Plasma assists titanium nitride and surface modified titanium nitride nanoparticles from titanium scraps for magnetic properties and supercapacitor applications

Plasma methods are efficient processing for metal recovery from metal scrap, bearing minerals, electronic waste, etc. In this work, pure titanium nitride nanoparticles (TiN NPs) were synthesized from titanium scraps by the thermal plasma arc discharge (TPAD) method. TPAD synthesized TiN NPs have a highly crystalline nature with cubic and spherical morphologies with average particle sizes of 30–100 nm. Further, prepared TiN NPs involving surface modification (SM) or etching processes were investigated by using the non-thermal DC glow discharge plasma technique with air atmosphere at different processing times. SM@TiN NPs have a comparatively low crystalline, which was confirmed from the powder X-ray diffraction technique. SM@TiN NPs have very interesting core shell morphologies, which are due to the surface interactions of ionized air molecules. TiN and SM@TiN NPs have room-temperature ferromagnetic properties with high saturation magnetization (Ms) up to 2.6 and 3.0 emu/g and very high coercivity (Hc) of 235.5 Oe, respectively. TiN and SM@TiN NPs have superior energy storage performance with an outstanding specific capacitance of 192.8 and 435.1 F/g at a current density of 2 A/g with pseudocapacitive behavior. These results reveal that TiN and SM@TiN NPs have highly promising electrodes for supercapacitor applications.     

耐蚀合金中TiN析出机制

摘要：TiN颗粒尺寸及其分布对耐蚀合金性能有明显的影响，因此有必要对TiN在铸坯中的分布及其析出行为进行研究。采用扫描电镜(SEM)、金相显微镜（OM）观察了TiN夹杂物在铸坯中的分布、尺寸及其形貌；基于热力学和动力学理论分析了耐蚀合金铸坯中TiN夹杂物的析出时机及其尺寸，结合试验结果和理论计算明确了TiN夹杂物在凝固后铸坯中的位置和尺寸与析出时机的关系，为控制TiN夹杂物提供理论指导。结果表明，冶炼过程中析出的TiN夹杂物尺寸较大，在凝固过程中被枝晶吞没，位于铸坯枝晶内和等轴晶内；微观偏析计算结果表明，在凝固分数为0.55时，TiN开始析出，最开始析出TiN夹杂物的逐渐长大，长大后的TiN易于被二次枝晶吞没，最终位于铸坯中的枝晶间和等轴晶内，后期析出的TiN则在枝晶间和等轴晶间。固相中析出的TiN夹杂物长大较慢，尺寸细小，最终位于奥氏体晶界。     

Influence of TiN dopant on microstructure of TiB2 ceramic sintered by spark plasma

In this study, the impact of TiN as a sintering aid on the relative density and microstructure of TiB₂ ceramic was investigated. Monolithic TiB₂ and TiB₂ doped with 5?wt% TiN were sintered at 1900?°C for 7?min dwell time under the pressure of 40?MPa by spark plasma. The addition of TiN affected the microstructure of TiB₂-based sample considerably depicting the finer grains in the as-sintered ceramic. X-ray diffraction evaluation indicated that no interaction occurred between the initial materials. However, detail investigation by the map analysis and energy dispersive spectroscopy results revealed the formation of in-situ nano-sized hBN secondary phase in the TiN-doped TiB₂. In addition, TiN played a remarkable role on increasing the relative density of TiN-doped TiB₂ ceramic producing a nearly fully dense ceramic with relative density of 99.9% in comparison with the monolithic ceramic having 96.7% relative density.     

Protective nature of nano-TiN coatings shaped by EPD on Ti substrates

The hardness and corrosion resistance of TiN coatings, processed by Electrophoretic Deposition (EPD) to cover polished and unpolished Ti substrates, have been evaluated. A deposition time of 5 min has been enough to obtain a cohesive layer of 7–8 μm in thickness. The coatings were thermally treated in vacuum atmosphere at 1200 °C for 1 h with heating and cooling rates of 5 °C min^?1. The surfaces have been covered homogeneously optimizing the properties of the Ti substrates. Uniform and dense TiN coatings have been obtained onto polished substrates, while on unpolished Ti the nitrogen diffuses toward the substrate, moderately dissolving TiN coating. The nanohardness values of the polished samples have been increased from 2.8–4.8 GPa up to 6.5–8.5 GPa. Besides, the corrosion current density has been reduced more than one order of magnitude obtaining a protective efficiency of 82%. These values have been compared with other works in literature where authors used complex and costly processing techniques, demonstrating the strong impact of the colloidal processing over the specific properties of the material.     

稀土含量对Ti6Al4V钛合金等离子渗氮层组织和摩擦学性能的影响

目的研究稀土含量对Ti6Al4V钛合金表面等离子体渗氮层结构和性能的影响。方法运用等离子表面改性技术对Ti6Al4V(TC4)钛合金进行等离子渗氮处理,渗氮过程中通入不同含量的稀土作为催渗剂,以获得钛合金表面强化层。利用金相显微镜和扫描电子显微镜(SEM)观察渗氮层组织,用X射线衍射仪(XRD)分析渗层相组成,用能谱仪(EDS)检测渗层的化学成分,用维氏显微硬度计测量渗层的显微硬度,用球-盘式摩擦磨损试验机和三维轮廓仪检测渗层的摩擦磨损性能。结果TC4钛合金表面等离子渗氮层结构包括表面化合物层(主要成分为δ-TiN)和扩散层(主要为N原子扩散形成的N-Ti固溶体),加入稀土可以促进N原子向基体的扩散,提高渗氮速度。渗层厚度增加,硬度和耐磨性能提高,扩散层使钛合金基体与化合物层之间的硬度梯度更加平缓。当稀土通入速率为60 mL/min时,渗层厚度可达155μm,表面硬度为1275HV0.05,摩擦系数降到0.27,磨损率明显降低。结论钛合金等离子渗氮过程中加入稀土可以有效提高渗速,改善渗氮层硬度,提高材料表面的耐磨性能。     

Effects of TiN addition on the properties of hot pressed TiN–Ti/Al2O3 composites

TiN–Ti/Al₂O₃ composites of varying TiN content (0–20?vol%) were prepared by vacuum hot-pressing sintering at different temperatures (1400?°C and 1500?°C) to investigate how TiN affected the mechanical properties and electrical conductivity of the composites. Sintered samples with added TiN exhibited better performance than those without it. The sample with 20?vol% TiN sintered 1500?°C had an optimal relative density of 99.49, Vickers hardness of 14.94?GPa, flexural strength of 321.55?MPa, and electrical resistivity of 1474.7?μΩ?cm. However, this increased temperature did not improve the best sample resistivity of 930.3?μΩ?cm, which was obtained at 1400?°C. Form SEM images and XRD patterns, the positive effect of TiN on composite mechanical properties may be ascribed to its good performance of high hardness and strength, a decrease of the brittle intermetallic phase, the form of AlTi₃N, and the impact of the fine-grained strength of the TiN phase.     

Highly conductive mesoporous hierarchical carbon hollow fibers fabricated via confinement of TiO2 coating by ALD

A polysulfone (PSF) hollow fiber composed of interconnected nanofibers within its wall was employed as a template to deposit with a layer of TiO₂ by atomic layer deposition. Direct nitridation of the TiO₂-coated PSF hollow fiber at 800 and 1000°C was conducted, and a new hierarchical structure of TiO_xN_1−x and TiN@nitrogen-doped carbon hollow fibers, respectively, was formed. The PSF fiber served as the source of carbon and was directly transformed to a nitrogen-doped carbon fiber because the shape change was confined by the TiO₂ coating. In the meantime, TiO_xN_1−x or TiN was formed after the nitridation of TiO₂. X-ray photoelectron spectrometric analysis indicated that there was no chemical bonding between the nitridized coating and the carbon nanofibers. It implies that the nitridation of TiO₂ and carbonization of PSF proceed independently and simultaneously in the nitridation process. Raman spectroscopic analysis also confirmed the formation of graphitic lattice and Ti–N bonding. Electrical measurement indicated that both fibers were highly conductive, with the electrical resistivity in the order of 10⁻⁵ Ω m, which is lower than those of amorphous carbon and graphite along the direction perpendicular to the basal plane.     

Microstructure and electrical conductivity of Mo/TiN composite powder for alkali metal thermal to electric converter electrodes

A Mo/TiN composite powder has been synthesized by a sol–gel method to improve the electrical performance and microstructural stability of the alkali metal thermal to electric converter electrode. The core (TiN)–shell (Mo) structure of the composite powder is confirmed by energy-dispersive X-ray spectroscopy and scanning electron microscopy. The composite powder is primarily composed of submicron (400–800 nm) particles that are coated on a core (>3–5 μm) particle. The Mo/TiN composite electrode exhibits high electrical conductivities of 1000 Scm⁻¹ at 300 °C and 260 Scm⁻¹ at 700  °C in an Ar atmosphere. The electrode exhibits excellent tolerance against grain growth during thermal cycling tests (R.T.↔800 °C), where the average growth rate of Mo grains in the Mo/TiN composite electrodes is controlled less than 0.5%/time (0.62→0.65 μm), while the growth rate in Mo electrodes is 306.7%/time (0.24→3.92 μm). It can be concluded that the Mo/TiN composite powder will suppress the degradation of the electrode and enhance the performance and durability of the unit cell at elevated temperatures.     

高功率脉冲磁控溅射制备的TiN薄膜 应力释放及其结合稳定性研究

目的 探究高功率脉冲磁控溅射（HPPMS）制备的氮化钛（TiN）薄膜在自然时效过程中,应力、薄膜/基体结合性能随时间的变化规律。方法 采用高功率脉冲磁控溅射（HPPMS）技术,通过调控基体偏压（-50、-150 V）,制备出具有不同残余压应力（3.18、7.46 GPa）的TiN薄膜,并采用基片曲率法、X射线衍射法、划痕法和超显微硬度计评价了薄膜的应力、薄膜/基体结合性能、硬度随时间的变化规律。结果 在沉积完成后1 h内,-50 V和-150 V基体偏压下制备的TiN薄膜压应力分别在3.12~3.39 GPa和7.40~7.55 GPa范围内波动,薄膜压应力没有发生明显变化;沉积完成后1~7天,平均每天分别下降28.57 MPa和35.71 MPa;7~30天,平均每天分别下降2.08 MPa和2.50 MPa;30~60天内,平均每天分别下降1.67 MPa和7.00 MPa。其压应力连续下降,且均表现出前期下降速率快,后期下降逐渐放缓的趋势。自然放置60天后,应力基本释放完毕,薄膜性质基本保持稳定。同时,薄膜/基体结合性能随时间逐渐变差,薄膜硬度下降。结论 HPPMS制备的TiN薄膜在自然时效过程中,其残余应力会随时间增加,连续下降,进而影响薄膜的力学性能。     

恒电位对TiN涂层在人工海水环境中腐蚀磨损的影响

目的研究不同恒电位对TiN涂层在人工海水环境中腐蚀磨损行为的影响。方法用多弧离子镀系统在316不锈钢上沉积TiN涂层。通过XRD测试、纳米压痕硬度测试、膜基结合力测试、电化学工作站测试、不同恒电位下磨蚀实验和涂层的磨痕截面轮廓测试,分别评价TiN涂层的相结构、硬度、结合力、电化学性能、摩擦系数、磨损率,并通过扫描电子显微镜对涂层表面形貌、截面形貌和磨痕形貌进行分析。结果在摩擦条件下,TiN涂层的开路电位随着滑动摩擦时间的增加而逐渐降低。TiN涂层在不同恒电位(-1V、-0.5 V、OCP、0 V)下滑动摩擦,平均摩擦系数分别为0.392,0.416、0.324、0.348。磨损率分别为1.8117×10-6、3.1123×10-6、4.5958×10-6、7.7724×10-6 mm3/(N·m)。在0.5 V下,涂层被磨穿。TiN涂层在人工海水环境中的主要腐蚀磨损破坏机制为磨粒磨损和疲劳点蚀。结论提高加载电位,涂层的磨损量和磨损率同步增大。在-1、-0.5 V,OCP下,由腐蚀促进磨损的损失量占TiN涂层损失总量的比重逐渐增大,依次为0%、41.78%、61.77%。在0 V时,TiN涂层产生了由磨损促进腐蚀的损失量,占TiN涂层损失总量的比例为6.1%。