热障涂层用陶瓷材料研究进展

寻求性能良好的涂层用陶瓷材料已经成为热障涂层技术领域的研究热点,本文综述了国内外锆基氧化物、A2B2O7型氧化物以及各类新型氧化物等热障涂层用陶瓷材料的研究成果,讨论了每一类材料在热物理性能研究方面存在的不足.指出未来应基于光子理论,设法降低ZrO2基陶瓷与A2B2O7氧化物的高温光子热导率,进一步提高涂层材料的隔热性能;系统研究元素掺杂对新报道陶瓷热物理性能的影响规律,并采用合适的工艺制备其对应热障涂层,实际考察涂层的综合性能;根据热传导和热膨胀基础理论,从材料设计的角度开发性能更加优良的新型涂层用陶瓷材料.     

掺杂Ni/Al对热障涂层抗高温氧化性和结合强度的影响

YSZ(Ni,Al)粉末颗粒通过电泳沉积技术在高温镍基合金600上沉积一层厚度均匀的YSZ(Ni,Al)复合热障涂层,并在室温下干燥24 h后,进行真空烧结致密化处理.真空致密化处理后的YSZ(Ni,Al)复合热障涂层在1100℃下氧化不同小时并测量涂层的结合强度.由于掺杂了镍铝氧化初期在涂层表面形成一层致密的氧化薄膜,有效地阻止了空气中的氧气进一步进入涂层内部从而提高了涂层的抗高温氧化性能,另外在陶瓷涂层YSZ中掺杂了金属元素,降低了陶瓷涂层与高温镍基合金的热膨胀系数的不匹配,使涂层表面更加平整致密,同时也提高了涂层与基体的结合强度.     

Yb2O3-Y2O3-Gd2O3-ZrO2热障涂层制备及性能研究

以Yb2O3、Y2O3 、Gd2O3稀土氧化物粉末和ZrOCl2·8H2O粉末为原料,采用化学共沉淀法制备了Yb2O3-Y2O3-Gd2O3-ZrO2 (YYGZO)热喷涂用粉末,采用大气等离子喷涂技术制备了YYGZO涂层,利用场发射扫描电镜(FESEM)、X射线衍射(XRD)研究了YYGZO粉末及涂层的微观组织形貌、相结构.结果表明,制备的热喷涂YYGZO粉末大部分呈规则实心球体状,且球形度良好,颗粒粒径均匀,大部分颗粒粒径分布为30～60μm,流动性能较好,满足大气等离子喷涂的要求.YYGZO涂层具有较好的高温相结构稳定性.所制备YYGZO热障涂层组织结构比较致密,涂层各个界面结合紧密,孔隙率约为9.23;,结合强度为35.2 MPa.     

溶液等离子喷涂氧化锆涂层力学性能的研究

采用溶液等离子喷涂技术(SPPS)制备了氧化钇部分稳定氧化锆(7YSZ)热障涂层(TBCs).热障涂层剥落失效的影响因素众多,其中很多都与涂层的力学性能相关.利用扫描电镜(SEM)、X射线衍射仪(XRD)和硬度计等研究了涂层的力学性能.结果表明,SPPS涂层的弹性模量约为58 GPa,硬度约为7 GPa,比大气等离子喷涂(APS)涂层高了15;左右;SPPS涂层的断裂韧性为1.8~2 MPa·m1/2,结合强度约为25 MPa.SPPS涂层因为低的孔隙率和更好的板条之间的结合带来了力学性能的提升.     

碳基材料表面TaC涂层的研究进展

碳材料在高温有氧环境中的易氧化性极大地制约了其在航天航空领域中的应用,而TaC涂层能够有效改善碳材料的烧蚀氧化性能.本文综述了TaC陶瓷涂层改性抗烧蚀氧化C/C复合材料的研究进展,包括单相TaC涂层、复合涂层体系、梯度涂层体系、固溶强化涂层体系和微纳结构增韧涂层体系以及TaC涂层的高温(>2000 ℃)氧化机理.并就目前碳基材料表面TaC涂层研究存在的问题,提出了今后研究的方向.     

Hf微量掺杂Sm2Ce2O7固溶体制备及热物理性能

采用高温固相烧结法制备了Sm2(Ge1-xHfx)2O7(x=0,0.025,0.05,0.075,0.1)固溶体,并对其相组成、显微组织及热物理性能进行了分析.结果表明,所合成的固溶体具有单一的萤石结构,其相对致密度均在90;以上.Hf掺杂增强了声子的散射程度,从而使其热导率与Sm2Ce2O7相比明显降低.Hf较小的离子半径使得其热膨胀系数随HfO2掺杂量增加而降低,但仍然满足热障涂层的要求.     

(Ti1-xAlx)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.     

（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.     

SiCf/SiC复合材料表面梯度抗氧化SiC涂层研究

SiC纤维增强SiC陶瓷基复合材料(简称SiCf/SiC复合材料)具有低密度、高温稳定性、抗氧化性、高耐腐蚀性等特点,在航天及航空发动机热结构部件及核聚变反应堆炉第一壁结构等方面有巨大的潜在用途.目前受工艺条件制约,SiCf/SiC复合材料中用来增强的SiC纤维纯度不高,C/Si原子比大于1.3,而采用传统先驱体浸渍裂解工艺(简称PIP)制备的基体材料除了纯度不高外,还含有孔隙和缺陷,不能满足高温氧化环境中服役要求.本文通过化学气相沉积工艺(CVD)在SiCf/SiC复合材料表面制备出一种高纯、低缺陷、耐高温、低氧扩散系数且与基体材料具有良好匹配性的SiC抗氧化梯度涂层,通过SEM分析基体与膜层的结合情况及涂层的微观形貌,通过XRD考察涂层的梯度组份及氧化前后涂层成份变化,进而探讨梯度涂层抗氧化机理.     

(Sm1-xAlx)2Ce2O7化合物的热物理性能

以Al2O3、Sm2O3和CeO2为原材料,采用固相反应法制备了(Sm1-xAlx)2Ce2O7化合物.对其相结构,显微组织和热物理性能进行了研究.结果表明,合成的(Sm1-xAlx)2Ce2O7化合物具有单一的萤石型晶格,该化合物致密度均在90;以上,晶粒界面明显.三价铝离子的引入能明显降低其导热性能,热膨胀性能虽虽然有所降低,但高温热膨胀系数大于YSZ,满足热障涂层的要求.     

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 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.     

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.     

Synthesis of spinacine and spinacine derivatives: crystal and molecular structures of Nπ-hydroxymethyl spinacine and Nα-methyl spinaceamine

The natural amino acid L-Spinacine (4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridine-6-carboxylic acid) has been synthesized following a new pathway which gives a chemically and optically pure product with an excellent yield. The crystal structures of a synthetic intermediate, N^π-hydroxymethyl-spinacine, and a spinacine derivative, N^α-methyl-spinaceamine, have been investigated through X-ray diffraction: Spi(πMeOH)·H₂O, monoclinicP2 _i,a=8.571(1),b=6.682(1),c=8.588(1) Å, and β=94.67(1)^o. Spm(αMe)·2HCl·H₂O, triclinicP l,a=7.492(4),b=10.799(3),c=7.040(2) Å, α=91.88(2), β=98.36(3) and γ=73.34(3)^o. Spi(πMeOH) crystallizes with a water molecule and displays a zwitterionic character. The carboxylate group is in equatorial position and forms a short electrostatic interaction of 2.618(2) Å between one of its oxygens and the protonated nitrogen of the tetrahydropyridine ring. The crystal packing is assured by strong O?H???O, O?H???N, N?H???N intermolecular hydrogen bonds and C?H???O close contacts. The biprotonated compounds Spm(αMe) crystallizes with two Cl^? anions and a water molecule. The positive charge on the imidazole ring is delocalized on the conjugated moiety N=C?N. The crystal is built up by clusters formed by two biprotonated Spm(αMe) molecules, four Cl^? anions and two water molecules linked together by hydrogen bonds.