孕镶金刚石硬质合金基底上沉积金刚石涂层工艺研究

为提高金刚石涂层和基底的结合力,采用化学气相沉积方法在普通硬质合金和孕镶金刚石硬质合金基底上分别沉积金刚石涂层,并通过扫描电镜、拉曼光谱和压痕分析对比研究其结合性能。结果表明:在孕镶金刚石硬质合金基底上可以实现金刚石的同质与异质外延生长;在孕镶金刚石硬质合金基底上沉积的金刚石形核率高,晶形大小均匀,涂层表面平整;孕镶金刚石基底金刚石涂层的结合力优于硬质合金基底金刚石涂层膜基界面的结合力。在孕镶金刚石硬质合金基底上沉积金刚石膜可扩大金刚石涂层的应用范围。      

沉积参数对硬质合金基体微/纳米金刚石薄膜生长的影响

基体温度、反应压力和碳源浓度等沉积参数决定热丝化学气相沉积金刚石薄膜的性能。运用正交试验方法,研究参数对硬质合金基体金刚石薄膜生长的综合作用。采用场发射扫描电镜（FE-SEM）、原子力显微镜（AFM）和拉曼（Raman）光谱检测薄膜的形貌结构、生长速率和成分。结果表明：随着基体温度的降低,金刚石形貌从锥形结构向团簇状结构转变;低反应压力有利于纳米金刚石薄膜的生成;生长速率受反应压力和碳源浓度综合作用的影响。     

第三组元铝元素对TaMo高温合金涂层组织和性能的影响

通过磁控溅射法在硅基材上制备了不同基底温度的TaMo和TaMoAl涂层,用原子力显微镜（AFM）和X射线衍射仪（XRD）研究了加入第三组元Al元素的情况下,TaMo涂层的表面形貌和组织结构,用显微硬度计和划痕试验仪测试了涂层的显微硬度和膜基结合力等力学性能。结果表明,两种基底温度工艺下铝元素的加入对TaMo涂层的组织结构和表面形貌均有显著影响。另外,在350℃的基底加热工艺下铝元素的加入提高了TaMo涂层的显微硬度和膜基结合力。     

低表面粗糙度金刚石涂层刀具的制备

降低表面粗糙度是改善金刚石涂层刀具使用性能的有效手段.采用微波等离子体化学气相沉积(MPCVD)金刚石膜,通过在沉积过程中调整工艺参数,先后在硬质合金基体上沉积了2层不同的金刚石薄膜.研究了基体位置、甲烷浓度等对薄膜表面形貌的影响.用扫描电子显微镜(SEM)、原子力显微镜(AFM)和压痕法对样品进行了分析测试,结果表明,该方法在保证金刚石涂层质量的同时有效降低了薄膜表面的粗糙度,表面粗糙度值Ra＜0.2 μm.     

Ti6Al4V合金上类金刚石膜的摩擦学性能及腐蚀行为

采用离子束沉积技术在医用Ti6Al4V合金表面制备类金刚石薄膜（DLC）,利用原子力显微镜、Raman光谱、X射线光电子能谱（XPS）及UMT-2摩擦磨损试验机对薄膜的形貌、结构、摩擦学性能进行表征。采用动电位极化对涂层前后基底的耐腐蚀性能进行测试。结果表明：制备薄膜为类金刚石碳结构,基底偏压对薄膜形貌、结构有较大影响;偏压为–100 V时制备的薄膜表面粗糙度低（6.5 nm）,sp3/sp2 比值高,摩擦学性能优异;经DLC膜保护的合金基底耐腐蚀性能获得明显改善。     

二氧化碳对金刚石膜生长的影响

利用微波等离子体化学气相沉积法,以H₂/CH₄/CO₂为混合气源,在Si基底上沉积金刚石膜,分析了微波功率和CO₂对金刚石膜生长的影响。利用Raman光谱、扫描电子显微镜（SEM）和X射线衍射（XRD）表征金刚石膜,以得到样品质量、表面形貌、晶粒取向等信息。结果表明:适当提高微波功率,可以促进金刚石晶粒长大并提高（100）取向度;加入适量CO₂,能提高金刚石膜质量和生长速率,并保持表面形貌不会发生明显变化,但随着CO₂含量的增加,金刚石表面形貌发生较大变化,薄膜质量和沉积速率先提高后降低。      

氧气和形核密度对金刚石薄膜生长的可控性研究

在2 kW微波等离子体化学气相沉积装置中,以CH4,H2和O2为反应气体制备金刚石膜,主要研究氧气和形核密度对金刚石膜表面形貌和生长速率的影响。在实验过程中,O2的掺入对相同形核密度表面形貌、质量有影响,其中氢气与甲烷在形核时的体积浓度比为200∶6,生长时的体积浓度比为200∶4,通入0.2 mL/min的O2有助于增大表面金刚石颗粒,并提高金刚石膜的质量,在拉曼表征中只有一个金刚石特征峰。采用不同形核密度时,氧气的通入促进金刚石膜的沉积,并能抑制非晶C的沉积,因为沉积过程中的非晶C质量分数急剧下降,从而提高金刚石膜的生长速率,由1μm/h提高到了1.5μm/h。     

甲烷浓度对CVD金刚石膜表面粗糙度的影响

研究了化学气相沉积金刚石膜时甲烷浓度与金刚石膜表面粗糙度的关系。结果表明，随甲烷浓度的增加金刚石膜表面粗糙度下降。表面粗糙度主要由金刚石膜的晶粒大小和二次形核决定，晶粒越细，表面粗糙度越低，在金刚石晶界二次形核及长大，也促使金刚石膜表面粗糙度降低。     

灯丝／基体距离对金刚石涂层质量的影响

热丝CVD法金刚石膜生长中基体温度对金刚石薄膜的质量有很大的影响,而基体与灯丝的距离决定着基体沉积温度的高低。本实验采用单一变量法,在其它工艺参数不变的情况下,研究不同基体与灯丝距离对CVD金刚石涂层的质量的影响。采用扫描电镜、Raman光谱、洛氏硬度计对试样的表面形貌、成分和涂层与基体的结合力进行泓定。结果表明,当采用两步法基体预处理,在碳源体积浓度为2％、沉积气压为3kPa、反应功率为4kW时,得到最优金刚石涂层质量的热丝与基体的距离为5mm。     

基底对类金刚石薄膜组织性能的影响

采用等离子体增强化学气相沉积技术,在3种不同基底上(不锈钢、铝合金、氮化硅)制备了类金刚石薄膜(DLC),并对薄膜进行了相关的性能评价。结果表明,3种基底上制得的DLC薄膜结构致密,表面光滑且具有良好的均匀性;AFM表征结果表明,沉积的薄膜为无定型结构;Raman光谱分析显示沉积的薄膜为类金刚石薄膜;在非金属上采用等离子体化学气相沉积技术可以制备出DLC薄膜。与铝合金、氮化硅相比,选用不锈钢作为基底的薄膜硬度和弹性模量与基底差异更小,膜基结合力较强,可达13.55N;基底为氮化硅的薄膜摩擦因数较低,为0.094 8,但膜基结合力较差,仅为6.63N。此外,在相同工艺下,基底种类对薄膜的成分和耐摩擦磨损性能影响显著,但对薄膜的表面形貌和粗糙度无明显影响。     

X-ray diffraction study of Ba0.985Na0.015Ti0.985Nb0.015O3, Ba0.6Na0.4Ti0.6Nb0.4O3 and Ba0.3Na0.7Ti0.3Nb0.7O3 compositions

The Ba_0.985Na_0.015Ti_0.985Nb_0.015O₃, Ba_0.6Na_0.4Ti_0.6Nb_0.4O₃ and Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ compositions of the (1 − x) BaTiO₃–xNaNbO₃ (BTNNx) system have been studied by X-ray diffraction and by measurements of dielectric properties. The specimens with composition BTNN (x = 0.015, 0.40 and 0.70) have been refined by the JANA program from X-ray powder diffraction data. Ceramic samples with composition (1 − x) BaTiO₃ + xNaNbO₃ (where x = 0.015, 0.40 and 0.70) were prepared by calcinations from appropriate mixture of BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅. The calcined powder was sintered at temperature range 1200–1400 °C. As the composition x increased from 0.015 (and 0.70), the ferroelectric ceramics (x = 0.015, FE) with tetragonal phase changed to the ferroelectric relaxors (RFE, x = 0.40). RFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to 180 K) due to a frustration between RFE and FE state. These ceramics present the classical ferroelectric character when 0 ≤ x < 0.075 and 0.55 < x ≤ 1 and relaxor character when 0.075 ≤ x ≤ 0.55.     

Magnetic, electrical and plastic properties of Fe76Nb2Si13B9, Fe75Ag1Nb2Si13B9 and Fe75Cu1Nb2Si13B9 amorphous alloys

Influence of 1 h annealing in vacuum on magnetic, electrical and plastic properties of Fe₇₆Nb₂Si₁₃B₉, Fe₇₅Ag₁Nb₂Si₁₃B₉ and Fe₇₅Cu₁Nb₂Si₁₃B₉ melt spun ribbons were carefully investigated. It was shown that in all cases soft magnetic properties can be significantly enhanced by applying 1-h annealing at characteristic temperatures T_op. This optimization annealing causes that permeability increases more than 15-times and magnetic losses (tangent of loss angle) achieves a minimum in relation to the as quenched state. Using structural examinations (X-ray and HRTEM) it was shown that for the Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy the optimized microstructure corresponds to a nanocrystalline αFe(Si) phase whereas in other alloys to a relaxed amorphous phase free of iron nanograins. As a consequence of this fact the Fe₇₆Nb₂Si₁₃B₉ and Fe₇₅Ag₁Nb₂Si₁₃B₉ alloys show higher plasticity in comparison to the nanocrystalline Fe₇₅Cu₁Nb₂Si₁₃B₉ alloy. Temperatures of the first stage of crystallization, and related diffusion parameters were determined using measurements of resistivity versus temperature with different heating rates.     

Fe2+-Ni2+-NH3-NH4+-C2O42-H2O体系的沉淀配合平衡热力学

针对草酸盐配位共沉淀热分解还原法制备超细铁镍合金粉过程中Fe2+-Ni2+-NH3-NH4+-C2O42--H2O体系的溶液平衡建立热力学分析模型,并根据模型进行相关计算,揭示反应体系中各物质随pH值、氨及草酸浓度的变化关系。结果表明:溶液中的Fe主要以[Fe(C2O4)n]2 2n络合物形式存在,而铁氨络合物含量很低。当氨含量较低时,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在;氨含量较高时,在酸性条件下,溶液中的Ni主要以[Ni(C2O4)n]2 2n存在,在碱性条件下,则主要以[Ni(NH3)n]2+存在。低pH值下,Ni的沉淀率较Fe的高,而高pH值下,Ni的沉淀率则较Fe的低。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

New Zr6CoAs2-type compounds: Y6CoBi2, Ho6CoBi2 and Tm6CoBi2

Results of a powder X-ray diffraction investigation of new ternary compounds are reported. The compounds Y₆CoBi₂ [a=0.8312(1) nm, c=0.4144(1) nm], Ho₆CoBi₂ [a=0.8246(2) nm, c=0.4095(1) nm], and Tm₆CoBi₂ [a=0.8155(2) nm, c=0.4066(1) nm] crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

Zur Kenntnis von RbBa3Ca4Cu3V7O28

Single crystals of RbBa₃Ca₄Cu₃V₇O₂₈ were prepared above the melting point of the reaction mixture. It crystallizes with hexagonal symmetry, space group C_6V⁴-P6₃mc, a 11.1751, c 12.434 Å, Z = 2. RbBa₃Ca₄Cu₃V₇O₂₈ is the second member of a new structure type of the copper-oxovanadates. Ba²⁺ shows an unusual 12-fold coordination. The two calcium positions are coordinated by trigonal prisms and octahedra respectively. The copper coordination is characterized by a stretched square pyramid. The Cu²⁺ ions are outside the centre nearly in plane of the pyramids.

Zusammenfassung

Einkristalle von RbBa₃Ca₄Cu₃V₇O₂₈ wurden oberhalb des Schmelzpunktes der Reaktionsmischung erhalten. Die Verbindung kristallisiert hexagonal, Raumgruppe C_6V⁴-P6₃mc, a 11.1751, c 12.434 Å, Z = 2. RbBa₃Ca₄Cu₃V₇O₂₈ ist das zweite Beispiel für einen neuen Strukturtyp der Kupfer-Oxovanadate, mit 12-fach koordinierten Ba²⁺ -Ionen. Die zwei Calciumpositionen sind trigonal prismatisch bzw. oktaedrisch koordiniert. Die Koordination der Cu²⁺-Ionen ist durch eine gestreckte Pyramide charakterisiert. Cu²⁺ ist auβerhalb des Polyederzentrums nahezu in der quadratischen Fläche der Pyramide angeordnet.     

Al2O3-Sm2O3-CeO2电解质的性能（英文）

采用溶胶-凝胶法和低温燃烧技术制备Ce1-xSmxO2（x=0,0.1,0.2,0.3）和掺杂Sm和（2%-8%）Al2O3的二氧化铈;研究其合成、结构、致密化、导电性和热膨胀等性能,并利用XRD研究其结构和相组成。结果表明,于1300°C烧结球团,获得致密的陶瓷,于1250°C在Ce0.8Sm0.2O0.2中加入2%和4%的Al2O3以促进烧结。利用扫描电子显微镜观察烧结后球团的表面形貌,使用双探针交流阻抗谱研究总离子电导率。     

电弧喷涂制备Fe65Cr20Mo7B3.5SiMn1.5W3涂层

在Q235低碳钢板上利用电弧喷涂工艺进行喷涂,以制得Fe65Cr20Mo7B3.5SiMn1.5W3涂层。喷涂材料为自行配制的丝材,按照35%的填充率将配好的粉填充到U型不锈钢外皮中,经过多道拉拔、挤压工艺制成Φ2mm的粉芯丝材。采用X射线衍射仪、扫描电镜、能谱分析仪、透射电镜对涂层的物相和组织形貌及成分进行了表征;采用差示扫描量热仪、显微硬度仪等设备对涂层的热稳定性及显微硬度进行了检测和分析。试验结果表明:涂层组织形貌呈典型的层状组织结构,由变形良好的带状粒子相互搭接堆积而成。涂层含有50.63%的非晶相,同时含有纳米级的晶相。涂层组织均匀、结构致密、孔隙率低,并且涂层硬度高达1040.5HV0.3,属硬质涂层,具有良好的热稳定性。     

Synthesis and electrochemical properties of LiNi0.4Mn1.5Cr0.1O4 and Li4Ti5O12

Spinel compound LiNi_0.4Mn_1.5Cr_0.1O₄ (LNMCO) and Li₄Ti₅O₁₂ (LTO) were synthesized by the sol-gel method and the solid-state method, respectively. The particle sizes of the products LiNi_0.4Mn_1.5Cr_0.1O₄ and Li₄Ti₅O₁₂ were 0.5 to 2 um and 0.5 to 0.8 um, respectively. All samples exhibited excellent electrochemical properties. A LiNi_0.4Mn_1.5Cr_0.1O₄/Li₄Ti₅O₁₂ (LNMCO/LTO) cell was fabricated and was demonstrated to exhibit good electrochemical properties at the high current rate of 1 C. When the specific capacity was determined based on the mass of the LNMCO cathode, the LNMCO/LTO cell delivered 125 mAh g⁻¹ at 1 C and 77 mAh g⁻¹ at 5 C. The capacity retentions after 30 cycles were 94.4 % and 83.1 %, respectively.