活化煤矸石在水泥基材料中的早期水化动力学研究

采用活化煤矸石(CCG)部分取代波特兰水泥的方式,对比研究了CCG对CCG-水泥复合胶凝材料的凝结时间、力学性能和水化热反应等的影响.利用水化热法研究了CCG-水泥复合胶凝体系的水化特性;并基于Krstulovic-Dabic模型,分析了CCG-水泥复合胶凝体系的水化反应机理.试验结果表明,活化煤矸石取代硅酸盐水泥熟料的最佳掺量为30％,此掺量下,能保证良好的力学性能与工作性能;CCG对CCG-水泥复合胶凝材料的早期水化无明显影响,后期活化煤矸石中的铝相、硅相会与氢氧化钙反应发生火山灰效应;活化煤矸石能增大水泥水化结晶成核与晶体生长(NG)、相边界反应(Ⅰ)过程的反应程度并降低扩散(D)阶段的反应程度;同时能降低NG、I过程的反应速率,并在不高于30％的掺量下,对D过程的反应速率有一定的增强作用.     

水化热抑制剂对复合胶凝材料体系早期水化动力学的影响

本文研究了水化热抑制剂(TRI)对水泥-粉煤灰-矿渣复合胶凝材料早期水化过程。通过改变矿物掺合料在胶凝材料中的质量占比以及TRI的掺量,研究了胶凝材料的水化特性,并基于Krstulovic-Dabic水化动力学模型计算了反应速率常数、几何晶体生长指数等动力学参数。结果表明,矿物掺合料和TRI复合使用会延缓胶凝材料水化并降低最大放热速率;复合胶凝材料的水化过程均有结晶成核与晶体生长、相边界反应以及扩散3个阶段,Krstulovic-Dabic水化动力学模型能较好地模拟各复合胶凝材料的水化过程;矿物掺合料和TRI会影响复合胶凝材料水化产物的结晶成核以及晶体生长,并降低复合胶凝材料各阶段的水化速率。     

石灰石粉对水泥水化及C-S-H成核的动力学影响

通过等温量热试验研究了掺入不同掺量和细度的石灰石粉时水泥水化的放热速率及放热量,分析其随时间的变化规律.同时对水化放热速率及放热量曲线进行动力学分析,通过计算拟合得到水泥-石灰石粉体系的KNG、KI、KD等水化动力学参数,分析石灰石粉掺量、细度对水泥水化动力学过程及其对C-S-H成核的影响,探究石粉加速水泥水化的关键因素.研究结果表明:石灰石粉加速了水泥早期水化,C-S-H成核效率随石粉掺量增大先增大后减小,10％掺量时最大,C-S-H成核效率随石灰石粉细度的增大而增大.水泥水化的NG过程随石粉掺量增大而逐渐延长,I过程随石灰石粉掺量增大而缩短.     

石灰石粉-粉煤灰细度变化对水泥基胶凝材料体系水化动力学的影响

为研究混磨不同细度石灰石粉-粉煤灰对水泥基胶凝材料水化进程和早期力学性能的影响规律,本文采用等温量热法测定了不同细度复合胶凝体系在水化温度为20 ℃时的水化放热速率和放热量,根据Krstulovic-Dabic提出的水化动力学模型计算了复合胶凝体系水化反应各阶段的动力学参数。结果表明:增加石灰石粉和粉煤灰的细度可促进复合胶凝体系水化产物的结晶成核与晶体生长,缩短水化诱导期结束时间和达到最大放热速率时间,加速水泥的水化反应速率。石灰石粉和粉煤灰细化会缩短相边界反应过程时间,使复合胶凝体系在水化程度更高时发生反应控制机制转变。抗压强度试验表明增加细度可明显提高胶砂试件的早期强度,其后期强度保持稳定。     

氯氧镁水泥水化历程的影响因素及水化动力学

为了深入研究氯氧镁水泥的水化机理,进而对其性能进行预测和改进,采用美国TAM Air热导式等温量热仪研究了氯氧镁水泥的水化动力学。测定了不同条件下氯氧镁水泥体系的水化放热过程,根据水化放热曲线,研究了该体系水化各阶段的动力学过程,探讨了实验因素对该体系水化过程的影响,并通过实验数据拟合得到了氯氧镁水泥水化过程的动力学方程。结果表明:氯氧镁水泥水化过程的不同阶段受不同作用机理控制,加速期是受成核控制的自动催化反应时期,衰减期受扩散作用控制,而减速期受自动催化反应和扩散作用双重控制。同时,原料MgO的活性、反应温度及矿物外加剂的种类和数量都不同程度地影响了该体系的水化过程。     

不同温度下矿渣-水泥复合胶凝体系水化反应特性研究

研究了不同水化温度对矿渣-水泥复合胶凝体系水化反应特性的影响.研究表明:随着水化温度的降低,复合胶凝体系的水化放热速率、非蒸发水含量、强度均呈现出降低的趋势,负温条件下复合胶凝体系的水化反应特性与常温一致;通过计算获取各个阶段的反应速率曲线,可较好地对由量热实验数据绘制的复合胶凝体系实际水化速率dα/dt曲线进行分段的模拟;将不同温度下复合胶凝体系水化放热量的数据转换为水化反应程度α,对既有模型进行验证.结果表明,现有模型可较准确的预测低温下复合胶凝体系的水化反应程度.     

粉煤灰-矿粉-水泥三元体系水化放热模型研究

通过直接法研究了在水泥中掺入不同掺量的粉煤灰和矿粉时样品的水化放热速率曲线,通过各样品的水化放热曲线研究粉煤灰-矿粉-水泥三元体系水化放热模型.通过试验实测结果与模型计算结果相比,两者最大误差为8.1％,最小误差仅为3.4％,发现胶凝材料的水化过程符合根据水泥水化建立的水化动力学模型.     

基于Krstulovic-Dabic模型的复合胶凝体系水化特性研究

将粉煤灰、矿粉、膨胀剂、纳米硅、粘改剂等掺合料按一定比例加入基准水泥中,采用等温量热仪测试了复合胶凝体系在5℃、20℃和30℃下的水化放热速率曲线.同时基于Krstulovic-Dabic模型,计算了相应的水化动力学参数,讨论了温度和掺合料对水化动力学参数的影响,探讨了复合胶凝体系复杂的水化机理.结果表明,复合胶凝体系的水化放热速率峰值随温度升高呈指数增加,而峰值到达时间则随温度升高呈指数减小,水化动力学参数随温度升高显著增大.掺合料的加入降低了复合胶凝体系的水化动力学参数和水化放热速率峰值,并使放热峰值提前出现,特别是膨胀剂和纳米二氧化硅作用显著.计算得到的反应速率曲线与测试得到的实际速率曲线的拟合精度受到温度和掺合料的影响.     

矿渣水泥水化动力学的研究

应用恒温导热量热仪对矿渣水泥和波特兰水泥的水化动力学进行了研究。实验结果表明,水泥水化在不同反应阶段具有不同的反应机理,所适用的动力学公式及动力学参数亦不同。加速期由自动催化(auto catalytic)反应控制,减速期由化学反应和扩散过程双重控制,衰减期由扩散过程控制。矿渣水泥对温度的敏感性高于波特兰水泥,原因是矿渣玻璃相具有较高的表观活化能。提高温度(热激发)对矿渣水泥的水化更为有利。在研究中采用两种活性不同的矿渣,它们的活性之差别可以从水化动力学参数K、E与N(与反应机理有关的常数)反映出来。     

含不同掺量矿渣或粉煤灰的复合胶凝材料的水化动力学

采用等温量热法测定了矿渣掺量分别为0、30%、50%、70%、90%和粉煤灰掺量分别为0、20%、35%、50%、65%的复合胶凝材料在298K时的水化放热速率和放热量。根据Krstulovic-Dabic水化动力学模型计算了反应速率常数、几何晶体生长指数等动力学参数,并讨论了水化反应各阶段的反应速率与反应程度的关系。结果表明:不同矿渣掺量和不同粉煤灰掺量的复合胶凝材料的水化过程均可表示为结晶成核与晶体生长、相边界反应和扩散3个阶段。所用动力学模型能较好地表征矿渣掺量在70%以内及粉煤灰掺量在65%以内的复合胶凝材料的真实水化过程。矿渣掺量90%的复合胶凝材料的水化机理发生了改变,所用动力学模型不再适用。     

Many Drugs of Abuse May Be Acutely Transformed to Dopamine,Norepinephrine and Epinephrine In Vivo

It is well established that a wide range of drugs of abuse acutely boost the signaling of the sympathetic nervous system and the hypothalamic–pituitary–adrenal (HPA) axis, where norepinephrine and epinephrine are major output molecules. This stimulatory effect is accompanied by such symptoms as elevated heart rate and blood pressure, more rapid breathing, increased body temperature and sweating, and pupillary dilation, as well as the intoxicating or euphoric subjective properties of the drug. While many drugs of abuse are thought to achieve their intoxicating effects by modulating the monoaminergic neurotransmitter systems (i.e., serotonin, norepinephrine, dopamine) by binding to these receptors or otherwise affecting their synaptic signaling, this paper puts forth the hypothesis that many of these drugs are actually acutely converted to catecholamines (dopamine, norepinephrine, epinephrine) in vivo, in addition to transformation to their known metabolites. In this manner, a range of stimulants, opioids, and psychedelics (as well as alcohol) may partially achieve their intoxicating properties, as well as side effects, due to this putative transformation to catecholamines. If this hypothesis is correct, it would alter our understanding of the basic biosynthetic pathways for generating these important signaling molecules, while also modifying our view of the neural substrates underlying substance abuse and dependence, including psychological stress-induced relapse. Importantly, there is a direct way to test the overarching hypothesis: administer (either centrally or peripherally) stable isotope versions of these drugs to model organisms such as rodents (or even to humans) and then use liquid chromatography-mass spectrometry to determine if the labeled drug is converted to labeled catecholamines in brain, blood plasma, or urine samples.     

ICP-MS法测定地球化学样品中As、Cr、Ge、V等18种微量痕量元素的研究

建立了测定地球化学样品中包括As、Cr、Ge、V等18种微量、痕量元素的ICP-MS方法。地化试样用HF-HNO3混酸分解后,以1 1 HNO3溶解干渣。由于制样不使用盐酸,避免了Cl对As、Cr、Ge、V的质谱干扰。用国家一级地球化学标准物质GBW 07309制备溶液优化仪器工作参数,并用于校准。方法测定限(6s)为:0.007~6.4μg/g,精密度(RSD%,n=12)为:29%~9.4%,经过国家一级地球化学标准物质的分析验证,结果与标准值吻合。方法已应用于国土资源调查的试样分析。     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

基于ATRP法制备的触角状亲水性羟胺树脂的吸硼性能的研究

以大分子引发剂氯乙酰化聚苯乙烯微球(PS-acyl-Cl)经原子转移自由基聚合(ATRP)法引发丙烯酰胺(AM)和甲基丙烯酸缩水甘油酯(GMA)单体的共聚接枝,制得一种触角状亲水性环氧载体(PS-acyl-g-P(AM-co-GMA)),再经二乙醇胺(DEA)的环氧基开环胺化反应,得到一种含多个-NCH2CH2OH螯合配基的多齿-五元螯合环的触角状亲水性羟胺树脂(PS-acyl-g-P(AM-co-GMA)-DEA)。将此树脂用于硼吸附研究,结果表明,PS-acyl-g-P(AM-co-GMA)-DEA树脂对硼的吸附满足Langmuir方程,为单分子层吸附;饱和吸附量约为37.7 mg·g-1,且树脂5 min即可达到吸附平衡,与其它已报道的吸硼树脂相比,该树脂具有更高的吸附量和吸硼速率。吸附动力学研究表明,树脂吸附硼的过程主要由颗粒扩散过程控制。重复使用5次后该树脂的吸附量基本不变,解吸率均在90%以上,重复使用性能良好。