高电阻温度系数的La0.67(Ca0.33-xSrx)MnO3多晶陶瓷制备与电学性能研究

采用溶-凝胶法在1450 ℃烧结12 h的条件下,制备了x组分为0、0.01、0.03、0.05、0.06、0.07的La0.67(Ca0.33-xSrx)MnO3 (LCSMO)多晶陶瓷,通过R-T、XRD和SEM测试分析,结果表明,溶胶-凝胶方法制备的LCSMO多晶陶瓷其物相较纯,阻温特性良好,晶粒尺寸大,致密度高.在未掺Sr时,该体系电阻温度系数(TCR)达到最高值42.5;.随着Sr掺杂比增加,金属-绝缘体转变温度TP升高,TCR降低,而在TP达到室温时,LCSMO多晶陶瓷具有较大的TCR(9;以上).在LCSMO多晶体系中如此大的TCR较为罕见,使其具有重要的潜在应用价值.     

室温铁磁Sr4-xErxCo4O10.5+δ(0.6≤x≤1.2)多晶电输运和磁性能

采用固相反应法制备Sr4-xErxCo4O10.5+δ(0.4≤x≤1.2)多晶,系统研究了Er掺杂对体系结构、电输运和磁性质的影响.X射线衍射结果表明室温下x=0.4时多晶为立方晶系,空间群为P3m3,0.6≤x≤1.2时,为四方晶系,空间群为I4/mmm,四方相晶格常数随着Er含量增加而减小.扫描电子显微镜结果表明,随着Er掺杂量增加,晶粒细化,晶界增加.采用四探针法测量多晶的电阻率-温度曲线,结果表明多晶样品在80～ 300 K为半导体电输运行为,且随Er化学计量比增加样品电阻率和热激活能增大.采用超导量子干涉仪测量多晶的磁化强度-温度曲线和磁滞回线,结果表明0.6≤x≤1.2时Sr4-xErxCo4O10.5+δ多晶具有室温铁磁性,Tc≈320 ～ 335 K,室温铁磁性可能源于A位Sr和Er离子有序及CoO4.5+δ层中Co离子自旋倾斜净磁矩不为零.     

烧结工艺对La0.67Ca0.33MnO3多晶物理性质的影响

利用溶胶-凝胶法成功制备了La0.67Ca0.33MnO3粉末,并通过优化烧结工艺获得了物理性能优异的La0.67Ca0.33MnO3多晶靶材.利用X射线衍射仪和扫描电子显微镜分别测试了样品的物相、结构和微观形貌,并利用四探针法测试了靶材的电阻率-温度曲线.结果表明,影响TCR的主要因素有晶粒的化学均匀性、晶粒尺寸和晶界的数量,样品具有接近室温的金属-绝缘转变温度(TM1 =274 K)和高的电阻温度系数(TCR=13.5;).     

高电阻温度系数(La0.67Ca0.33MnO3)1-x∶Agx多晶陶瓷的研究

采用溶胶-凝胶法制备了(La0.67Ca0.33 MnO3)1-x∶Agx(x=0.00、0.10、0.15、0.20、0.3、0.4、0.5)系列多晶陶瓷样品,通过XRD、SEM和标准四探针法对材料晶体结构、表面形貌和电学性能的分析研究Ag的添加对材料性能的影响.结果表明:随着Ag添加量的增加,样品的晶格常数逐渐增大,这是由于Ag取代La3+、Ca2+进入晶格使其发生膨胀;并且样品的金属-绝缘体转变温度(Tp)随Ag添加量的增加而升高,从270 K(x=0)升高到281 K(x=0.5),这是由于Ag对La3+、Ca2+的替换导致Mn4+/Mn3+比例增大而提高了双交换作用.值得注意的是,当0.00≤x≤0.15时,TCR值随x的增大而增大,当x=0.15时达到最大值58.6;·K-1;0.15≤x≤0.5时,TCR反而随之降低,这可能是由于高添加量导致材料的烧结质量降低.     

预烧温度对La0.67Ca0.33MnO3陶瓷结构及电学性能的影响

采用溶胶-凝胶法成功制备了La0.67Ca0.33MnO3粉末,并通过改变预烧温度获取电学性能优异的陶瓷.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、四探针法对不同预烧温度处理后的La0.67Ca0.33MnO3陶瓷的物相、结构、微观形貌和电学性能进行测试,分析预烧温度对材料的晶粒尺寸和电学性能的影响,从而摸索出最佳预烧温度.实验结果表明:样品的结晶性能好物相纯,随着预烧温度的增加,晶粒尺寸、致密度、收缩率和电阻温度系数(TCR)在不断减小,电阻率先减小后增加.在300℃预烧,1450℃烧结得到的样品具有较高的TCR值达到了40.8;·K-1.     

Bi1.7Pb0.3Sr2Ca2Cu3O10多晶制备工艺对其电学性能影响的研究

采用溶胶-凝胶法成功制备了Bi1.7Pb0.3Sr2Ca2Cu3O10(BPSCCO)粉末,通过优化制备工艺获得了电学性能优良,转变温度在114 K左右的Bi1.7Pb0.3Sr2Ca2Cu3O10多晶靶材.利用X射线衍射仪测试了样品的物相和结构,并利用四探针法测试了靶材的电阻-温度曲线.对比了不同螯合剂对溶胶-凝胶法制备BPSCCO多晶的影响,发现以葡萄糖酸为螯合剂克服了传统工艺周期长、pH难调控的缺点.在此基础上,探究了热处理工艺对Bi1.7Pb0.3Sr2Ca2Cu3O10多晶电学性能的影响,得到了其最适预烧温度(600 ～ 700℃)、烧结温度(820～830℃)及烧结时间(48 h).     

室温铁磁Sr3YCo4O10.5+δ多晶的制备及其性能研究

采用传统简便的固相烧结法制备了四方相的室温铁磁Sr3YCo4O10.5+δ多晶.热分析、X射线衍射和扫描电镜结果表明Sr3 YCo4 O10.5+δ多晶最终烧结温度应在963℃以上,较佳的烧结温度为1180℃.Sr3YCo4O10.5+δ多晶在80～300K为半导体电输运行为,较佳烧结温度多晶的室温电阻率～78.8 mΩ·cm;多晶热电势在317～1018 K随温度增加而减小,317 K时为70.74 μV/K.磁化强度-温度曲线、磁滞回线结果表明,多晶在受外加磁场、温度及晶体场的影响下,内部Co3+自旋态及磁畴壁、磁矩方向发生改变,导致多晶磁化强度变化及多晶磁性的改变.外磁场(0.1 T)下的ZFC曲线在320 K出现磁化强度最大为0.46 emu/g的Hopkinson峰,居里温度(Tc) =323 K,而FC曲线在奈尔温度(TN)=264 K时磁化强度达到最大为1.1 emu/g,TC=320 K.ZFC、FC方式下多晶均表现为室温铁磁性.     

Mn掺杂Ca0.16Sr0.04Li0.4Nd0.4TiO3微波介质陶瓷介电性能的研究

采用传统固相法制备了MnO2掺杂Ca0.16Sr0.04Li04Nd04TiO3微波介质陶瓷,并借助X射线衍射仪、扫描电子显微镜、网络矢量分析仪和精密阻抗分析仪对微波陶瓷的物相结构、表面形貌、介电性能和电学微结构进行了分析.结果表明掺杂MnO2部分进入Ca0.16Sr0.04Li0.4Nd04TiO3陶瓷晶格Ti4位中并导致衍射主峰衍射角向高角度轻微偏移,所得陶瓷晶粒大小约5 μm.随着MnO2含量的增加,观察到显著的Mn-Li氧化物杂相,过高的MnO2掺杂使得Ca0.16Sr0.04Li04Nd04TiO3陶瓷晶粒的主要生长方向由(200)变为(220).MnO2含量的增加使得陶瓷介电常数εr从140降至122,品质因子Qf从1450显著升至1960 GHz,谐振温度系数Τf较为稳定且均为40 ppm/℃左右.陶瓷内部由Li+陶瓷表面电学阻抗、晶界阻抗、晶壳和晶核形成的晶粒阻抗构成,其中晶界的电阻贡献主要来自于Li+挥发或析出形成的阳离子空位电导;晶壳和晶核电阻为电子-空穴与氧空位相互耦合形成的电导.微波陶瓷的介质损耗主要来自于晶粒区域晶核的高度半导化各构成电学微结构部件载流子束缚能力大小与活化能规律趋于一致.     

Bi2O3掺杂Sr0.92Ca0.08TiO3基陶瓷结构与介电性能的研究

通过固相反应法以Ca2+、Bi3+取代Sr2+制备出Sr0.92-1.5xBixCa0.08 TiO3(0.155≤x≤0.195)固溶体,同时加入固定量的MnCO3和ZnO作为改性剂和助烧剂,并通过XRD衍射仪、SEM扫描电镜和LCR分析仪对样品的结构和介电性能进行分析.结果 表明,当x≥0.165时陶瓷样品中出现第二相;随着Bi3+含量的增加,介电常数先增大,后减小,且介质损耗先减小后增大.当x=0.16时,得到介电常数ε=1 153、介质损耗tgδ1KHz=3.5×10-4、绝缘强度Eb=9.37 kV/mm的高介低损耗的高压电容器陶瓷介质材料.     

Sr3YCo4-xMgxO10.5+δ(0≤x≤0.04)多晶的制备和热电输运性质研究

采用固相反应法制备Sr3YCo4-xMgxO10.5+δ(0≤x≤0.04)系列多晶,研究了Mg掺杂对体系结构、电输运和热电性质的影响.结果表明系列多晶为四方晶系,由于掺入的Mg2+(0.066 nm)部分替代了Co3+/4+(0.053 nm/0.061 nm),使晶格膨胀;多晶热电势在340~830 K随温度升高而下降,且Mg掺杂对热电势影响不大,表明Mg掺杂对体系载流子浓度影响不大;多晶电阻率在100~300 K随温度升高而降低,且随着掺杂量增加电阻率降低,结合扫描电镜观察到多晶的气孔数目减少、晶粒连接紧密和热电势的结果认为Mg掺杂对体系电输运性质的影响机制主要是使气孔、晶界散射作用减弱、载流子迁移率变大,而Mg掺杂对载流子浓度的影响是次要的.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

First-principles coexistence simulations of supercooled liquid silicon

We perform first-principles coexistence simulations of the low-density and the high-density phases of supercooled liquid silicon and find a negative slope for the coexisting line in the temperature-pressure plane. Electron density maps and electron-localization function plots of the two phases of silicon show marked differences. The calculated differences suggest more localized electrons in the low-density liquid compared to the high-density liquid, coming from an increased population of covalent bonds, which further explain the calculated negative slope in the two phase coexistence regime. This is consistent with the presence of a pseudo-gap in low-density liquid silicon, absent in the high-density liquid which shows a metallic behavior.     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

CTAB与SDBS对碳酸锶粒子生长形态调控及机理研究

以表面活性剂CTAB和SDBS为化学添加剂,采用化学共沉淀法对碳酸锶晶体的生长形态进行调控,成功地制备出了实心的树枝状和花瓣为空心的花状碳酸锶粉体,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT-IR)等分析手段对样品进行了表征;最后重点对化学添加剂可能产生的影响机理进行了初步的探讨.结果表明,CTAB和SDBS在晶体生长的过程中能起到显著的影响作用,两者对粒子分散性能的作用效果相反,而且后者对晶体(013)和(213)晶面表面能降低的贡献明显大于前者.     

Crystal structures of the cis and trans isomers of a tetrathia[3.3.3.3]cyclophane

Both the cis and trans isomers of 3,11,18,26-tetrathiatricyclo[26.2.2.1^5,9.2^13,16.1^20,24] hexatriaconta-5,7,9,20,22,24-hexene have been prepared and structurally characterized. Each of these centrosymmetric tetrathia dimers includes two cyclohexane rings in chair conformations with either 1,4-cis or 1,4-trans bonding and two meta-substituted benzene rings. The cis isomer packs into the monoclinic space group P2₁/a with a = 10.485(3)Å, b = 10.3956(18)Å, c = 14.1343(10)Å, = 105.200(13)°, Z = 2 and refined to an R factor of 0.046. The trans isomer crystallizes in the monoclinic space group P2₁/c with a = 10.7217(12)Å, b = 5.6797(7)Å, c = 25.415(5)Å, = 96.001(12)°, Z = 2 and refined to an R factor of 0.043. In the cis structure each benzene ring faces a cyclohexane ring while in the trans structure the cyclohexane rings face one another.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

电沉积法制备ZnO纳米棒阵列及其发光特性

本文以掺F的SnO2导电玻璃为基板,以硝酸锌水溶液为电解液,采用三电极恒电位体系电沉积制备ZnO纳米棒阵列,系统考察了硝酸锌浓度和沉积电位等工艺参数对ZnO纳米棒阵列的微观形貌及其发光性能的影响规律.结果表明,硝酸锌浓度和沉积电位对纳米棒阵列的形貌有显著影响,控制适宜的工艺条件可以制备出直径分布均匀、结晶性好且纯度高的六方纤锌矿ZnO纳米棒阵列.荧光光谱分析表明,电沉积制备出的ZnO纳米棒阵列在385 nm附近有一个强荧光发射峰,且发光性能稳定、对纳米棒阵列微观形貌的细微变化不敏感,使其在发光二极管和激光器等领域具有广阔的应用前景.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.