铁掺杂对锰酸镧锶体系磁电性质的影响

通过测量样品的X射线衍射、电阻率-温度(p-T)曲线及磁电阻-温度(MR-T)曲线,研究了Fe掺杂对La0.67Sr0.33Mn1-xFexO3(0≤x≤0.200)陶瓷体系磁电性质的影响.结果表明:在x=0时,样品呈典型的铁磁金属性,随着Fe含量的增加,样品p-T曲线存在金属一半导体转变峰,并且该峰随Fe替代量的增加向低温方向移动.在x=0.200时,在实验温区观察不到金属-半导体转变峰.在高铁含量时只能在低温观察到磁阻效应.这些现象主要是由于样品中的Mn3 被Fe3 所替代,部分Mn3 -O2-Mn4 铁磁双交换作用键被打断,样品中的铁磁与反铁磁作用的相互竞争以及样品内部电子局域化所形成的极化行为等因素影响所致.     

La0.67-xSmxSr0.33MnO3陶瓷中的相分离和输运特性

测量了La0．67-xSmxSr0.33MnO3(x=0．00,0．10,0．20,0．30,0．40,0．50,0．60)陶瓷的磁化强度-温度曲线、电子自旋共振谱曲线和电阻率-温度曲线。实验结果表明：x=0．00,0．10时,样品为长程铁磁有序;x=0．20,0．30时,样品为自旋团簇玻璃态;x=0．40,0．50,0．60时,样品在低温时表现为反铁磁状态;x=0．30和0．40的样品在Curie温度Tc以上温区发生相分离。高掺杂(x=0．60)样品的输运行为发生异常,在Tc附近发生绝缘体-金属相变后,又发生金属-绝缘体相变,这在ABO3结构中很少出现。陶瓷的磁电行为变化取决于掺杂引起的额外磁性和晶格畸变效应。     

La0.3Ca0.7Mn1-xVxO3体系的电荷序和自旋序

通过对样品La0.3Ca0.7Mn1-xVxO3(x=0.05,0.10,0.134,0.20)的磁化强度-温度(magnetization-temperature, M-T)曲线、电阻率-温度(resistivity-temperature, p-T)曲线、电子自旋共振谱的测量,研究了Mn位V掺杂La0.3Ca0.7MnO3体系电荷序和自旋序的影响.结果表明:当0.05≤x≤0.134时,体系存在电荷有序(CO)相,体系自旋序随温度降低发生顺磁(paramagnetism, PM)-荷有序(charge ordering, CO)-反铁磁(antiferromagnetism, AFM)变化.当x=0.20时,电荷有序融化,体系出现再入型自旋玻璃行为.     

掺杂少量Sm时La0.67-xSmxSr0.33MnO3(0.00≤x≤0.30)的磁电性质

通过测量样品的磁化强度-温度(M-T)曲线、电阻率-温度(ρ-T)曲线及磁电阻(magnetoresistance)-温度(MR-T)曲线,研究了Sm掺杂(x=0.00,0.10,0.20,0.30)对La0.67-xSrmxSr0.33MnO3磁电性质的影响.发现在铁磁相主要是单磁子散射起作用,表现为金属型导电,可用公式ρ=ρ0+AT2拟合,其中ρ为温度T时的电阻率;ρ0为0 K时的电阻率;A为常数.顺磁相的输运机制主要是小极化子跃迁起作用,可以用公式ρ=BTexp·(Ea/kBT)拟合,其中Ea为激活能;kB为Bolzman常数;B为常数.在相变温区是顺磁相的小极化子与铁磁相的单磁子2种输运性质共存.     

钙钛矿锰氧化物(La_(1-x)Nd_x)_(0.5)Ca_(0.5)MnO_3(0≤x≤1)的结构,磁性和电输运性质

系统研究了(La1-xNdx)0.5Ca0.5MnO3(x=0,0.2,0.4,0.6,0.8,1.0)系列样品的结构、磁性质和电输运性质。研究表明,所有样品的结构都为钙钛矿正交结构(空间群Pbnm),随着掺杂浓度x的增大,样品的晶格参数a,b,c和晶胞体积V都呈减小的趋势;磁性质的研究表明所有样品在低温下均出现电荷有序态,且电荷有序转变温度随着Nd3+的掺杂浓度x的增加而升高;除了Nd0.5Ca0.5MnO3(x=1.0)外,其它样品均出现顺磁-铁磁转变,其转变温度(即居里温度)随着Nd3+的掺杂浓度x的增加而降低;(0.2≤x≤0.8)样品的铁磁态均出现在电荷有序温度以下,表现出再入型(reentrant)铁磁态性质;电输运性质的研究表明,所有样品的电阻率随温度的升高而下降,表现为绝缘体性质。     

La（0.3）Ca（0.7）Mn（1–x）VxO3体系的电荷序和自旋序（英文）

通过对样品La0.3Ca0.7Mn1–xVxO3（x=0.05,0.10,0.134,0.20）的磁化强度–温度（magnetization–temperature,M–T）曲线、电阻率–温度（resistivity–temperature,ρ–T）曲线、电子自旋共振谱的测量,研究了Mn位V掺杂对La0.3Ca0.7MnO3体系电荷序和自旋序的影响。结果表明：当0.05≤x≤0.134时,体系存在电荷有序（CO）相,体系自旋序随温度降低发生顺磁（paramagnetism,PM）–电荷有序（charge ordering,CO）–反铁磁（antiferromagnetism,AFM）变化。当x=0.20时,电荷有序融化,体系出现再入型自旋玻璃行为。     

La8/9Sr1/45Na4/45MnO3/0.5x（V2O5）复合体系的电输运及磁电阻

用固相反应法制备了 La8/9Sr1/45Na4/45MnO3/0.5x（V2O5）（x = 0,0.04,0.08,0.12,0.16,0.20）系列样品,通过 X 射线衍射谱、扫描电子显微镜、电阻率–温度（ρ–T）和磁电阻–温度（RM–T）的关系,研究了样品的电输运性质及 RM温度稳定性。结果表明：所有样品表现为从高温区绝缘体导电到低温区金属导电的绝缘体–金属相变,随 V2O5复合量增大,绝缘体–金属转变温度 Tp向高温移动;V2O5复合量较小（x≤0.08）时 ρ–T 曲线出现双峰,V2O5复合量较大（x≥0.12）时 ρ–T 曲线双峰消失;所有样品在低温区随温度降低 RM持续增大,表现出低场磁电阻特征,在高温区的本征磁电阻随 V2O5复合量增大而逐渐减小;对于 x = 0.16、0.20 的样品,在 0.8 T 磁场,319～283 K,RM基本保持 6.4%和 5.8%不变。RM温度稳定性的产生原因可能是表面相引起的隧穿磁电阻与体相引起的本征磁电阻竞争的结果。在高温区体相内部双交换引起的本征磁电阻占优势,在低温区界面的磁无序引起的隧穿磁电阻占优势,最终在中间温区产生不随温度变化的 RM。     

Ga掺杂的La_(1/2)(Pr_(1/4+3y/4)Ca_(3/4-3y/4))_(1/2)Mn_(1-y)Ga_yO_3的磁性和电输运性质

实验详细研究了Ga掺杂对锰基氧化物La1/2(Pr1/4+3y/4Ca3/4-3y/4)1/2Mn1-yGayO3(Mn3+:Mn4+=5:3,y=0,0.02,0.05,0.08和0.10)的磁性和电输运性质的影响。实验发现,用Ga3+离子替代Mn3+离子会显著地抑制样品的铁磁性和金属导电特性。随着Ga掺杂量从0增加到0.10,样品的居里温度TC、金属-绝缘转变温度TM I和最大磁电阻所对应的温度均向低温方向偏移,然而样品的电阻率以及最大磁电阻却显著地增加。除了在金属-绝缘转变温度TM I附近出现的本征庞磁电阻外,我们在低温区域还发现了显著的磁电阻效应,这种低温磁电阻是由多晶样品中的晶界效应导致的。另外,通过对宏观磁性的分析,我们没有发现Pr3+离子对磁性的贡献。实验结果表明:磁稀释和无序效应在决定样品的磁性和电输运性质方面起到了重要的作用。     

B位掺杂钙钛矿结构化合物LaSr2Mn2-xFexO7的电磁性能

研究了以Fe离子(Fe3 )掺杂取代部分锰(Mn)离子的层状钙钛矿结构化合物LaSr2Mn2-xFexO7(O≤x≤O.3)的电性和磁性.结果发现:Fe3 的掺杂抑制了LaSr2Mn2-xFexO7低温的反铁磁性交换作用,使Neel温度TN由x=0的138K降至x=0.3的l0lK.同时,LaSr2Mn2-xFex07的自旋玻璃态、电荷有序和金属一绝缘体转变温度都由于Fe3 取代Mn离子而受到抑制.产生上述现象的原因是因为Mn位被取代导致产生无序状态.由于Fe3 取代Mn粒子,致使双交换作用通道被打破,化合物的电阻率随x的增加而迅速增加.所有化合物的电阻率在低温阶段都可以用Mott的变程跳跃理论来拟合;在高温阶段可以用最近小声子极化理论来拟合.     

Ca2+掺杂对BiFeO3陶瓷结构和磁、介电性能的影响

以Bi(NO3)3·5H2O、Fe(NO3)3·9H2O和Ca(NO3)2·4H2O为原料、乙二醇甲醚为溶剂、柠檬酸为络合剂,采用溶胶–凝胶法制备Bi1–x Cax FeO3(x=0、0.05、0.10、0.15、0.20)陶瓷样品。结果表明:所有样品的主衍射峰与纯相BiFeO3相吻合,样品晶粒尺寸随Ca2+掺杂量的增加而减小,在室温下各样品均具有完整的磁滞回线,样品铁磁性显著提高。当x=0.10时,剩余比磁化强度达到最大值(0.11A·m2/kg)。在外加磁场为398 kA/m时,样品的比磁化强度在644 K附近出现明显的反铁磁相变,反铁磁相变温度TN随掺杂量的增加而升高。在300~900 K,样品顺磁相变温度TP,以及TN和TP处比磁化强度的差值随Ca2+的增加均呈现先上升,在x=0.10时达到最大值,之后又呈下降趋势。样品在850K时比磁化强度出现明显变化,变化幅度随Ca2+掺杂量的增加而减小,在x=0.10时最小,之后又增大。不同磁场下样品剩余比磁化强度随温度变化表明:Bi1–x Cax FeO3陶瓷样品存在变磁性,当x=0.10时,变磁性最为明显。磁电耦合效应观测结果表明:样品的磁电耦合系数为负值,介电常数随外磁场变化反应灵敏,在x=0.10时磁电耦合效应为–14.2%,是纯相BiFeO3(其磁电耦合效应为–5%)的近3倍,表明掺杂适量Ca2+可增强样品的磁电耦合性能。     

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.     

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.     

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.