外加剂对钙矾石形貌的影响

采用增大硼酸等外加剂组分掺量的方法,用溶液法合成了钙矾石。采用X射线衍射、扫描电子显微等方法研究了碳酸锂等3种混凝土外加剂对钙矾石形成和形貌的影响。结果表明:缓凝剂硼酸显著抑制了钙矾石的生长。硼酸掺量的增加降低了钙矾石的长宽比,从100左右降低至10左右;掺量为5%时,反应形成了扁柱状的钙矾石;碳酸锂抑制了钙矾石晶体宽度的生长,但可加快钙矾石的形成速度;聚羧酸减水剂抑制了钙矾石晶体宽度上的生长,形成的钙矾石晶体变长变细,提高了钙矾石晶体的长宽比,但促进了钙矾石成核。     

外部因素对钙矾石晶体结构及形貌的影响综述

钙矾石是硫铝酸盐水泥、通用硅酸盐水泥以及其他无熟料水泥等胶凝材料的重要水化产物之一,其晶体结构由中心柱和平行中心柱的沟槽组成。沟槽结构围绕中心柱呈六边形排列,硫酸根和水分子在沟槽中通过氢键网络将整个结构连接在一起。在水泥等胶凝材料的水化反应中,钙矾石晶体容易受到所处环境等外部因素的影响。其中反应物离子的过饱和度、温度、减水剂、氯离子、晶种等外部因素往往会改变钙矾石晶体结构中水分子和氢键的数量,进而改变晶体结构的稳定性及形貌等。此外,在合成钙矾石晶体过程中,搅拌桨型式及转速等也会影响钙矾石晶体结构和形貌,从而造成认知的不统一。本文在系统综述钙矾石晶体结构基础上,详细汇总了各种外部因素对钙矾石晶体结构和形貌的影响,同时介绍了各种研究手段,并对钙矾石晶体形成与形貌的研究方向提出了建议。     

硫酸盐侵蚀下钙矾石的形成和膨胀机理研究现状

钙矾石是水泥混凝土硫酸盐侵蚀过程中的重要产物之一,钙矾石的形成可能会引起混凝土膨胀、开裂,本文在讨论水泥混凝土中钙矾石的形成和形貌的基础上,从钙矾石的形成环境-反应机理-形貌-膨胀机理出发综述了不同反应机制下形成的钙矾石对应的膨胀性能及钙矾石型硫酸盐侵蚀的膨胀机理,最后对钙矾石型硫酸盐侵蚀现状进行了总结.     

合成条件对钙矾石形貌的影响

钙矾石是硫铝酸盐水泥水化的主要产物,决定着硫铝酸盐水泥的性能,而在硅酸盐水泥混凝土中影响也非常重要。钙矾石的形成条件决定了其形貌,其形成时间影响着水泥和混凝土的性能。采用化学合成方法合成钙矾石,研究了不同合成条件对钙矾石形成和形貌的影响。结果表明:不同原料合成的钙矾石形貌显著不同且长宽比差异显著;适当提高温度能够促进钙矾石的形成,80℃条件下反应可以形成钙矾石且形貌多样,100℃条件下反应钙矾石不能稳定存在;随着液相p H值的增加,钙矾石的长宽比逐渐减小;硼酸抑制钙矾石在(001)方向的生长。     

钙矾石对Cr6+和Cr2+的固化及稳定性

通过溶液法人工合成钙矾石,分析比较了水化形成过程中钙矾石对Cr6+和Cr2+固化机制及其稳定性.结果表明,Cr6+和Cr2+均可对钙矾石晶格结构产生一定影响,但两者在钙矾石中固化机制并不完全相同.Cr6+挤入钙矾石晶格层间结构,改变了分子对称性,对钙矾石晶体结构有较大影响;而Cr2+对钙矾石晶体结影响较小.在水化液相中重金属离子含量较低时,钙矾石对Cr2+、Cr6+俘获能力较高,且少量Cr2+对钙矾石晶体生长发育促进作用;而重金属离子含量较高时,钙矾石对Cr6+俘获能力明显下降,但对Cr2+的固化能力仍较高.钙矾石对Cr2+固化受环境条件影响较小,同时少量Cr2+在一定程度上有利于稳定碳化条件下钙矾石晶形结构;而钙矾石对Cr6+的固化受外界环境因素影响较大,且碳化、冻融、氯盐侵蚀多因素复合对其固化稳定性有极大影响.     

氢氧根对半水硫酸钙晶体形貌的影响机理

以二水硫酸钙为原料在氢氧化钠-水体系中水热合成不同形貌的半水硫酸钙晶体,并通过XRD、XPS和电导率等手段对水热产物进行表征,研究了OH^-对水热产物晶体形貌的影响机理。结果表明,在碱性条件下可获得不同形貌的半水硫酸钙晶体,随着OH^-浓度的增大,纤维状形貌水热产物的含量减小而短柱状形貌的含量增多,且当OH^-浓度为1.0×10^-2 mol/L时水热产物以短柱状形貌为主。OH^-影响半水硫酸钙晶体形貌的原因：OH^-会消耗溶液中的Ca²⁺,从而促进二水硫酸钙的溶解,而Ca²⁺浓度的减少不利于半水硫酸钙晶体的成核生长;同时,OH^-对二水硫酸钙的促溶作用会增加溶液中SO₄^2-的浓度,从而促进半水硫酸钙晶体沿（110）和（200）晶面的生长;此外,OH^-在（002）晶面选择性吸附并与该晶面的Ca²⁺反应生成Ca（OH）⁺和Ca（OH）₂,从而阻碍半水硫酸钙晶体沿该晶面的生长。在以上3种作用下半水硫酸钙晶体形貌由纤维状向短柱状转变。本研究可为碱性条件下生产不同形貌半水硫酸钙晶体提供一定的理论依据。     

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。     

溶液pH对电沉积氧化亚铜薄膜的影响

采用醋酸铜-醋酸钠酸性溶液和硫酸铜-乳酸碱性溶液,分析了不同pH下电沉积Cu2O薄膜的形貌及结构,讨论了镀液体系及溶液pH对Cu2O薄膜生长的影响,测定了不同形貌的Cu2O薄膜的光学透射性能.结果表明,溶液的氢氧根、羧基、羟基中的氧原子会影响Cu2O薄膜的结构及形貌.酸性溶液中,Cu2O薄膜易形成混晶结构;而碱性溶液中,随着pH的变化,Cu2O薄膜有不同的择优取向.酸性溶液中Cu2O薄膜形成网状结构,碱性溶液中易形成锥形结构.     

熟料-无水石膏系统与粉煤灰-石灰-无水石膏系统的水化产物

本文用XRD和SEM对CA和FLA不同龄期的水化产物数量和形貌进行了分析.随龄期增加,CA中CaSO4数量慢慢减少,而FLA中CaSO4数量则快速减少.3 d龄期时CA中有一些钙矾石晶体,此后随龄期增加钙矾石数量无明显增加;3 d龄期时FLA中只有很少的钙矾石晶体,此后随龄期增加,钙矾石数量显著增加.3 d后CA中CaSO4·2H2O的数量都很少;随龄期增加,FLA中CaSO4·2H2O的数量先增加后减少.3 d后CA中Ca(OH)2数量随龄期增加基本保持不变,而FLA中Ca(OH)2数量随龄期增加逐渐减少.CA中水化硅酸钙凝胶为典型的成簇生长的呈放射状分布的纤维状形貌,而FLA中水化硅酸钙凝胶则为无定形物质.3 d时CA中钙矾石晶体为短柱状,而FLA中钙矾石为短针状;70 d后CA和FLA中都能见到长针状钙矾石.     

碱-集料反应的一些理论问题

评述了碱-集料反应的一些理论问题以及活性集料分布规律。碱-硅反应膨胀主要是由渗透压力和钙矾石膨胀所致。碱-硅反应产物组成SiO_2/Na_2O=0—25(分子比)。Ca(OH)_2提供了生成钙矾石膨胀相和R(Na,K)CSH的物质。碱-Kingstone白云岩反应膨胀是碱-硅反应、黄铁矿分解形成钙矾石和蒙脱石吸水膨胀等综合因素引起的。     

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.