深振荡磁控溅射制备柔性硬质纳米涂层的研究进展

柔性硬质纳米涂层具有高致密性、高表面完整性、高硬度、高韧性和高裂纹抵抗力特性,是新一代高性能纳米涂层的一个重要发展方向,但其制备难度高,难以利用传统涂层制备技术实现。深振荡磁控溅射(deeposcillation magnetron sputtering, DOMS)技术是一种新型的高功率脉冲磁控溅射技术,现已成为国际涂层研究领域的热点。DOMS技术通过一系列调制的电压微脉冲振荡波形,能够实现完全消除电弧放电和靶材近全离化,获得高密度、低离子能量和高束流密度的等离子体,能制备出具有低缺陷、高表面完整性、高致密性的高性能纳米涂层,并且对纳米涂层的成分、结构和性能实现"剪裁化"的可控制备。本文综述了柔性硬质纳米涂层的特征以及DOMS制备柔性硬质纳米涂层的最新进展。     

高功率脉冲磁控溅射制备金属氮化物涂层EI北大核心CSCD

高功率脉冲磁控溅射(HiPIMS)作为目前研究热门的物理气相沉积方法之一,已经在刀具材料、不锈钢、聚合物、复合材料等基体上实现硬质涂层、生物涂层、耐腐蚀涂层、耐高温氧化涂层、绝缘涂层等多种类型涂层制备。通过高功率脉冲磁控溅射与复合方法及后续热处理等工艺方法复合,调节高功率脉冲磁控溅射的脉冲频率、峰值功率、占空比、多脉冲和双极性实现对靶材离化率、等离子体空间分布、涂层沉积速率、相结构、微观结构、元素成分、内应力等等离子体参数和涂层物相结构的调整,以提高基体材料的硬度、耐磨损、耐腐蚀、耐高温氧化及生物相容性等综合使役性能。特别是在应用于金属氮化物涂层的制备及性能研究方面,具有巨大的工程应用价值。结合目前硬质涂层材料的应用现状,探讨高功率脉冲溅射技术沉积涂层的特性和技术优势,介绍20多年来高功率脉冲磁控溅射技术在制备单元单层、多元多层、纳米多层与多元复合、高熵合金及含Si、O、C等金属氮化物硬质涂层工艺及性能等方面应用的研究进展。     

三靶共溅射纳米复合Cr-Al-Si-N涂层的 制备及摩擦学性能研究

目的 利用高功率脉冲磁控溅射技术离化率高、溅射离子能量高等优点,在Cr-Al-N涂层中添加Si元素研制a-Si3N4包裹nc-(Cr,Al)N的纳米复合涂层,通过改变反应沉积时的N2/Ar比来调控涂层成分与结构,实现纳米复合Cr-Al-Si-N涂层性能优化。方法 采用高功率脉冲与脉冲直流复合磁控溅射技术制备Cr-Al-Si-N涂层。利用扫描电镜、X射线衍射仪、能谱仪、应力仪、纳米压痕仪、划痕测试仪和摩擦试验机,研究N2/Ar比对涂层成分、结构、力学性能以及摩擦学行为的影响。结果 涂层主要由面心立方结构的CrN与AlN相组成,且沿(200)晶面择优生长。当N2/Ar流量比为3∶1时,涂层与基体结合最好,临界载荷约为36.5 N;摩擦系数和内应力较低,分别为0.5和-0.48 GPa。当N2/Ar流量比为4∶1时,H/E值和H3/E*2值升至最高,分别为0.11和0.24 GPa,磨损率最低,约为1.9×10-4 μm3/(N?μm)。结论 当N2/Ar流量比为4∶1时,三靶共溅射制备的Cr-Al-Si-N涂层硬度较高,耐磨性能最好。     

沉积偏压对AlCrTiN纳米复合涂层力学与抗高温氧化性能的影响

沉积偏压对涂层的结构与性能具有重要影响,为研究其对AlCrTiN纳米复合涂层成分、组织结构、力学与抗高温氧化性能的影响规律,采用磁控溅射技术,改变沉积偏压(-30、-60、-90、-120 V)制备四种AlCrTiN纳米复合涂层。利用X射线衍射仪、扫描电子显微镜、纳米压痕仪等仪器表征涂层的组织结构、成分、力学性能和抗高温氧化性能。研究结果表明：不同偏压下制备的AlCrTiN纳米复合涂层均为NaCl型fcc-(Al,Cr,Ti)N相结构。随着沉积偏压增大,涂层由沿(111)晶面择优生长转变为无明显的择优生长取向,晶粒尺寸降低,残余应力和硬度增大。偏压为-90 V与-120 V时,涂层表面更加致密,具有更高的硬度和弹性模量。在800℃与900℃氧化1 h后,所有涂层表面均生成一层连续致密的Al₂O₃膜。随着沉积偏压增加,氧化膜厚度逐渐降低,表明抗高温氧化性能逐渐增强,这是因为高偏压下涂层组织更致密,且晶粒更细小。研究成果对AlCrTiN纳米复合涂层的综合性能提升与工程化应用具有一定指导意义。     

[例60]等离子体增强磁控溅射镀膜在石化行业阀组中的应用

正等离子体增强磁控溅射技术是在磁控溅射时外加钨丝放电来增强等离子体的密度,显著提升涂层的沉积速率和均匀性,并匹配可调控的等离子体能量,从而实现超厚、超硬涂层的制备。采用该技术制备的TiSiCN、TiAlVSiCN等涂层具有非晶包覆纳米晶(5～20 nm)的结构,涂层厚度可控制在≤30μm范围内,纳米硬度30 GPa,具有优良的抗冲蚀性能和结合强度。     

偏压对MPP制备AlTiSiN纳米复合涂层结构及性能的影响

目的实现对AlTiSiN纳米复合涂层微观组织结构的调控及力学性能优化。方法利用可调控脉冲磁控溅射技术,通过调控基体偏压(-50～-250 V)制备了不同偏压条件下的AlTiSiN纳米复合涂层。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能量色散谱仪(EDS)、原子力显微镜(AFM)、薄膜综合性能测试仪及球盘摩擦试验仪,测试了涂层的微观组织结构、组成成分、表面形貌、力学性能及摩擦学性能。结果偏压对涂层元素组成影响不大。微观组织结构方面,不同偏压条件下制备AlTiSiN纳米复合涂层的晶面衍射峰宽化现象明显,呈现纳米晶组织结构。-200V条件下制备的涂层的晶面衍射峰呈"馒头峰"形态,表明涂层结晶性能出现明显下降,呈类非晶组织结构;偏压升至-250V时,高能离子对涂层生长表面的持续轰击作用,使得涂层生长表面升温明显,导致结晶性能出现明显改善。涂层表面光滑致密,表面粗糙度最低可达1.753nm。力学性能方面,随基体偏压的升高,涂层硬度在取得最大值后逐渐下降,最高硬度可达25.9 GPa,H/E*系数可达0.13。摩擦学性能方面,偏压为-200 V时,涂层磨损率取得最小值4.7×10~(-15) m~3/(N×m)。结论改变基体偏压,成功实现了涂层微观组织结构的调控生长,进而达到了优化涂层组织结构、力学性能及摩擦学性能的目的。     

Cu含量对Ti-Al-Si-Cu-N纳米复合涂层微观结构和高温氧化行为的影响（英文）

通过磁控溅射技术,在AISI-304不锈钢表面制备了不同Cu含量的Ti-Al-Si-Cu-N纳米复合涂层。通过扫描电镜(SEM)、能谱(EDS)仪、X射线衍射(XRD)仪、纳米压痕仪和自制压痕仪等设备研究Ti-Al-Si-N和Ti-Al-Si-Cu-N纳米复合涂层的结构和在800℃氧化的行为。结果表明:随着涂层中Cu含量的增加,涂层表面的微孔数量减少,涂层更加致密,涂层晶粒尺寸减小,择优取向由(111)向(110)逐渐转变。涂层的硬度由14.76 GPa增加至19.42 GPa。Cu含量为1.72%(原子分数)的Ti-Al-Si-Cu-N弹性模量最小,为104.5GPa。Cu元素对Ti-Al-Si-Cu-N纳米复合涂层抗氧化性能有两方面的影响:一是促进Al元素的扩散,二是在氧化膜表面形成裂纹和微孔缺陷。Ti-Al-Si-N涂层比Ti-Al-Si-Cu-N涂层具有更好的抗氧化性能。     

等离子体增强磁控溅射制备TiAlVSiCN涂层的抗冲蚀性能

目的 提高不锈钢基体的抗固体颗粒冲蚀性能.方法 在不锈钢基体表面,通过等离子体增强磁控溅射系统(PEMS),采用不同偏压工艺制备TiAlVSiCN纳米复合涂层.通过SEM、HRTEM观察涂层的微观形貌与组织,利用XRD、SAD分析涂层的物相组成与晶体结构,并通过划痕仪、纳米硬度计以及冲蚀试验机探究不同工艺涂层的结合强度、纳米硬度以及抗冲蚀性能差异.结果 采用PEMS制备出一系列不同偏压条件下的TiAlVSiCN涂层,涂层组织致密,呈柱状,主要包括纳米晶Ti(Al,V)(C,N)相和非晶相.偏压显著影响涂层的晶粒尺寸和非晶相分布,高偏压下的涂层主要由20～50 nm的Ti(Al,V)(C,N)纳米晶及其周围弥散分布的非晶相组成,而低偏压下的涂层主要由100 nm的Ti(Al,V)(C,N)纳米晶和连续分布的非晶相组成.高偏压下制备的涂层厚度超过20μm,纳米硬度可达(34.6±14.1)GPa,具有优良的结合强度(>65 N)和抗冲蚀性能,其抗冲蚀性能相比不锈钢基体提高近8倍.结论 通过与偏压参数的匹配控制,PEMS可有效调控纳米复合涂层的组织结构,实现硬度与弹性模量的良好匹配,制备出具有优良抗冲蚀性能、厚度达到20μm以上的TiAlVSiCN纳米晶-非晶复合涂层.     

Si掺杂对纳米硬质CrAlN涂层结构及性能影响

采用真空阴极电弧离子镀技术在V-4E工具钢表面制备了CrAlN、CrAlSiN两种多元纳米硬质涂层。采用划痕仪、工具显微镜、显微硬度计、球磨仪、SEM、EDS、XRD、TEM及XPS分析了涂层的力学性能、摩擦学性能以及微结构。结果表明:与CrAlN涂层相比,CrAlSiN涂层中Si的掺杂能使晶粒细化,提高涂层硬度和耐磨性、优化膜基结合水平;CrAlSiN涂层中的立方相CrN由(111)择优取向向(200)择优取向转变,晶粒尺寸明显减小,相结构为非晶态Si_3N_4包覆纳米晶复合混合框架结构。     

硬质纳米复合薄膜的热稳定性、抗氧化性与韧性

综述了纳米复合薄膜的硬度增强特性和热稳定性、在高温条件下(≥1 000℃)的抗氧化性和热稳定性、在X射线下呈非晶态的薄膜在高温条件下的热稳定性、以及具有高韧性新型硬质纳米复合薄膜的相关性能。这些新型高韧性硬质纳米复合薄膜具有较低的等效弹性模量E*(H/E*0.1),高弹性恢复系数(We≥60%),优异的摩擦学性能,以及良好的抗断裂能力。等效弹性模量E*=E(1-ν2),E为弹性模量,ν为泊松比。     

Effects of Post-weld Heat Treatment on Microstructure,Mechanical Properties and the Role of Weld Reinforcement in 2219 Aluminum Alloy TIG-Welded Joints

In as-welded state, each region of 2219 aluminum alloy TIG-welded joint shows diff erent microstructure and microhardness due to the diff erent welding heat cycles and the resulting evolution of second phases. After the post-weld heat treatment, both the amount and the size of the eutectic structure or θ phases decreased. Correspondingly, both the Cu content in α-Al matrix and the microhardness increased to a similar level in each region of the joint, and the tensile strength of the entire joint was greatly improved. Post-weld heat treatment played the role of solid solution strengthening and aging strengthening. After the post-weld heat treatment, the weld performance became similar to other regions, but weld reinforcements lost their reinforcing eff ect on the weld and their existence was more of an adverse eff ect. The joint without weld reinforcements after the post-weld heat treatment had the optimal tensile properties, and the specimens randomly crack in the weld zone.     

The First Phase of the SRIF Industrialized Base in ＂West Area＂ Has Been Put into Operation

After nearly two years＇ tense construction, the first phase of industrialized base of Shenyang Research Institute of Foundry （SRIF）, located at the Tiexi Casting and Forging Industrial Park in the west of Tiexi District, has now been completed and formally put into operation.     

THERMODYNAMICS STUDY ON THE DECOMPOSITION OF CHROMITE WITH KOH

Institute of Process Engineering, Chinese Academy of Sciences, China, has proposed a method for oxidative leaching of chromite with potassium hydroxide. Understanding the mechanism of chromite decomposition, especially in the potassium hydroxide fusion, is important for the optimization of the operating parameters of the oxidative leaching process. A traditional thermodynamic method is proposed and the thermal decomposition and the reaction decomposition during the oxidative leaching of chromite with KOH and oxygen is discussed, which suggests that chromite is mainly destroyed by reactions with KOH and oxygen. Meanwhile, equilibrium of the main reactions of the above process was calculated at different temperatures and oxygen partial pressures. The stable zones of productions, namely, K2CrO4 and Fe2O3, increase with the decrease of temperature, which indicates that higher temperature is not beneficial to thermodynamic reactions. In addition, a comparison of the general alkali methods is carried out, and it is concluded that the KOH leaching process is thermodynamically superior to the conventional chromate production process.     

INFLUENCE OF HEAT TREATMENT ON DAMPING BEHAVIOUR OF THE MAGNESIUM WROUGHT ALLOY AZ61

The effect of isochronal heat treatments for 1h on variation of damping, hardness and microstructural change of the magnesium wrought alloy AZ61 was investigated. Damping and hardness behaviour could be attributed to the evolution of precipitation process. The influence of precipitation on damping behaviour was explained in the framework of the dislocation string model of Granato and Lücke.     

Theoretical Analysis for the Motion and Temperature of Melt Droplets in Spray Degassing Process

The motion of melt droplets in spray degassing process was analyzed theoretically. The height of the treatment tank in spray degassing process could be determined by the results of theoretical calculation of motion of melt droplets. To know whether the melt droplets would solidify during spraying process, the balance temperature of melt droplets was also theoretically analyzed. Then proof experiments for theoretical results about temperature of melt droplets were carried. In comparison, the experimental results were nearly similar to the calculation results.     

Growth Kinetics of Single Inclusion Particle in Molten Melts

On the basis of the single-particle framework, a new theory on inclusion growth in metallurgical melts is developed to study the kinetics of inclusion growth on account of reaction and collision. The studies show that the early growth of inclusion depends on reaction growth and Brawnian motion collision, and where the former is decisive, the late growth depends on turbulence collision and Stokes＇ collision, and where the former is dominant; collision growth is very quick during the smelting process, lessened in the refining process, but nearly negligible in the continuous casting process.     

An Easy Way to Quantify the Adhesion Energy of Nanostructured Cu/X(X=Cr,Ta,Mo,Nb,Zr) Multilayer Films Adherent to Polyimide Substrates

An approach based on film buckling under simple uniaxial tensile testing was utilized in this paper to quantitatively estimate the interfacial energy of the nanostructured multilayer films(NMFs) adherent to flexible substrates. The interfacial energies of polyimide-supported NMFs are determined to be *5.0 J/m2 for Cu/Cr, *4.1 J/m2 for Cu/Ta,*2.8 J/m2 for Cu/Mo, *1.1 J/m2 for Cu/Nb, and *1.2 J/m2 for Cu/Zr NMFs. Furthermore, a linear relationship between the adhesion energy and the interfacial shear strength is clearly demonstrated for the Cu-based NMFs, which is highly indicative of the applicability and reliability of the modified models.     

High-Speed Friction Stir Welding of SiC_p/Al–Mg–Si–Cu Composite

A 17 vol% SiCp/Al–Mg–Si–Cu composite plate with a thickness of 3 mm was successfully friction stir welded(FSWed) at a very high welding speed of 2000 mm/min for the first time. Microstructural observation indicated that the coarsening of the precipitates was greatly inhibited in the heat-affected zone of the FSW joint at high welding speed, due to the significantly reduced peak temperature and duration at high temperature. Therefore, prominent enhancement of the hardness was achieved at the lowest hardness zone of the FSW joint at this high welding speed, which was similar to that of the nugget zone. Furthermore, the ultimate tensile strength of the joint was as high as 369 MPa, which was much higher than that obtained at low welding speed of 100 mm/min(298 MPa). This study provides an effective method to weld aluminum matrix composite with superior quality and high welding efficiency.     

新型的治疗阿尔茨海默氏症药物(1-二甲基磷酰基-2,2,2-三氯)-乙基-1-醇烟酸醋对体外神经细胞的作用

目的: 观察本实验室合成的一种治疗阿尔茨海默氏症(AD)的药物(1-二甲基磷酰基-2, 2, 2 -三氯)-乙基^-1-醇烟酸醋(NMF),对体外培养的皮层神经细胞活性的影响以及对海人藻酸(KA)所致的神经损伤的保护作用。方法: 采用体外培养皮层神经元的方法,解剖分离 15 d胚胎小鼠皮层神经细胞, 接种于 96孔板,48 h 后加药并培养 72 h,以 MIT 法 观察 NMF 对小鼠皮层神经细胞活性的影响;同时将接种于 24 孔板的细胞预先给予 NMF,d 3 时加或不加KA处理后,以台盼蓝染色鉴别并计数死、活细胞,可得出细胞的存活率。结果: NMF 明显促进胎鼠皮层神经元活性,其中 NMF1、0. 1、10nmol·L^-1促进神经元活性增殖率分别高达 34.7%、37.4%、36. 7%, NMF 明显促进正常胎鼠皮层神经元存活卒,与对照组比较,10nmol·L^-1 NMF 对皮层神经元的存活率分别提高 39.3%、73.5%。 NMF能显著 对抗 KA 所致的神经元损伤,与 KA 损伤组相比, NMF0.1、10、10nmol·L^-1对损伤皮层神经元的保护率分别为 77.30%、80.10%、84.15%。结论: NMF 明 显促进胎鼠皮层神经元的洁性、提高正常皮层神经元,的存活卒,并能有效地保护KA所致的神经元损伤,提示 NMF 是一种很有潜力的治疗 AD 的药物。     

A STUDY OF TEMPERATURE-DEPENDENT VALENCE BOND STRUCTURE OF TITANIUM

On the basis of energy and shape method for the determination of the valence bond (VB) structures of crystal, the valence bond structure of titanium is redetermined at room temperature and calculated in the whole temperature range of 0-1943K. The outer shell electronic distribution of Ti is e_c~(2.9907) · (s_c~(0.4980) d_c~(2.4927)) ef1.0093 in crystal. The temperature dependences of the VB structures of hcp and bcc phases are the same. The VB structures of hcp and bcc phases monotonically increase or decrease with the increase in temperature, but show discontinuous changes at the phase-transformation temperature 1155K.