了矿渣最大有益掺量,矿渣的掺量低于此值时,可使材料的性能得到改善。     

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%。     

硫酸根离子对CaO-Al2O3-P2O5-SiO2体系耐水性的影响

研究了硫酸根离子对CaO-Al2O3-P2O5-SiO2体系耐水性的影响,通过XRD、SEM及孔结构分析手段对其耐水性机理进行分析。结果表明:在CaO-Al2O3-P2O5-SiO2体系中掺入适量的硫酸根离子,不会改变其主要水化产物的组成。浸水180d后,掺石膏的试件211S的耐水性指数较未掺石膏的试件211提高10.2%,劈裂强度提高6.7%,Ca2 、[AlO4]5-离子溶出浓度分别下降11.59%、7.2%,211S具有优异的孔结构。掺入硫酸根离子可以明显的提高该体系的后期强度和耐水性。     

粉煤灰掺合料对砼微观结构的改善

用扫描电镜研究了粉煤灰细石混凝土和普通硅酸盐水泥制成的细石混凝土中的Ca(OH)2、C-S-H及混凝土断面的形貌特征。结果表明,掺加粉煤灰能很好地改善混凝土的微观结构。     

不同煅烧温度下形成的含氟硫A矿对水泥水化性能的影响

为研究不同煅烧温度下，含氟硫熟料中不同性能、形貌特征的A矿与水泥水化形成钙矾石的关系以及A矿对水泥水化性能的影响，采用工业原料并尽量模拟立窑内煅烧状况，对经1350℃和1425℃温度下煅烧的熟料进行了A矿形貌、A矿水化率及A矿与钙矾石形成关系等系列试验。试验结果表明，在传统的煅烧温度下（1400～l425℃）烧成的熟料．其A矿的固溶程度及A矿含量均比低温（1350℃）烧成的高；掺氟硫复合矿化剂烧制的熟料的A矿具有较高的水化速度，熟料强度较高．其制成的水泥在水化时，液相成分受高固溶程度A矿的水化所控制，所形成的钙矾石较低温煅烧的稳定．且A矿水化产物的形成与钙矾石（AFt）的形成较协调，水泥石机械强度更高。     

Autogenous shrinkage of concrete: a balance between autogenous swelling and self-desiccation

According to physical analyses, the driving force of autogenous shrinkage of concrete is the change in the capillary pressure induced by self-desiccation in its cement matrix. Self-desiccation is caused by the balance between the absolute volume reduction (chemical shrinkage) and the building up of the capillary network. The aim of this study was to quantify the influence of the cement characteristics on the chain of mechanisms leading from hydration to autogenous deformations. Four parameters were selected: (i) for clinker, the amount of C₃A and free lime and the SO₃/K₂O ratio; (ii) for cement, the fineness. To master the experimental area, 16 cements were prepared at the laboratory from pure raw materials. An important number of characterizing techniques were used in the experimental study. Their choice was based on the important parameters drawn from the physical analysis: setting time, suspension-solid transition, hydration kinetics through isothermal calorimetry and nonevaporable water, chemical shrinkage, evolution of relative humidity, capillary porosity and autogenous shrinkage. Using different techniques allowed to determine the precise mechanism of action of each parameter. Results showed that these mechanisms are generally different, even if their macroscopic consequences may be identical. This point will probably be useful for modeling and determining the industrial keys reducing the autogenous shrinkage. The physical mechanisms involved in autogenous deformations were further understood. In particular, this study shows that initial autogenous shrinkage should be considered as a balance between the self-desiccation and an initial swelling phase. The influence of the four parameters considered on this last phenomenon were also characterized.     

Behavior of blended cement mortars exposed to sulfate solutions cycling in relative humidity

In recent years, several cases of damage to concrete structures due to sulfate exposure have occurred essentially in the above ground parts of structures. Such distress, often characterized by white efflorescence and surface scaling, is driven by salt crystallization in pores and/or repeated reconversions of certain sulfates between their anhydrous and hydrated forms under cycling temperature and relative humidity (RH). However, the effect of the water/cementitious materials ratio (w/cm), pozzolanic additions, and other parameters on the durability of cement-based materials under such exposure conditions is still misunderstood. In this study, 12 cement mortars having different w/cm (0.30, 0.45, and 0.60) and made with ordinary portland cement (OPC) or OPC incorporating 8% silica fume, 25% class F fly ash, or 25% blast furnace slag were made. Standard bars from each of these mortars were submerged in both 10% magnesium sulfate (MgSO₄) and 10% sodium sulfate (Na₂SO₄) solutions; their expansion and surface degradation was monitored for up to 9 months. In addition, cylinders made from these 12 mortars were partially submerged in 50-mm-deep 10% MgSO₄ and 10% Na₂SO₄ solutions. Half of the cylinders were maintained under constant temperature and RH, whereas the others were subjected to cycling RH. The effect of the w/cm and mineral additions on the classic chemical sulfate attack and development of efflorescence was investigated, and the results are discussed in this article.