反应电火花沉积TiN/Ti复合涂层机理与性能

利用DZ-1400型电火花沉积/堆焊机,以工业纯钛TA2为电极,以工业纯氮为保护气和反应气,在TCA钛合金表面上制备了TiN/Ti复合涂层.用SEM、XRD、AES等仪器对涂层、物相、微观结构、元素组成及界面行为进行分析,测定了涂层的显微硬度,利用自制磨损试验机对比了涂层与淬火回火65Mn的磨损性能.结果表明,TiN/Ti复合涂层与基体形成良好的冶金结合,涂层主要由钛和反应合成的TiN、Ti2N相组成,组织致密、均匀、连续,涂层平均显微硬度可达1390HV0.1,约是基体硬度的6.3倍,涂层耐磨性良好.     

电火花沉积反应合成TiN增强金属基复合涂层

利用自制的电火花沉积充气密闭式保护装置和DZ-1400型电火花沉积机,以工业纯钛TA2为电极,以工业纯氮为保护气和反应气,在45钢试件表面上电火花沉积反应合成制备了TiN增强金属基陶瓷复合涂层.利用X射线衍射仪测定了涂层的物相组成,利用扫描电子显微镜观察分析了涂层的显微组织结构,利用硬度仪测试了涂层的显微硬度,利用自制磨损试验装置对比了涂层与淬火W18Cr4V高速钢的耐磨性能.结果表明,涂层与基体结合致密,涂层主要由电极材料钛、原位自生的TiN和基体材料铁组成,涂层的平均显微硬度可达1 323 HV0.1,涂层具有较好的耐磨性.     

低温等离子渗镍对工业纯钛微观组织及抗蚀性能影响

采用机械研磨方法使工业纯钛表面形成一层均匀的细晶强化层,然后在细晶强化层处进行低温等离子渗镍。使用X射线衍射(XRD),X射线光电子能谱(XPS)方法研究镍基涂层的成分与物相,采用扫描电镜(SEM)方法分析镍基涂层的表面形貌,利用极化曲线方法探讨镍基涂层的抗腐蚀性能。结果表明,工业纯钛的表层钝化膜成分为Ti O2,而低温渗镍工业纯钛的表层钝化膜成分为Ti O2、Ni O、Ni2O3和Ni(OH)2,该层钝化膜能够有效提升纯钛的抗腐蚀性能。     

电火花沉积反应合成TiN增强Fe基金属陶瓷涂层

利用自制的电火花沉积充气密闭式保护装置和DZ-1400型电火花沉积/堆焊机,以工业纯钛TA2为电极,以工业纯氮为保护气和反应气,在45#钢基体试样表面制各出了厚度为60～80 μm的TiN增强金属基陶瓷涂层.采用扫描电镜(SEM)观测了涂层微观结构和界面行为,分析了涂层形成机理,利用X射线仪(XRD)测定了涂层的物相组成,利用显微硬度仪测试了涂层的显微硬度,利用自制磨损试验机对比了涂层与淬火W18Cr4V高速钢的耐磨性.结果表明:涂层主要由TiN和FeTi两相组成,涂层组织致密、均匀、较连续,涂层与基体形成良好的冶金结合,涂层显微硬度HV高达15.88 GPa,约是基体硬度的5倍,涂层具有较好的耐磨性.     

钛双极板无定型碳涂层在PEMFC不同氟离子环境中的性能

采用直流平衡磁控溅射在TA2基材表面制备了无定型碳涂层,并采用电化学和表面接触电阻测试分析了TA2基材和无定型碳涂层在质子交换膜燃料电池（PEMFC）不同F^-浓度环境中的耐腐蚀性和导电性。无定型碳涂层的耐腐蚀性和导电性均优于TA2基材,随着F^-浓度由1×10^-6 mol/L逐渐增加到1×10^-3 mol/L,TA2基材和无定型涂层的缺陷密度增加,试样耐腐蚀性均有所下降。在高F^-浓度环境中（1×10^-3 mol/L）,无定型碳涂层在0.6 V电位下的腐蚀电流密度为0.68 μA/cm²,依然能够对基材形成良好的保护。此外,TA2基材表面制备无定型碳涂层后,试样的表面导电性有所提升,其界面接触电阻值由76.40 mΩ·cm²（TA2）下降至6.52 mΩ·cm²。     

含TiN中间层IrO2-Ta2O5涂层钛阳极的电催化性能

采用钛片在氮气中700 ℃退火的方法,在钛片表面原位生成TiN薄膜,并以此为基体采用热分解法制备IrO2-Ta2O5涂层钛阳极.研究含TiN中间层IrO2-Ta2O5涂层钛阳极及传统IrO2-Ta2O5涂层钛阳极的开路电位、析氧行为、循环伏安和电化学阻抗等性能.结果表明:含TiN中间层IrO2-Ta2O5涂层钛阳极具有非连续状裂纹结构,且表面生长出大量IrO2纳米晶体,其电催化析氧性能优于传统IrO2-Ta2O5涂层钛阳极的电催化析氧性能;涂层烧结温度越低,电化学性能越好;当烧结温度低于500 ℃时,TiN中间层可以显著延长IrO2-Ta2O5涂层钛阳极的工作寿命.     

钛合金表面反应电火花沉积TiN/Ti复合涂层

利用自制的电火花沉积充气密闭式保护装置和DZ-1400型电火花沉积/堆焊机,以工业纯钛TA2为电极,以工业纯氮为保护气和反应气,在TC4钛合金表面上反应电火花沉积制备了TiN/Ti复合涂层.利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、X射线光电子仪(XPS)分析了涂层的组织、物相和元素组成,利用显微硬度计测定了涂层的显微硬度,利用自制磨损试验装置对比涂层与淬火W18Cr4V高速钢的磨损性能.结果表明,涂层与基体形成良好的冶金结合,涂层主要由钛和反应合成的TiN组成,涂层的平均显微硬度可达1 388 HV0.1,是基体硬度的6倍以上,涂层具有较好的耐磨性.

Abstract：

TiN/Ti composite coating was deposited on TC4 titanium alloy substrate with the self-made special gas-filled-closed electric-spark deposition device and electric-spark deposition machine modeled DZ-1400, the industry pure titanium (TA2) was used as electrode and the industry pure nitrogen gas as shielding and reacting atmosphere. The microstructures, interfacial behavior, phase and element in the coatings were investigated by scanning electronic microscope, X-ray diffraction and X-ray photo spectrum. The microhardness of coatings was tested and its wear-resistance property was tested by the self-made abrasion machine and compared with Wi8Cr4V rapid steel treated by quenching. The results show that an excellent bonding between the coating and substrate is ensured by the strong metallurgical interface. The coatings are mainly composed of Ti and synthesized TiN. The highest microhardness of coating reaches to 1 388 HV0. 1, which is six times higher than that of the substrates. Wear resistance of the coatings is excellent.     

GO-PTFE-C涂层改性Ti金属板的防腐性能研究

目的提高钛金属板的抗腐蚀性能。方法采用水热浸渍两道工序在Ti双极板上制备GO-PTFE-C复合改性涂层。使用0.1 mol/L葡萄糖溶液作为碳源,在170℃+10 h条件下,于反应釜中完成碳涂层制备。对获得的涂层进行热处理,浸渍5%(质量分数)的聚四氟乙烯(PTFE)溶液和不同浓度氧化石墨烯(GO)的混合悬浮液后,在350℃热处理得到涂层。采用傅氏转换红外线光谱分析仪(FTIR)、扫描电子显微镜(SEM)和能谱仪(EDS)分析表面形貌和成分,选取三电极体系并利用电化学工作站(CHI 660e)表征改性前后双极板电化学性能,在模拟质子交换膜燃料电池(PEMFC)环境中测试其抗腐蚀性能。结果与单一的碳涂层相比,GO-PTFE表面具有更多的C=O官能团,同时由于聚四氟乙烯表面的F与含氧官能团的氧原子电子云的诱导效应,涂层附着力明显提高。其中,采用5%PTFE+3 g/L GO浸渍的涂层的腐蚀电流密度和接触角分别为0.008μA/cm~2和103.6°,恒电位极化测试(0.6 V和-0.1 V)显示,涂层的腐蚀电流密度均低于1μA/cm~2。结论以碳涂层为基体,浸渍GO和PTFE的混合液后,制备所得的钛基双极板在PEMFC的双极板中显示出巨大的应用前景。     

表面纳米化等离子渗镍对工业纯钛抗腐蚀性能的影响

采用机械研磨对工业纯钛表面纳米化处理,利用等离子双辉进行纯钛表面渗镍。借助SEM、XRD分析处理后的表面形貌、晶粒大小,利用极化曲线以及阻抗谱分析处理后的表面抗腐蚀性能。利用极化曲线以及阻抗谱对处理后的表面进行抗腐蚀性能进行分析。结果表明经过机械研磨处理后的钛表面产生了一层纳米晶,双辉等离子渗镍后的钛表面均匀包覆了一层镍的涂层,试样在模拟海水环境中的抗腐蚀性能有了明显提升,较未处理试样,自腐蚀电位提升了0.35 V,自腐蚀电流密度降低了1.87 A·cm~(-2),极化电阻增加了29.4Ω·cm。     

柔性钛电极电火花合成TiN涂层

文中提出一种利用柔性钛电极在钛合金TC4表面合成TiN涂层以改善工件表面性能的新方法.在加工中利用柔性钛电极与钛合金TC4表面进行电火花放电,同时通过钛电极内部向加工区域通入氮气,利用电火花放电能量在工件表面反应生成TiN涂层.测量其表面硬度并利用SEM,XRD等手段对其涂层微观形貌和组分进行测试.结果表明,在TC4工件表面制备出了TiN强化涂层,涂层致密、均匀、连续;TiN涂层厚度超过1 mm;涂层主要由TiN强化相组成,显微硬度高达1859.6 MPa;涂层表面的放电坑大而浅且存在刮削痕迹,柔性钛电极丝对TiN涂层有较强的刮削涂覆作用;TiN涂层与基体之间相互渗透形成冶金结合.     

Electrochemical characteristics and interfacial contact resistance of multi-layered Ti/TiN coating for metallic bipolar-plate of polymer electrolyte membrane fuel cells

Metallic bipolar-plates have advantages over non-porous graphite ones due to their higher mechanical strength and better electrical conductivity. However, corrosion resistance and interfacial contact resistance are major concerns that remain to be solved, since metals such as stainless steels may develop oxide layers that decrease electrical conductivity, thus lowering fuel cell efficiency. In this study, multi-layered nitride coatings consisting of Ti and TiN were deposited on 316L stainless steel (SS316L) by a D.C magnetron sputtering method to enhance the corrosion resistance and to lower the interfacial contact resistance (ICR) of metallic bipolarplates for a polymer electrolyte membrane fuel cell (PEMFC). Electrochemical methods were conducted and ICRs of the coated specimens were measured to investigate the potential of the coated metallic bipolar-plate for use in PEMFCs. The multi-layered Ti/TiN coating deposited on SS316 showed lower ICR values than the single-layered TiN coating, and improved corrosion resistance when the PEMFC was not in operation while the degradation of the coating layer was observed in both cathodic and anodic working environments.     

Corrosion behavior of TiN coated type 316 stainless steel in simulated PEMFC environments

The corrosion behavior of TiN coated type 316 stainless steel (SS) was investigated in simulated proton exchange membrane fuel cell environments, i.e. 0.01 M HCl + 0.01 M Na₂SO₄ solutions bubbled with pure oxygen and hydrogen gases, respectively, by using electrochemical measurement techniques. 316SS substrate can passivate spontaneously in simulated cathode environment, while it is in active state at the corrosion potential in simulated anode environment. TiN coatings have much better corrosion resistance and passivity under both simulated conditions. No significant degradation takes place in TiN coatings under the typical load conditions of fuel cell for 4 h. The loss of small part of coatings occurs during the immersion tests of TiN coatings in the oxygen environment for 1000 h and in the hydrogen environment for 240 h, respectively, but the exposed substrate areas are passivated in both environments. The results reveal that TiN coating can offer 316SS higher corrosion resistance and electric conductivity, and that further effort to improve the coating quality and to evaluate the long-term stability of 316SS/TiN coating systems under simulated conditions are deserved. In addition, the characteristics of corrosion process for TiN coatings on passivatable substrate were discussed in detail.     

304不锈钢表面TiN涂层的耐蚀性能

目的 提高304不锈钢的耐腐蚀性能.方法 采用磁控溅射技术在304不锈钢表面沉积TiN涂层,并采用SEM、XRD及GDOES对涂层的表面形貌、成分进行测试.通过极化曲线和电化学噪声技术评价TiN涂层和基体在pH=2.5的3.5%(质量分数)NaCl溶液中的腐蚀行为,并研究涂层的失效机制.结果 在304不锈钢表面沉积了厚约1μm且均匀、致密的TiN涂层.极化曲线分析表明,基体和TiN涂层试样出现了自钝化和点蚀现象,其中304不锈钢基体的腐蚀电位为-0.41 V,腐蚀电流密度为8.01×10-6 A/cm2,与之相比,TiN涂层的腐蚀电位(-0.28V)明显增大,腐蚀电流密度(6.34×10-8 A/cm2)显著降低.电化学噪声分析显示,在浸泡初期,TiN涂层电极电流暂态峰数量较少,强度较大,噪声电阻较低,而随着浸泡时间的延长,其电流暂态峰数量增加,强度降低,噪声电阻明显大于304不锈钢基体.腐蚀形貌观察表明,304不锈钢和TiN涂层表面均出现了点蚀.结论 TiN涂层能够明显改善基体的耐蚀性能.TiN涂层主要起物理阻碍作用,涂层的主要失效形式是涂层表面的微观缺陷和破裂.     

TA2钛板掺杂钒离子渗碳层的耐腐蚀性能

为提高钛基双极板的耐腐蚀性能和导电性,在TA2纯钛的表面进行双辉离子渗碳,另外为降低渗碳温度,在渗碳过程中掺杂钒。使用扫描电镜和能谱分析、X射线衍射对改性层的组织结构、化学成分、物相组成进行研究,并测得改性层的界面接触电阻率、耐腐蚀性能。结果表明,在优化的制备工艺参数下,在TA2表面生成结构致密的TiC改性层、钒掺杂渗碳改性层。当压实力为140 N/cm²时,730℃下制备的钒掺杂渗碳改性层、850℃下制备的TiC改性层、TA2基体的界面接触电阻率分别是1.17、3.66、14.71 mΩ/cm²。在模拟双极板的工作环境中,测得730℃下制备的钒掺杂渗碳改性层、850℃下制备的TiC改性层的自腐蚀电流密度分别是5.238、7.563μA/cm²,均比TA2基体的腐蚀电流密度低1个数量级。在离子渗碳的过程中掺杂钒可以有效降低渗碳的工艺温度,并且提高TA2基体的导电性和耐腐蚀性能。     

热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气环境中的腐蚀行为研究

目的 为详细研究热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气下的腐蚀行为及作用机理,同时为热浸镀Zn-Al-Mg镀层在湿热海洋大气环境中服役提供数据参考。方法 采用腐蚀失重、XRD、SEM、电化学等测试方法对热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气环境下的腐蚀行为进行研究。结果 腐蚀产物主要由Zn₅(OH)₈Cl₂·H₂O组成,腐蚀一段时间后,发现少量ZnO、Zn₅(OH)₆CO₃,腐蚀产物具有与锌腐蚀类似的层状结构,1 848 h呈“三明治”型,相比于上下两层暗色物质,中层亮色腐蚀产物富集更多的Cl元素。热浸镀Zn-Al-Mg镀层腐蚀速率大体随时间延长呈上升趋势,只在672～840 h腐蚀速率下降,对比镀锌在模拟环境和锌在湿热大气环境中的腐蚀,热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气中表现出较好的耐蚀性。结论热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气下腐蚀产物演变与腐蚀过程中Mg的参与有关。腐蚀672～840h阶段腐蚀速率...     

Preparation and corrosion behavior of electrodeposited Ni–TiN composite coatings

Ni–TiN composite coatings were successfully prepared by direct current (DC), pulse current (PC) and ultrasonic pulse current (UPC) deposition methods. The morphology, mechanical properties and the corrosion behavior of Ni–TiN composite coatings were investigated using atomic force microscope (AFM), scanning electronic microscope (SEM), X-ray diffraction (XRD) and gravimetric analysis. The results show that the Ni–TiN composite coatings synthesized by UPC deposition method possess a compact and exiguous surface morphology. The XRD results demonstrate that the average grain diameter of Ni and TiN in composite coating prepared by UPC deposition is 52.6 and 35.7 nm, respectively. In the corrosion tests, the coating prepared by UPC deposition exhibits the best corrosion resistance, whereas the coating fabricated by DC deposition suffers the most serious damage.     

氮化钛含量对热塑性涂层光热效应及自修复性能的影响

为了实现涂层破损的高效自修复,将纳米氮化钛与热塑性聚氨酯混合,制备了不同氮化钛含量的复合涂层。 利用扫描电子显微镜(SEM)、X 射线衍射仪(XRD)和紫外可见分光光度计(UV-Vis)分析了氮化钛的结构和光谱吸收特征;利用差示扫描量热仪(DSC)、热电偶、光学显微镜、扫描电子显微镜( SEM)、交流阻抗谱(EIS)等对复合涂层的热力学性能、光热转换性能、自修复性能及防腐性能进行测试。 结果表明:基于纳米氮化钛的表面等离激元特性,在热塑性聚氨酯中添加质量分数为 2%的氮化钛后,复合涂层具有良好的光热转换性能,在近红外激光照射后其表面温度高于聚氨酯的玻璃化转变温度。 当涂层表面有划口时,通过激光照射可以提高涂层的局部温度,使聚合物分子链运动并流向划痕界面,复合涂层的结构和防腐性能均得到恢复,并且修复后涂层中氮化钛仍分布均匀。 此外,氮化钛纳米颗粒还有助于填补涂层的微观孔隙,使复合涂层的防腐性能提高。     

质子交换膜燃料电池中TA1双极板的表面改性研究

针对TA1金属双极板,采用双辉光等离子方法制备出表面Zr改性层(Zr-TA1),研究了改性层的微观结构和性能。结果表明,Zr改性层厚度约为3μm且表面平整致密。在模拟PEMFC阴/阳极环境下,Zr-TA1的自腐蚀电位明显升高,腐蚀电流密度降低了1~2个数量级。Zr改性层提高了TA1的疏水性能,其接触角由TA1双极板的71o提高到Zr-TA1的94o。经改性的双极板在140 N·cm^-2的装配压力下,接触电阻由117.3 mΩ·cm²降低到了15.5 mΩ·cm²,极大地提高了样品的表面导电性能。     

Corrosion and tribological properties and impact fatigue behaviors of TiN- and DLC-coated stainless steels in a simulated body fluid environment

In this study, the corrosion and tribological properties of TiN and DLC coatings were investigated in a simulated body fluid (SBF) environment. The ball-on-plate impact tests were conducted on the coatings under a combined force of a 700 N static load and a 700 N dynamic impact load for 10,000 impacting cycles. The results indicated that the TiN and DLC coatings could achieve a higher corrosion polarization resistance and a more stable corrosion potential in the SBF environment than the uncoated stainless steel substrate SS316L. The good corrosion protection performance of TiN could be due to the formation of a Ti-O passive layer on the coating surface, which protected the coating from further corrosion. The superior corrosion property of the DLC coating was likely attributed to its chemical inertness under the SBF condition. The TiN and DLC coatings also exhibited an excellent wear resistance and chemical stability during the sliding tests against a high density polyethylene (HDPE) biomaterial. Compared to the DLC coating, the TiN coating has a better compatibility with the HDPE. However, the impact tests showed that the fatigue cracks and the coating chipping occurred on the TiN coating but not on the DLC coating.     

铝合金双极板磁控溅射Ag掺杂类石墨薄膜表面改性研究

目的研究在铝合金样品表面制备Ag掺杂类石墨薄膜对样品导电、耐蚀性能的影响。方法采用磁控溅射离子镀技术,在6061铝合金表面沉积了Ag掺杂类石墨层,对样品微观形貌、接触电阻和电化学腐蚀性能进行了观察测试。结果类石墨薄膜厚度随着Ag靶电流的提高而增大。与铝合金基体相比,镀膜样品的接触电阻降低了2个数量级,腐蚀电流密度降低了2~3个数量级。Ag靶材电流为0.04 A时,镀膜样品接触电阻(1.5 MPa压强)为1.93 m?·cm~2,腐蚀电流密度低至10~(-5.5) A/cm~2数量级。结论沉积有Ag掺杂类石墨薄膜的样品达到了极低的表面接触电阻与较低的腐蚀电流密度,使镀膜后的铝合金样品具有优异的导电性能与较好的耐腐蚀性能。