（Ti（1-x）Alx）N硬质涂层的研究进展

TiAlN作为一种三元复合纳米涂层材料,具有非常好的性能.该涂层克服了TiN涂层所存在的一些缺陷,其硬度远远高于TiN涂层,最高可达47GPa, 并且具有很好的热稳定性,在700℃高温下仍很稳定,而TiN涂层在500℃时就已被氧化.TiAlN涂层还具有抗磨损,摩擦系数小,热膨胀系数及热传导系数低等特性,这些特性与涂层中Al含量的多少有关,Al含量的改变会导致涂层微观结构的改变,从而使其性能发生变化.氮分压和基底温度对TiAlN涂层的性质有着极其重要影响.本文结合国内外对TiAlN涂层的最新研究进展,对TiAlN涂层的应用,制备方法,结构,抗氧化性及硬度作了简要论述.     

PVD-TiAlN和PVD-TiAlSiN涂层氮化硅刀具的切削性能研究

采用物理气相沉积(Physical vapor deposition,PVD)工艺在氮化硅陶瓷刀具表面分别沉积TiAlN和TiAlSiN涂层.采用扫描电子显微镜(SEM)研究TiAlN和TiAlSiN涂层表面形貌和微观结构,X射线衍射仪(XRD)研究涂层晶体结构,显微硬度计表征涂层硬度.采用TiAlN和TiAlSiN涂层氮化硅刀具对灰铸铁进行连续干切削试验,分别研究TiAlN和TiAlSiN涂层对刀具寿命、磨损性能的影响,并探讨涂层刀具磨损机理.实验结果表明:TiAlSiN涂层晶粒比TiAlN涂层细小,从而具有更高的表面硬度.TiAlN涂层可将氮化硅陶瓷刀具寿命提高50;左右,TiAlSiN涂层可将刀具寿命提高1倍.切削过程中,TiAlN涂层刀具在磨损初期的主要磨损机理是磨粒磨损和少量粘结磨损,而后转为严重的粘结磨损;而TiAlSiN涂层刀具主要的磨损机制为磨粒磨损和粘结磨损.     

纳米结构TiN薄膜的制备与性能研究

利用自行研制的磁过滤等离子体设备,在室温条件下的不锈钢基底上成功地制备了性能良好的纳米结构TiN薄膜.运用原子力显微镜和X射线衍射仪对其结构和形貌进行了表征.利用纳米硬度仪测量了TiN薄膜的硬度和弹性模量.结果显示:沉积的TiN薄膜表面非常平整光滑,致密而无缺陷;硬度远高于粗晶TiN的硬度;TiN晶粒尺寸在30～50nm;沉积过程中在基底上施加的负偏压会影响纳米结构TiN薄膜的结构和性能.     

Al2O3/TiB2/AlN/TiN复合陶瓷材料的力学性能及显微结构

将金属Al、Al3Ti和TiB2以AlTiB中间合金的形式引入Al2O3基体材料中,采用热压原位反应生成法制备了Al2O3/TiB2/AlN/TiN复合陶瓷材料.复合材料在烧结过程处于过渡液相烧结,并有新相AlN和TiN生成;对热压烧结后材料的硬度、断裂韧性和抗弯强度进行了测试和分析;分析了复合材料力学性能随AlTiB体积百分含量的变化规律;探讨了复合材料断面断裂方式的变化对其力学性能的影响;并对AlTiB中间合金的细化特性进行了分析.     

Ni-W-纳米Al2O3复合涂层沉积特性的研究

采用复合电镀的方法制备出Ni-W-纳米Al2O3复合涂层,研究了Al2O3添加量、温度和超声波分散等沉积条件对复合涂层沉积特性如沉积速率、Al2O3复合量和显微硬度的影响.结果表明,随着纳米Al2O3添加量的增加,复合涂层的沉积速率、Al2O3复合量和显微硬度不断增加,但当Al2O3添加量达到15g/L时沉积速度开始下降,Al2O3添加量达到17.5g/L时硬度开始下降;适宜的镀液温度大约为80℃,超声波分散时间大约为1h.     

活性填料对聚硼硅氮烷制备不锈钢陶瓷涂层性能的影响

采用陶瓷先驱体聚合物聚硼硅氮烷(PBSZ)为原料,并加入B4C粉填料以及Al粉活性填料,制备耐高温不锈钢材料的陶瓷涂层.研究了在氮气条件下所获得涂层的性能和微观形貌以及填料对涂层性能的影响.利用TG-DTA、XRD分析了先驱体的裂解过程及产物物相,并用SEM对涂层微观结构及成分进行了分析.结果表明,Al粉的加入,促进了聚硼硅氮烷的裂解,减少了涂层的体积收缩,从而有效地提高了涂层与基体的粘结强度.在1000℃氮气条件下,涂层材料主要为Al4C3,AlN,SiC,B4C,Al等相.在适当的工艺条件下,所获得的陶瓷涂层韧性良好,且具有较好的抗氧化性.微观研究表明,陶瓷涂层最佳厚度约为50 μm,涂层表面均匀、致密,与不锈钢基体之间结合良好.     

Cr12模具钢表面真空烧结Ni60-TiC涂层的摩擦磨损性能

本文采用热压烧结方法在Cr12模具钢表面制备Ni60-TiC涂层,按照TiC的比例含量分别为0;、15;、25;以及35;,制备出4种配比的试样.采用维氏硬度计进行了显微硬度测试,采用摩擦磨损实验并结合SEM及EDS对Ni60-TiC涂层试样观测和分析,得出TiC加入量对涂层硬度以及摩擦性能的影响.结果表明:涂层中加入适量的TiC有助于提高涂层硬度以及摩擦性能,且涂层中TiC含量为25;时效果最为显著.     

固化剂对磷酸盐粘结剂固化行为的影响研究

本文以H3PO4和Al(OH)3为原料制备磷酸铝粘结剂,探讨了不同固化剂ZnO、CuO、Cr2O3对其固化行为的影响.采用XRD、邵氏硬度仪、TG-DSC等分析手段研究了磷酸盐粘结剂的物相组成、硬度、吸湿率及其固化机理等.结果表明:当P/Al摩尔比为3∶1.3时,磷酸铝粘结剂的理论固化温度为262℃,固化后产物为AlH2P3O10·H2O.固化剂的加入可以有效地缩短固化时间和提高涂层性能,以CuO为最佳.当CuO添加量不低于8wt;时,磷酸盐粘结剂固化时间最短,为2.5 h;吸湿率最低,为4.21wt;.当CuO添加量为6wt;时,涂层硬度最大,为99.2 HA.其对应的理论固化温度为145℃,固化产物为Al4(PO4)3(OH)3·xH2O和少量的Cu4P2O9·H2O.     

镁合金表面制备Al2O3/Ni复合涂层抗腐蚀性的研究

为了改善镁合金的抗腐蚀性,用电泳沉积法在AZ91D镁合金表面沉积两种不同比例的Al2O3/Ni复合涂层.在干燥器皿中放置12h后,放入真空烧结炉中,在300℃下保温4h.通过X射线衍射,扫描电子显微镜和能谱仪对涂层的形貌,物相和微观结构进行分析;将试样浸泡在3.5wt;的NaCl溶液中,通过电化学极化曲线和阻抗谱对涂层的抗腐蚀性进行测试.结果显示,与纯Al2O3涂层相比,Al2O3/Ni复合涂层由于添加了Ni,涂层孔隙率降低,同时降低了涂层与基底热膨胀系数的不匹配程度,提高了结合强度.在四种不同比例的涂层中,Al2O3与Ni质量比为1:3的复合涂层,表面结构更加均匀致密化,涂层的抗腐蚀性能最好.     

金刚石涂层的纳米压痕力学性能研究

用HFCVD法在硬质合金刀具上制备了CVD金刚石涂层,利用纳米压痕仪研究了CVD金刚石涂层的硬度和弹性模量等力学性能.结果表明,反应室气压、衬底温度、反应气体中CH4含量、沉积时间等参数改变了CVD金刚石膜中sp2成分含量、晶界数量及晶界上缺陷,从而影响CVD金刚石涂层的纳米硬度和弹性模量.较高或较低的衬底温度都会导致硬质合金刀具上CVD金刚石涂层的纳米硬度、弹性模量降低;随着反应室气压、反应气体中CH4含量的增加,硬质合金刀具上CVD金刚石涂层的纳米硬度、弹性模量降低;沉积时间低于6 h时,沉积时间对硬质合金刀具上CVD金刚石涂层的纳米硬度、弹性模量影响显著,沉积时间超过6 h后,沉积时间对硬质合金刀具上CVD金刚石涂层的纳米硬度、弹性模量逐渐趋向稳定.     

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.