α半水脱硫石膏流动度经时性及减水剂适用性

研究了α半水脱硫石膏流动度经时性及其影响因素,对掺减水剂石膏流动度经时性与流动度经时损失的内在原因进行了分析。α半水脱硫石膏流动度经时损失大,水化6 min流动度损失20%以上,α半水脱硫石膏快速水化对游离水消耗与束缚,以及双电层结构破坏,ξ电位迅速降低是导致流动度经时损失的内在原因。萘系减水剂(FDN)的分散作用主要依赖ξ电位的静电斥力,其分散稳定性差,流动度经时损失大;聚羧酸减水剂(PC)主要依靠空间位阻发挥分散作用,其分散稳定性较好,流动度经时性损失较小。高效减水剂应具备空间位阻效应,复配缓凝剂是抑制α半水脱硫石膏流动度经时损失的有效方法。     

氨基磺酸系高效减水剂对水泥的分散作用研究

研究了氨基磺酸系新型高效减水剂ASP对水泥净浆的分散作用机理。对照商品萘系高效减水剂FDN，研究了掺加减水剂后水泥胶粒的ζ电位及水泥颗粒对减水剂的吸附量。结果表明，掺加ASP和FDN后水泥颗粒的ζ电位基本相同，而ASP在水泥颗粒的吸附量较FDN的小，ASP对水泥的良好分散作用是由静电斥力和空间位阻共同作用的结果。ζ     

聚羧酸减水剂空间位阻表征方法探讨

聚羧酸高效减水剂的作用机理为静电斥力和空间位阻效应,其中以空间位阻效应为主.根据高聚物在固/液界面吸附行为,探讨以吸附层厚度和吸附构象作为主要参数来表征和研究聚羧酸减水剂吸附在水泥颗粒表面引起的空间位阻效应;讨论了X射线光电子能谱(XPS)、俄歇电子能谱(AES)、原子力显微镜(AFM)、光子相关光谱(PCS)、单分子力谱(SMFS)、流体力学、椭圆偏振、Monte Carlo模拟等方法在表征减水剂空间位阻的可行性、相关研究成果及其局限性,展望了聚羧酸减水剂空间位阻效应的研究前景.     

聚羧酸系减水剂的制备及性能研究

在水溶液中,以活性单体聚合法合成了一种含羧基、磺酸基、聚氧乙烯基等功能基团的聚羧酸系减水剂,原料配比MAS∶AA∶PA=1∶3∶1,反应时间3 h,温度90℃,引发剂用量2%。该减水剂在建筑石膏中掺量为0.7%时,减水率可达18.7%,且可以抑制建筑石膏流动度经时性损失,还同时提高硬化体的强度。静电斥力和空间位阻效应的协同作用是减水剂在建筑石膏中的主要作用。     

聚羧酸系减水剂的制备及性能研究

在水溶液中,以活性单体聚合法合成了一种含羧基、磺酸基、聚氧乙烯基等功能基团的聚羧酸系减水剂,原料配比MAS∶AA∶PA=1∶3∶1,反应时间3 h,温度90℃,引发剂用量2%。该减水剂在建筑石膏中掺量为0.7%时,减水率可达18.7%,且可以抑制建筑石膏流动度经时性损失,还同时提高硬化体的强度。静电斥力和空间位阻效应的协同作用是减水剂在建筑石膏中的主要作用。     

XPS测定减水剂吸附层厚度

通过XPS谱图和XPS信息深度的计算方法测定了减水剂在胶凝颗粒表面的吸附层厚度。结果显示,木质素磺酸盐减水剂（LS）、改性木质素磺酸盐减水剂（GCL1-T）、萘系减水剂（FDN）和氨基磺酸盐减水剂（ASP）在水泥颗粒表面的吸附层厚度分别为8.70、10.87、1.50、7.26 nm;GCL1-T和FDN在粉煤灰表面的吸附层厚度分别为6.76 nm和0.95 nm。此方法可较准确描述减水剂在胶凝颗粒表面吸附层厚度的相对大小。由测定结果可进一步推断,FDN的分散机理以静电斥力效应为主;而空间位阻效应在LS、GCL1-T和ASP的分散机理中不可忽略。     

聚羧酸减水剂的结构与陶瓷原料的适应性研究

通过对聚羧酸减水剂与粘土颗粒作用机理的分析以及对现有减水剂在水泥和陶瓷当中适应性的研究,提出:梳型减水剂分子不能在层状结构的粘土颗粒表面形成有效吸附,从而不显示减水效果。线型聚羧酸减水剂分子可以和层状结构的粘土颗粒形成线-面有效结合,从而以静电斥力和空间位阻两种作用发挥减水效果。     

聚羧酸减水剂对α-半水脱硫石膏的水化进程及其硬化体微结构的影响

采用扫描电镜、压汞测孔仪等微观分析方法,结合宏观物理力学性能实验,测试了加入聚羧酸减水剂后α-半水脱硫石膏的水化温升、水化率、硬化体的强度、孔结构以及显微结构,并研究聚羧酸减水剂对α-半水脱硫石膏水化硬化性能的影响。结果表明,聚羧酸减水剂对石膏水化进程影响较小;在一定的掺量内,聚羧酸减水剂能大幅提高石膏硬化体强度,改善硬化体孔结构,降低石膏孔隙率,细化孔径,这是聚羧酸减水剂提高α-半水脱硫石膏硬化体强度的内在原因。     

聚羧酸系高性能减水剂对高铝浇注料基质浆体ζ电位的影响研究

本文采用BDL-B型表面电位粒径仪,测定了高铝浇注料基质浆体在不同减水剂作用下的ζ电位;采用NXS-11A旋转粘度计测量了浇注料基质浆体的粘度,研究了减水剂对基质浆体ζ电位及粘度的影响.研究表明,加入适量的减水剂,能降低体系的ζ电位与粘度,ζ电位与粘度具有相似的变化规律.从理论上分析了浆体粒子吸附减水剂、扩散双电层与ζ电位的形成机理.STP、KS-20均为阴离子型分散剂,吸附于浆体粒子表面,ζ电位降低,通过静电斥力作用达到分散效果,KS-JS70、LMS-P为非离子型减水剂,依靠聚氧乙烯链吸附于粒子表面,通过空间位阻作用达到分散效果.随着减水剂加入量的增加,减水剂在粒子表面吸附达到饱和,ζ电位变化趋于平缓.     

氨基磺酸单环芳烃型高效减水剂的制备及其在水泥颗粒表面的作用机理

以对氨基苯磺酸钠、苯酚和甲醛等为原料合成出了氨基磺酸单环芳烃型(AS)高效减水剂,研究了反应单体的摩尔比以及工艺参数对AS高效减水剂对水泥颗粒分散效果的影响。运用现代测试分析方法(IR、GPC)对合成出的氨基磺酸单环芳烃型(AS)高效减水剂进行了官能团和相对分子质量分布的表征,从氨基磺酸单环芳烃型(AS)高效减水剂的表面张力、起泡能力和ξ电位以及其稳定性等方面研究了AS高效减水剂在水泥颗粒表面的作用机理,研究表明静电斥力和空间位阻效应和润滑作用、润湿作用的共同作用,使AS单环芳烃型高效减水剂对水泥颗粒有更好的分散能力和很好的保持性。     

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.     

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.     

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.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.