2-（4-氯苯氨基）甲基苯酚降解的动力学研究

采用高效液相色谱技术,开展了Fenton试剂对2-（4-氯苯氨基）甲基苯酚（CMP）的氧化降解动力学的研究。考察了初始双氧水摩尔浓度、亚铁离子摩尔浓度和温度等因素对CMP降解速率的影响,结果表明,当双氧水摩尔浓度、亚铁离子摩尔浓度增大和温度升高时,CMP的氧化速率明显加快。在30~45℃的温度范围内,其氧化降解符合假一级反应动力学模型,反应的表观活化能Ea为102.90kJ/mol。     

茂名油页岩的热解特性

利用热重分析仪在非等温条件下对茂名两个矿区的四种油页岩进行了热解试验研究,试验中以高纯氮气作为载气,采用不同的升温速率(10、20、40、50、100℃/min)加热到900℃。粒径范围0~0.2 mm。由失重曲线可知,油页岩的热解主要集中在200~600℃的温度区间。最后根据试验数据建立了热解动力学模型,利用阿累尼乌斯直接作图法求得表观活化能(E)和频率因子(A)等动力学参数。     

中性钠盐碱矿渣水泥水化动力学研究

通过等温导热仪对中性钠盐碱矿渣水泥水化热的测定, 研究了中性钠盐碱矿渣水泥的水化历程, 探讨了其水化动力学参数, 指出水泥水化速度常数具有“即时性”, 确立了中性钠盐碱矿渣水泥不同水化阶段时活化能的计算方法, 明确了各水化阶段水化机理的特征。     

O2/CO2气氛下污泥与烟煤混合燃烧特性

在热重分析仪上开展不同参数条件下污泥和烟煤混合燃烧实验,分析污泥掺混比、升温速率和O2/CO2体积比对燃烧特性的影响,进行燃烧动力学分析.结果表明:O2/CO2气氛下,烟煤掺烧污泥的混合燃烧特性表现为污泥与烟煤燃烧叠加的结果;随着升温速率由10℃/min增加至25℃/min,着火和燃尽温度均升高,着火时间延迟和燃尽时间延长,表观活化能升高;随着O2/CO2体积比的增大,着火温度和燃尽温度均降低,着火时间提前且燃尽时间缩短,表观活化能降低,当O2体积分数超过30%时,燃烧性能改善的幅度越来越小.     

HPAM/Cr(Ⅲ)体系的交联动力学

采用黏度法研究HPAM/Cr(Ⅲ)体系的宏观交联动力学,发现可将交联过程分为诱导期,加速期和终止期3个阶段。在30~60℃范围内,加速期的表观活化能Ea=56.11kJ·mol~(-1)。同时,采用紫外-可见吸光光度法研究HPAM/Cr(Ⅲ)体系的微观交联动力学,可将交联过程分为快速交联阶段和慢速交联阶段2个阶段。结果表明:快速交联阶段的反应速率较慢速交联阶段的反应速率快很多,对吸光度的增加起决定作用,同时得到快速交联阶段在30~60℃范围内的表观活化能Ea=60.95kJ·mol~(-1)。通过黏度法与紫外-可见光度法的结合,可以从宏观和微观上更加清晰地认识HPAM/Cr(Ⅲ)体系交联动力学,为油田上深部调剖提供一定的理论支持。     

硅酸盐水泥水化动力学简化模型

为了更加清晰地阐明水灰比对硅酸盐水泥水化进程的影响,分析了硅酸盐水泥的水化动力学模型(Tomosawa模型,T模型),并将其简化为由传质过程、相界面反应和扩散过程所组成的简化T模型．结合化学结合水法测定水化程度,应用T模型及简化T模型对两种不同水灰比水泥浆体的水化动力学进行研究．结果表明:水泥水化动力学模型中的参数受水灰比的影响各异,其中与传质过程相关的参数几乎不受水灰比的影响;与相界面反应相关的参数受水灰比的影响较小;而与扩散系数相关的参数受水灰比影响显著．简化T模型可以较好地分段模拟水化速率随水化程度变化的总体趋势,且该趋势不受水灰比影响,但是相界面反应控制向扩散过程控制转变时的临界水化程度受到水灰比的影响,且随水灰比增加,临界水化程度增大．     

米糠蜡非等温热分解动力学研究

采用差示扫描量热仪(DSC)测定了米糠蜡的相变温度、熔化温度、最终分解温度,结果表明:米糠蜡的最终熔化温度为82℃、分解温度为425℃;用TG/DSC分析仪在不同升温速率下对米糠蜡进行测试,Kissinger法得到米糠蜡热分解反应的表观活化能、反应级数等动力学参数,结果表明:米糠蜡在200℃以下具有良好的热稳定性,Kissinger法得到的米糠蜡表观活化能为167.43 kJ/mol,反应级数n为0.34.     

丙烯腈-丁二烯-苯乙烯共聚物热降解反应动力学

研究了丙烯腈-丁二烯-苯乙烯共聚物热分析动力学参数.采用热重差热分析法,分别测定了在氮气气氛中5、10、15、20℃/min 4种不同升温速率下的的热降解过程,得到了4条热重和差热曲线,并用Kissinger法对其热降解过程进行了动力学分析.结果表明:提高升温速率,热重曲线向高温方向移动,温度滞后越严重.初始分解温度及终止分解温度更高,温度区间也变宽.升温速率的不同对最终失重率影响不大,最终失重率都在90%以上.随着升温速率的增加,差热曲线峰变高且峰顶温度向高温方向移动.通过Kissinger法分析在不同升温速率下丙烯腈-丁二烯-苯乙烯共聚物热降解反应的热重差热数据得出反应的活化能为160.9kJ/mol、表观指前因子为27.61、热降解反应级数为0.965 4等动力学参数.     

C8H4O5Na2·H2O脱水过程的热分析动力学研究

为了获得一水合5-羟基间苯二甲酸钠(C8H4O5Na2.H2O)固态样品脱水过程的动力学三因子(反应级数n、表观活化能Ea、指前因子A)及相应的动力学方程,应用DSC技术获得化合物4个不同升温速率下的脱水过程曲线,利用多重扫描速率法,以"非模型等转化率法"为基础,采用9种积分法和微分法相结合的热分析动力学方法处理程序进行定量表征.结果显示C8H4O5Na2.H2O脱水阶段的反应为化学反应机理,表观活化能Ea为183.07kJ.mol-1,指前因子A为3.02×1018s-1,动力学方程为(dα/dT)=(3.02×1018)/β(1-α)2exp(-2.202×104/T).     

聚合物-水泥基注浆材料早期流变及水化特性

为制备满足复杂地层加固工程需求的高性能水泥基注浆材料,探究以偏铝酸钠(SA)、聚羧酸(Sp)及高吸水性树脂(SAP)为组分的聚合物体系及其掺量对新拌水泥浆体流变特性与泌水率的影响,并采用水化放热监测与倒置荧光显微技术,对不同体系下水泥浆体早期水化进程及微米级颗粒的悬浮分散形态进行分析.结果表明:新拌水泥浆液流动性和泌水率与SA、SAP掺量呈负相关,随Sp掺量增加而提高. Sp及SAP延缓了水泥早期水化进程,改性样延迟近1 h进入水化诱导期,诱导期内水化放热速率显著降低.在不同掺量SA的促凝效应、Sp的分散效应以及SAP的"水库"作用下,新拌水泥浆液表现为初始及经时流动度大于200 mm的高流态期可分别被控制在10、20、30 min内且析水率小于5%(稳定性浆液),接近临界期时流动度陡降、流变参数突增并迅速凝结的流变特性.结合微观结构观测结果,建立了新拌水泥浆体流变演化模型,揭示多聚合物协调效应下水泥浆体呈现分散-储水-流变-水化的早期流变机制.     

Influence of elevated curing temperature on the properties of cement paste and concrete at the same hydration degree

Three different curing temperatures(20 ℃, 40 ℃, and 60 ℃) were set, so that the nonevaporable water(w_n) contents of plain cement pastes cured at these three temperatures were measured to determine the hydration degree of cement. Tests were carried out to compare the pore structure and strength of cement paste, as well as the strength and permeability of concrete under different temperature curing conditions when their cements were cured to the same hydration degree. The experimental results show that either at a relatively low hydration degree(w_n=15%) or high hydration degree(w_n=16.5%), elevated curing temperature has little influence on the hydration products of cement paste, while it has a negative influence on the pore structure and compressive strength of cement paste. However, this negative effect is weaker at high hydration degree. The large capillary pore(100 nm) volumes of cement pastes remain almost the same at high hydration degree, regardless of curing temperatures. As for the concrete, elevated curing temperature also has negative influence on its compressive strength development, at both low hydration degree and high hydration degree. And this negative effect is stronger than that on cement paste's compressive strength at the same hydration degree. On the whole, elevated curing temperature has little influence on the resistance of concrete to chloride ion penetration.     

复合浆体中粉煤灰和水泥水化反应程度的测定

采用盐酸选择溶解法测定粉煤灰的水化程度,再结合水化热法计算复合浆体中水泥的水化程度。试样结果表明,在水化早期粉煤灰仅作为惰性材料填充于复合浆体的孔隙中。随着粉煤灰掺量的增大,水泥的水化程度越高,单位体积中水化产物的总体数量仍为减少。     

丙烯腈催化水合制丙烯酰胺的反应动力学

研究了以胶体铜为催化剂，丙烯腈水合制丙烯酰胺反应动力学。实验表明，吸附、表面反应、解析，在反应过程中占有重要地位，属子多相催化反应动力学。若以吸附在铜颗粒表面的丙烯腈与液相中的水之间的反应为控制步骤，导出的化学反应动力学方程与实验结果较好的一致，在实验温度４０℃～９０℃范围内，求得活化能Ｅｏ＝１３．１４ＫＪ·ｍｏｌ－１。     

Hydration heat effect of cement pastes modified with hydroxypropyl methyl cellulose ether and expanded perlite

Hydration heat effect of cement pastes and mechanism of hydroxypropyl methyl cellulose ether (HPMC) and expanded perlite in cement pastes were studied by means of hydration exothermic rate, hydration heat amount, FTIR and TG-DTG. The results show that HPMC can significantly delay the hydration induction period and acceleration period of cement pastes. As mixing amount increased, hydration induction period of cement pastes enlarged and accelerated period gradually went back. At the same time, the amount of hydration heat gradually decreased. Expanded perlite had worse delay effects and less change of hydration heat amount of cement pastes than HPMC. HPMC changed the structure of C-S-H during cement hydration. The more amount of HPMC, the more obvious effect. However, EXP had little influence on the structure of C-S-H. At the same age, the content of Ca (OH)2 in cement pastes gradually decreased as the mixing amount increase of HPMC and expanded perlite, and had better delay effect than that single-doped with HPMC or expanded perlite when HPMC and expanded perlite were both doped in cement pastes.     

EFFECTS OF DIFFERENT BURNING PROCESSES ON THE FORMATION KINETICS OF CEMENT CLINKER

Two different methods of burning cement clinker, a rapid burning method and an ordinary burning method used in rotary kiln, respectively, were compared in the laboratory. By means of determining fCaO in the clinkers, rule constant Kr and diffusion activation energy Ea in the two processes of clinker formation were calculated by using Ginstling-Brounshtein diffusion equation and Arrhenius equation. The results show that two processes have very different kinetic constants at the same temperature range 1280-1320C. The rate constant Kr at each temperature in the rapid burning process is much greater than that in the ordinary burning process and the former activation energy Ea is much smaller.     

初凝后水泥浆体的弹性模量研究

在复合材料力学理论与流变学开尔文模型基础上建立了一个用以描述水泥浆体水化早期弹性模量成长的模型.该模型从微观角度出发,在假设水泥颗粒与水化产物为圆球状且水泥浆体形成的孔结构为圆孔形的基础上,应用线弹性理论与有孔介质力学理论研究随着时间的增加、水化度不断增大的情况下,硬化水泥浆体的有效弹性模量.将该有效弹性模量与流变学开尔文模型理论结合起来得出初凝后水泥浆体弹性模量时变方程.研究结果表明:该模型可用于描述水泥浆体初凝后的弹性模量变化,且其变化规律与精度和实验数据符合良好.     

单环芳烃型高效减水剂对水泥水化浆体微观影响

从水化热、水化产物、水泥浆体孔隙结构、微观结构变化4个方面,研究了单环芳烃型高效减水剂对水泥水化反应的影响.使用TAM Ai进行水化热测定表明,掺加单环芳烃型高效减水剂可延缓水泥初期水化和明显降低水化热,MRI分析表明同龄期的掺单环芳烃型高效减水剂水泥浆体与空白样相比孔隙总体积与总孔隙率都有增加的趋势,水泥浆体孔径分布变化不大.XRD、TG-DTA、SEM分析表明掺加单环芳烃型高效减水剂抑制水泥水化过程中水化产物Ca(OH)<,2>和水化硅酸钙产生,不影响水化产物与水化过程最终结果,掺加单环芳烃型高效减水剂使氢氧化钙、钙矾石与C-S-H等水泥水化产物细化.     

电阻率法研究早期水泥净浆孔结构的演变过程

采用无电极电阻率法原位连续监测3种水灰比（0.23、0.35和0.53）水泥净浆早期水化过程中电阻率的变化全过程,同时结合等温量热仪测试的水化程度,建立水泥净浆随时间发展过程中浆体电阻率与孔结构发展的定量关系。结果表明：根据电阻率及其微分曲线的变化规律可以把水泥水化过程分为4个阶段：溶解期、诱导期、加速期和减速期。水灰比越低,毛细孔隙率和收缩因子变小,曲折因子变大,致使浆体电阻率升高,而孔溶液电阻率却下降。     

Influence of cellulose ethers on hydration products of portland cement

Cellulose ethers are widely used to mortar formulations,and it is significant to understand the interaction between cellulose ethers and cement pastes.FT-IR spectra,thermal analysis and SEM are used to investigate hydration products in the cement pastes modified by HEMC and HPMC in this article.The results show that the hydration products in modified cement pastes were finally identical with those in the unmodified cement paste,but the major hydration products,such as CH(calcium hydroxide),ettringite and C-...     

Hydration Characteristics of Sodium Sulfate Slag Cement System

The hydration characteristics by thermal analysis ( DTA ) were determined, and an isothermal calorimeter (IC) was used to study the pastes . The experimental results indicate: (1) The main hydration products of SSC are C-S-H( I ) gel with a low Ca/Si ratio, crystalline Thomsonite-type and AFt-type phases containing certain alkali cations; (2) No phases of the AFm-type and high alkaline Ca( OH)2 in SSC system could benefit the hydrated cements to improve its strength and durability; (3) Crystalline Thomsonite-type and AFt-type phases containing Na will greatly reduce free alkali and alleviate the harmness of alkali aggregate reaction ( AAR) in SSC system; (4) Similar to ordinary Portland cement( OPC), the hydration process of SSC could be classified into five stages : initial, induction, acceleration, deceleration and decay; (5) Regardless of the activator used, the apparent activation energy is higher with the increased slag in cement system, and the rising temperature could promote the hydration of SSC.