Nd扩渗BaTiO3陶瓷的电性能与XPS研究

采用气相法对钛酸钡陶瓷扩渗Nd元素, 经Nd扩渗BaTiO3陶瓷的电性能发生了十分显著的变化. 通过正交实验, 确定了最佳扩渗条件, 当Nd的浓度为2%, 扩渗时间为4 h, 扩渗温度为860 ℃时, BaTiO3陶瓷的导电性最好,其室温电阻率从4.3×109 Ω*m下降为37.45 Ω*m, 而且随着温度升高, 交流电导逐渐增大, 导电性更强. Nd扩渗使BaTiO3陶瓷的介电常数增加, 而介电损耗降低, BaTiO3陶瓷的介电性能得到了显著改善. 经Nd扩渗BaTiO3陶瓷的介电常数随着温度的变化呈明显的PTC效应, 其居里温度降低为118.1 ℃. 经XPS测试分析, 给出了Nd扩渗BaTiO3陶瓷体系中各元素结合能位置的峰值, 并表明 Nd扩渗BaTiO3陶瓷中Nd, Ba, Ti都存在变价, 因而导致了BaTiO3陶瓷导电性的增强.     

稀土对BaTiO3陶瓷的气相化学热扩渗及其电性能研究

采用气相法对钛酸钡陶瓷扩渗稀土元素，稀土扩渗使BaTiO₃陶瓷的电性能发生了显著变化。室温电阻率明显下降，从4.3×10⁹Ω·m变为4.84Ω·m;随着频率增大和温度升高，交流电导逐渐增大，BaTiO₃陶瓷的导电性更强。稀土扩渗使BaTiO₃陶瓷的介电常数明显增加，尤其在低频下增加显著;介电常数随温度的变化呈明显的PTC效应，并使BaTiO₃陶瓷的居里温度升高为124.9℃。经XRD分析，扩渗的稀土元素并没有进入BaTiO₃陶瓷的晶格中，而是存在于晶界上。经XPS测试分析，稀土扩渗后的BaTiO₃陶瓷中钡、钛、稀土等都存在着不同程度的变价，因而导致了BaTiO₃陶瓷电阻率的降低。TG-DTA曲线分析表明，稀土扩渗后的BaTiO₃陶瓷有较好的高温热稳定性。     

镨气相扩渗PbTiO3陶瓷的制备及其电性能

采用气相化学热扩渗方法制备了Pr改性的PbTiO3陶瓷,并对扩渗后PbTiO3陶瓷的组成、结构及电性能的变化进行了研究。通过XRD,SEM及Pr元素的面扫描分析证实Pr元素已经渗入到PbTiO3陶瓷体相,且分布均匀,并生成了Pr2Ti2O7等新的化合物,由此导致了PbTiO3陶瓷导电性的显著增强。在Pr扩渗PbTiO3陶瓷的实验中,通过正交试验法确定了扩渗的最佳工艺条件,即Pr元素的扩渗质量分数为0.015,扩渗时间为3 h,扩渗温度为860℃,此时PbTiO3陶瓷的导电性最好,其室温电阻率从2.0×1010下降为9.487Ω·m。对改性的PbTiO3陶瓷进行了交流复阻抗分析,随着温度的升高,扩渗后的PbTiO3陶瓷的导电性更强,其晶粒电阻和晶界电阻均随温度升高而呈逐渐下降的趋势,已不存在PTC效应,有向导电体过渡趋势。     

稀土气相扩渗BaTiO3基PTC陶瓷的NTCR效应

采用稀土气相扩渗法制备了La改性的BaTiO3基PTC陶瓷,并对其室温电阻率的变化及温-阻效应进行了研究.结果表明,BaTiO3基PTC陶瓷经La气相扩渗后,室温电阻率从2.7×109Ω.m下降到220Ω.m,在25-500℃范围内,电阻率随温度升高单调递减,从220Ω.m降至5.8Ω.m,产生了明显的NTCR效应.结合XRD,SEM,EDAX以及介电性能测试结果分析了La气相扩渗BaTiO3基PTC陶瓷NTCR效应的形成机理,建立了NTCR效应的物理结构模型.     

沉淀法制备Sm3+,Er3+与Nd3+一次共掺杂的BaTiO3基半导体陶瓷电容器

在共沉淀法的基础上,通过双施主不同浓度的Nd3+和Sm3+,Er3+(4.0%～5.0%)掺杂,研究了BaTiO3基表面型陶瓷电容器的电性能,结果表明,Sm3+和Er3+的掺杂可以提高居里温度,但使介电常数降低,其含量为25%时可获得绝缘电阻500 MΩ左右,C/S为0.5895μf·cm-2电性能参数.     

钕掺杂对（Ba0.6Sr0．4）TiO3／MgO陶瓷结构和性能的影响

采用X射线衍射、扫描电镜及介电性能测试,研究了Nd掺杂对42%(Ba0.6Sr0.4)TiO3/58%MgO(质量分数)复相陶瓷微结构和低频介电性能的影响.结果表明,添加O%～0.6%Nd203的材料均由(Ba,Sr)TiO3和Mgo两相组成,不含其他物相.随着Nd2O3掺杂量的增加,材料的晶粒尺寸变大,晶粒结合更加紧密.适量的Nd2O3掺杂可以获得适中的介电常数和较高的介电可调度,并使材料的介电损耗显著改善.0.4%(质量分数)的Nd2O3掺杂使材料的居里温度从-24.6℃迅速降低至-79.2℃,并改善了材料的温度稳定性.这时材料具有很好的介电性能,室温下(约25℃),100 kHz时介电常数为103.0,介电损耗为0.0005,2V·μm-1偏置电场下样品的介电可调度为9.15%(10 kHz),能够满足移相器的应用要求.     

低温-低压水热合成Ba1-xSrxTi1-ySnyO3纳米材料及其 结构与性能研究

采用低温-低压水热法,在150℃,0.5MPa以下合成了一系列Ba1-xSrxTi1-ySnyO3固溶体纳米粉末(0≤x≤0.5≤y≤0.4),经XRD物相分析和d-间距-组成图证明,产品为立方晶系的完全互溶取代固溶体,结果符合Vegard定律,TEM形貌观察,粒子为均匀球形,平均粒径80nm。通过制陶实验,分别测定了该系列固溶体的室温介电常数、介电损失以及介电常数随温度的变化。结果发现,用该方法在BaTiO3中掺入适量锶和锡,由于掺杂离子均匀进入母体晶格,引起Tc降低,介电性能改善显著,当x=0.1,y=0.08时,室温介电常数达17000,比BaTiO3纯相提高10倍,而介电损失却降低88%。     

稀土改性BaTiO3粉体的制备及其导电性分析

采用溶胶-凝胶法制备了纯BaTiO3粉体,并以La、Pr、Nd、Sm、Gd和Er等稀土元素通过液相掺杂、气相掺杂和液-气共掺3种不同的方式对其进行改性,以提高BaTiO3粉体的导电性.实验结果表明:各种稀土均可降低BaTiO3粉体的电阻率,效果最好的是Sm.不同掺杂方式中液-气共掺的效果最好,通过液相掺杂、气相掺杂和液-气共掺,BaTiO2粉体的电阻率由4.30×109Ω·m分别降至2.38×105,4.34×104和35.4 Ω·m.XRD、SEM、FTIR分析表明.液相掺杂时进入BaTiO3粉体的稀土元素主要集中在晶界处,而气相掺杂后稀土元素主要进入晶格内部,可能取代了Ti4+在晶格中的位置.半径较小的稀土元素更容易迁移而偏离钛氧八面体的中心位置,由此导致稀土掺杂后BaTiO3粉体的电阻率显著降低.     

MgO对La2O3-TiO2系陶瓷性能的影响

研究了MgO的加入对La2O3-TiO2陶瓷的烧结和介电性能的影响, 并对影响机制作了初步探讨. 结果表明添加MgO的La2O3-TiO2陶瓷能在1200～1280 ℃之间烧结. 随着MgO量的增加, 材料的介电常数下降, 介电常数的温度系数增加. 在1～40 MHz频率下没有添加MgO和添加2.4%的试样的介电常数分别为41和36, 介电损耗都在10-4数量级上, 在10 kHz下介电常数的温度系数分别为-24×10-6/℃和82×10-6/℃, 是一种性能良好的介质材料.     

镨对锌单取代杂多化合物气相扩渗的电性能及XPS研究

报道了采用气相法对K7ZnBW11O39配合物进行Pr的化学热扩渗, 研究了材料的电性能, 并结合XPS等表征手段对其导电机理加以了初步的分析. 通过配合物的TG-DTA分析确定了扩渗温度,扩渗后材料的ICP分析测试表明, 微量Pr可渗入到试样中. 经XRD分析发现, 扩渗后,化合物的晶型发生了改变, 得到了新的化合物. 利用四电极法和交流阻抗法对扩渗前后样品的导电性能进行了测试, 结果表明材料的导电性能发生了十分显著的变化, 扩渗后试样的电导率为2.98×10-2 S*cm-1, 比扩渗前的电导率3.54×10-6 S*cm-1提高了约104倍. XPS能谱及交流阻抗谱分析显示可能存在氧空穴导电.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.