钼添加对CrN涂层抗氧化性能的影响（英文）

研究钼添加对CrN涂层微观结构和抗氧化性能的影响,采用反应磁控溅射法在硅片和高速钢片上制备不同Mo含量的Cr-Mo-N涂层,并在500～800℃的高温空气中退火1 h,用X射线衍射(XRD)、拉曼光谱和扫描电子显微镜(SEM)对涂层退火前后的微观形貌进行表征。沉积的Cr N和Cr-Mo-N涂层均表现出基于Cr N晶格的B1面心立方相(fcc)。Mo离子取代CrN晶格中的Cr离子,形成CrMo-N固溶体。在600℃时,XRD和拉曼光谱表明,Mo含量较高的Cr-Mo-N涂层中形成MoO_3相,表面较粗糙,含氧量较高。在700℃时,CrN涂层由于内应力的作用,其横截面形貌为疏松的柱状晶,并有一定的多孔区,而Cr-Mo-N涂层则为致密的柱状晶结构。低Mo含量(17at%)的Cr-Mo-N涂层比Cr N涂层具有更好的抗氧化性。     

磁控溅射Cr/CrN和Cr/CrN/CrAlN涂层的抗高温氧化性能

为了提高航空紧固件涂层的高温工况防护能力,采用磁控溅射技术在钛合金表面分别制备 Cr/ CrN 交替涂层和 Cr/ CrN / CrAlN 涂层,研究氧化时间和氧化温度对涂层高温氧化性能影响。 利用 SEM、EDS 和 XRD 进行微观形貌和物相成分分析,采用热重法分析氧化增重量( w) 和氧化速率常数( k) ,使用显微硬度计测试涂层高温氧化后硬度。 结果表明:随着氧化时间和氧化温度的增加,涂层硬度均降低,但 Cr/ CrN / CrAlN 涂层下降趋势更缓; 两种涂层的 w 和 k 均上升,其中 Cr/ CrN / CrAlN 涂层 w 和 k 增幅均低于 Cr/ CrN 交替涂层,950 ℃ 氧化 96 h 后 Cr/ CrN / CrAlN 涂层和 Cr/ CrN 交替涂层的 w 值分别为 40 mg / cm ² 和 135. 7 mg / cm ² ,其对应的 k 分别为 0. 1996 和 0. 4092,说明 Cr/ CrN / CrAlN 涂层抗高温氧化性更好。 Cr/ CrN / CrAlN 涂层活化能 E_a 值比 Cr/ CrN 交替涂层高 48. 5%,Cr/ CrN / CrAlN 涂层在高温下产生 Cr₂O₃ 和 Al ₂O₃ 的混合氧化物,结构更致密,Cr/ CrN / CrAlN 涂层抗高温氧化性能高于 Cr/ CrN 交替涂层。     

轰击离子能量对V2AlC MAX相涂层结构及力学性能的影响

采用物理气相沉积（PVD）磁控溅射沉积方法,通过改变轰击离子能量制备高密度的V₂AlC涂层,并探究不同轰击离子能量对涂层结构和性能的影响。利用能谱仪测试、X射线衍射、拉曼光谱、扫描电镜、原子力显微镜对涂层的化学组成、相结构、表面与截面形貌进行分析,同时利用纳米压痕测试评价V₂AlC涂层力学性能。结果表明,提高轰击离子能量从15 eV到35 eV可以有效使得V₂AlC涂层致密化,且降低涂层表面粗糙度~50%（从~20.2 nm到~11.9 nm）,同时提高涂层的硬度~50%（从~14 GPa到~21 GPa）,与杨氏模量~20%（从~309 GPa到~363 GPa）。但当轰击离子能量升高到50 eV时,Al元素含量急剧下降,涂层由V₂AlC相转变为V₂C与VC多相混合。轰击离子能量的提高有效改善V₂AlC涂层的结构,提高V₂AlC涂层的硬度,杨氏模量,但需控制轰击离子能量改变范围才可实现结构与性能最优化。     

退火对激光熔覆AlCoCrFeNiTi0.5高熵合金涂层组织和耐磨性的影响

对激光熔覆AlCoCrFeNiTi_0.5高熵合金涂层进行900℃退火,保温5h处理。主要对退火前后样品的微观结构和耐磨性进行研究。XRD结果表明,退火后的AlCoCrFeNiTi_0.5高熵合金涂层,其相组成有Co₃Ti和BCC结构的AlFe固溶相,出现典型的成分均匀的网状调幅分解组织;退火后的平均显微硬度达到989HV_0.5,比退火前提高了73.5%;耐磨性测试结果显示,退火后磨损量比退火前降低了92.5%,磨损宽度是退火前的50%。     

占空比对脉冲电弧离子镀AlCrSiN涂层热稳定性和抗氧化性的影响

采用脉冲和直流电弧离子镀技术制备AlCrSiN涂层,研究占空比对涂层结构和性能的影响。采用扫描电镜观测涂层的生长形貌和化学成分,利用XRD分析涂层的相组成,结合光电子能谱技术分析涂层中元素化学键价,并通过纳米压痕法检测涂层的硬度和弹性模量。此外,对涂层进行真空退火和氧化处理,以评价涂层的高温结构和力学稳定性以及抗氧化性。结果表明：AlCrSiN涂层均为非晶Si₃N₄包裹纳米晶（Al, Cr）N的纳米复合结构;脉冲电弧沉积可以改善涂层的表面质量、提高组织致密性和硬度。占空比为1%时,AlCrSiN涂层具有最小的表面粗糙度（47 nm）和最高的硬度（31.5 GPa）。AlCrSiN涂层具有良好的热稳定性,950℃退火后其硬度仍高于30 GPa。AlCrSiN涂层的抗氧化温度超过1000℃;占空比的增加涂层的抗氧化性略有提升。     

等离子渗镀CrON复合涂层结构与抗铝液熔蚀性能

采用等离子渗氮/电弧离子镀复合方法在H13模具钢表面制备出CrON涂层,研究氧流量对CrON复合涂层结构及抗铝液熔蚀性能的影响。结果表明,随着氧流量的增加,所制备的涂层主要物相由氮化物向氧化物转变,在氧流量较低时主要呈现面心立方CrN结构,而在氧流量为200 mL/min时制备的涂层形成典型的Cr₂O₃晶体相特征。掺入适量的氧,CrN涂层柱状晶生长受到抑制,涂层结构更加致密。涂层表面缺陷和粗糙度随着氧含量的增加而增大。CrON复合涂层在铝液中的失效形式是局部点蚀。由于形成致密的结构和良好的热稳定性,在氧流量为50 mL/min时制备的涂层具有优异的抗铝液熔蚀能力,而氧流量较高时表面生成致密的Cr₂O₃抗氧化层也有利于提高抗铝液熔蚀性能。     

反应磁控溅射制备CrN涂层的热稳定性

目的 研究了真空、大气2种环境下CrN涂层的热稳定性与氧化行为。方法 采用反应磁控溅射技术在(100)取向的P型单晶硅基底上制备了CrN涂层。利用真空热脱附谱(TDS)、场发射扫描电子显微镜(FESEM)、拉曼光谱(Raman)、X射线衍射(XRD)和扫描电子显微镜(SEM)以及加装的能谱仪(EDS)等表征方法,研究了在不同温度下涂层的热稳定性与氧化行为。结果 在真空退火时,TDS结果表明CrN涂层中的N在664 ℃左右开始释放,在温度达到1 000 ℃时释放结束。而在温度高于900 ℃时释放速率和释放量开始迅速上升,在温度达到930 ℃时达到峰值。在加热过程中,涂层中的CrN相部分转变为Cr2N相,在温度达到1 000 ℃时,完全转变为CrSi2相。在大气环境中,当温度达到700 ℃时,涂层开始被氧化,涂层表面生成了一层约136 nm厚的致密氧化层,同时在氧化层下方生成了一层CrOxN1?x的过渡层,并且涂层也出现了Cr2O3的拉曼峰。当温度达到800 ℃时,Cr2O3氧化物拉曼峰和衍射峰的数量和强度显著增加,说明涂层表面生成的氧化物的结构由简单变为复杂,并且结晶性增强。此外,氧化物颗粒逐渐长大,氧化层厚度增加,在温度达到850 ℃时,氧化层厚度达到429 nm。当温度高于700 ℃时,CrN涂层沿着厚度方向的元素扩散行为是O元素的向内扩散和N、Cr元素的向外扩散,并且释放的N在氧化层下方富集,并没有释放出去。结论 CrN涂层在真空中的热稳定性在900 ℃左右,在大气中的热稳定性在700 ℃左右。在大气中致密的Cr2O3氧化层的形成对O元素的向内扩散和N、Cr元素的向外扩散具有很好的阻挡作用。氧化层的这种阻挡作用对涂层的内部起到保护作用,延缓了涂层进一步的氧化和分解,这是CrN涂层热稳定性较好的原因。     

CrN/CrAlSiN涂层海水环境下的摩擦学性能

为提高海洋装备摩擦零部件的摩擦学性能,采用多弧离子镀技术在316L不锈钢上制备了CrN/CrAlSiN涂层。通过XRD、XPS表征涂层的物相及成分,SEM和TEM表征涂层的形貌和微观结构,并用纳米压痕仪测试其硬度,采用摩擦磨损试验机对涂层在大气和海水环境中的摩擦磨损性能进行测试。结果表明:CrN/CrAlSiN涂层的微观结构主要有CrN相、AlN相以及非晶态Si_3N_4包裹CrN、AlN相,(111)择优取向最为明显;基于微观结构与CrN过渡层的设计,CrAlSiN涂层硬度高达35.5 GPa;较之于316L基底,涂层致密的结构使其在海水环境下表现出更好的耐腐蚀性能;在大气和海水环境下,CrN/CrAlSiN涂层的摩擦因数及磨损率均明显降低,在海水环境下达到最优。     

微波退火时间对HfO2薄膜结构和光电性能的影响

采用原子层沉积(ALD)方法在硅衬底上沉积了氧化铪(HfO₂)薄膜,对其进行不同时间的微波退火(MWA)。采用X射线衍射(XRD)、拉曼光谱(Raman)、原子力显微镜(AFM)、紫外可见光谱(UV-Vis)、椭偏仪(SE)和阻抗分析仪对薄膜的物相结构、形貌和光电性能进行表征,研究了微波退火时间对薄膜结构、光学和电学性能的影响。结果表明：沉积态的HfO₂薄膜具有非晶态性质;当微波退火时间从5 min增至20 min时,HfO₂薄膜的折射率几乎不变,结晶性增强,表面粗糙度降低,但介电常数却减小。     

退火对激光熔覆制备FeCrNiCoMn高熵合金涂层组织与性能的影响

采用气雾化法制备了FeCrNiCoMn合金粉末,并在45钢基体上激光熔覆制备出了FeCrNiCoMn高熵合金涂层。分别采用SEM、EDS、XRD对粉末、涂层的微观形貌及相结构进行了分析,并测试了涂层的硬度。对涂层在300℃、550℃、700℃时退火4 h,研究涂层的抗高温软化性。结果表明:气雾化制备的合金粉末具有较好的球形度,FeCrNiCoMn涂层由单一的FCC相构成,组织为椭球状的枝晶与枝晶间形貌;不同温度退火后的涂层保持FCC相不变;在550℃以下退火,涂层组织无变化,但在700℃退火后,涂层组织变化明显;退火前后涂层的硬度无明显变化。     

Syntheses and mechanical properties of Cr-Mo-N coatings by a hybrid coating system

Effects of Mo content up to 30.4 at.% on the microstructure and mechanical properties of CrN coatings are reported in this study. Ternary Cr-Mo-N coatings were deposited onto steel substrates (AISI D2) using a hybrid coating method of arc ion plating (AIP) using Cr target and DC magnetron sputtering technique using Mo target in N₂/Ar gaseous mixture. The synthesized Cr-Mo-N coatings formed a substitutional solid solution of (Cr,Mo)N where larger Mo atoms replaced Cr in CrN crystal. The Cr-Mo-N coatings showed increased hardness value of approximately 34 GPa at 21 at.% Mo, compared with 18 GPa for pure CrN. The friction coefficient decreased from 0.49 for pure CrN coating to 0.37 for Cr-Mo-N with 30.4 at.% Mo. This result is believed to be due to tribo-layer formation of MoO₃ which is known to function as a solid lubricant.     

Microstructure and thermal stability of a Ni-Cr-Co-Ti-V-Al high-entropy alloy coating by laser surface alloying

A Ni-Cr-Co-Ti-V-Al high-entropy alloy (HEA) coating with a BCC phase and (Ni, Co)Ti₂ compounds was synthesized successfully by laser surface alloying on a Ti-6Al-4V substrate. The microstructure of as-synthesized coatings is typical, namely, the microstructure from the coating to the substrate changes from equiaxed grains to columnar grains. After remaining at 900 °C for 8 h, the constituent phases remain unchanged. However, owing to the unceasing dissolution of the Ti element, the lattice parameter of the BCC HEA phase changes from 3.06 Å to 3.16 Å. The thermoanalysis results show that the oxidation film on the Ni-Cr-Co-Ti-V-Al HEA coating is mainly composed of TiO₂, V₂O₅, and NiO. The oxidation resistance of this HEA coating may be due to the existence of NiO and the alloying elements Al, Cr, and Co; the oxidation phenomenon should be responsible for the mass increase in the thermogravimetry process. The differential scanning calorimetry and the dynamic differential scanning calorimetry curves show that the synthesized HEA coating is stable below 1005 °C.     

Effect of Annealing Temperature on Tribological Properties and Material Transfer Phenomena of CrN and CrAlN Coatings

This study evaluates the effects of annealing temperature and of the oxides produced during annealing processes on the tribological properties and material transfer behavior between the PVD CrN and CrAlN coatings and various counterface materials, i.e., ceramic alumina, steel, and aluminum. CrAlN coating has better thermal stability than CrN coating in terms of hardness degradation and oxidation resistance. When sliding against ceramic Al₂O₃ counterface, both CrN and CrAlN coatings present excellent wear resistance, even after annealing at 800 °C. The Cr-O compounds on the coating surface could serve as a lubricious layer and decrease the coefficient of friction of annealed coatings. When sliding against steel balls, severe material transfer and adhesive wear occurred on the CrN and CrAlN coatings annealed at 500 and 700 °C. However, for the CrAlN coating annealed at 800 °C, much less material sticking and only small amount of adhesive wear occurred, which is possibly due to the formation of a continuous Al-O layer on the coating outer layer. The sliding tests against aluminum balls indicate that both coatings are not suitable as the tool coatings for dry machining of aluminum alloys.     

Performance of Al‐rich oxidation resistant coatings for Fe‐base alloys

The oxidation resistance of Al‐rich coatings made by chemical vapor deposition and pack cementation was examined on representative ferritic‐martensitic (FM, e.g. Grade 91, Fe‐9Cr‐1Mo) and austenitic steel substrates at 650°‐800 °C. To evaluate the potential benefits and problems with these alumina‐forming coatings, oxidation exposures were conducted in a humid air environment where the uncoated substrates experience rapid oxidation, similar to steam. Exposure temperatures were increased to accelerate failure by oxidation and interdiffusion of Al into the substrate. The difference in the coefficient of thermal expansion (CTE) between coating and substrate was found to cause cracking and coating failure during rapid thermal cycling on thicker coatings with Fe‐Al intermetallic phases. Therefore, thinner coatings with less Al and a ferritic Fe(Al) structure were evaluated more extensively and tested to failure at 700° and 800 °C on FM steels. The remaining Al content at failure was measured and used to improve a previously developed coating lifetime model. At 700° and 800 °C, thin coated austenitic specimens continue to exhibit protective behavior at more than double the lifetime of a similar coating on FM steel. The longer lifetime was attributed to the ferritic coating‐austenitic substrate phase boundary inhibiting Al interdiffusion.     

Oxidation behavior of magnetron sputtered double layer coatings containing molybdenum,silicon and boron

Protective coating systems were applied to Mo–9Si–8B (at.%) alloys to prevent oxidation at elevated temperatures. The coatings produced by magnetron sputtering and subsequent annealing consisted of an outer oxidation protection layer and an interlayer between this and the substrate. Three amorphous outer layers with different compositions were deposited: Mo–45Si–25B, Mo–55Si–10B and Mo–29Si–15B (all in at.%). The interlayer was selected to give a diffusion barrier with the composition of the Mo₅SiB₂ (T2) phase. All coatings were dense and well-adherent. During vacuum annealing the amorphous as-deposited coatings became crystalline exhibiting mainly the intermetallic Mo₅SiB₂ compound as interlayer and the MoSi₂, Mo₅Si₃ and MoB phases in the top layers. The samples were exposed to dry laboratory air in the pesting regime at 800 °C and above, i.e. at 1000 and 1300 °C for up to 100 h under cyclic conditions. All coatings were protective at 800 and 1000 °C for at least 100 h and showed a marked improvement in mass change compared to the uncoated substrate. For protection at 800 °C higher boron content is preferential, while at higher oxidation temperatures a lower boron content provides improved oxidation protection. At 1300 °C stress induced failures like cracking, spallation and buckling occurred due to the relatively high CTE mismatch between PVD coating and substrate. Even though, the mass change was still markedly reduced as compared to the bare substrate.     

Al, Si, and Al�CSi Coatings to Improve the High-Temperature Oxidation Resistance of AISI 304 Stainless Steel

Oxidation resistance of chromium steels is due to the formation of Cr₂O₃ on the surface. However, this surface layer destabilizes above 1,000 °C and does not protect the metal. In this study, three types of coatings were applied to AISI 304 stainless steel (SS), and the microstructure and oxidation resistance of the coatings were investigated. Aluminum coating, silicon coating, and the codeposition of Al and Si were deposited on an SS substrate by the pack cementation method. The microstructure of the samples was then examined by SEM and EDS, and phases were identified by XRD. The oxidation resistance of these samples was studied in air at 1,050 °C. The results showed that the best resistance to oxidation was obtained, in order, from the codeposition of Al?CSi, Al coating, and Si coating.     

等离子体增强磁控溅射CrSiN涂层摩擦磨损行为

目的基于细晶强化理论,借助新型涂层制备技术获得综合性能优良的CrSiN涂层,研究Si含量对涂层微观结构、力学性能及耐磨性能的影响规律。方法采用等离子体增强磁控溅射技术,制备四种含有不同Si含量的Cr Si N涂层。使用X射线能谱仪(EDS)、X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)和原子力显微镜(AFM),分析涂层的化学成分、晶体结构、微观形貌和表面粗糙度。使用纳米压痕/划痕仪测试涂层的显微硬度、杨氏模量和结合力。使用摩擦磨损试验仪考察涂层的摩擦磨损行为。结果 Cr Si N涂层中Si含量随着Si靶功率的增加而增加。所有涂层中均未检测到含Si物相,主要由Cr N相组成。随着Si含量的增加,CrN(111)衍射峰逐渐减弱直至消失,涂层由疏松的三角锥结构逐渐变为致密平整的CrN纳米晶和Si3N4非晶共存的复合结构,涂层表面粗糙度显著降低,涂层的显微硬度、杨氏模量、结合力及耐磨性能均呈现先增后降的趋势。结论 Si含量为18.5%的Cr Si N涂层具有最佳的耐磨性能,此时涂层的硬度、杨氏模量、结合力和平均摩擦系数分别约为27 GPa、327 GPa、30 N和0.289。     

Cyclic oxidation resistance of Ni–Al alloy coatings deposited on steel by a cathodic arc plasma process

The cyclic oxidation resistance of nickel-aluminide coatings deposited on steel using a cathodic arc plasma (CAP) process has been investigated. Our results show that nickel-aluminide films can be successfully deposited on carbon steel and stainless steel substrates by this process; NiAl₃ is the major phase in the deposited films. The thermal cycling behaviour suggests that such coatings can resist oxidation through physical blocking of oxygen, either by the coating itself or by the aluminium oxide scale subsequently formed in-service. Aluminium diffusion inwards to the substrate may also be beneficial to the thermal oxidation resistance. The coating protects stainless steel substrate materials at 500°C by transforming the NiAl₃ phase into NiAl, producing aluminium oxide on the open substrate surface. At 800°C, oxide flaking is suppressed by the trace amounts of nickel or aluminium which have partially diffused into the substrate.     

Preparation and oxidation behaviour of electrodeposited Ni–CeO2 nanocomposite coatings

Ni–CeO₂ nanocomposite coatings with different CeO₂ contents were prepared by codeposition of Ni and CeO₂ nanoparticles with an average particle size of 7 nm onto pure Ni surfaces from a nickel sulfate. The CeO₂ nanoparticles were dispersed in the electrodeposited nanocrystalline Ni grains (with a size range of 10–30 nm). The isothermal oxidation behaviours of Ni–CeO₂ nanocomposite coatings with two different CeO₂ particles contents and the electrodeposited pure Ni coating were comparatively investigated in order to elucidate the effect of CeO₂ at different temperatures and also CeO₂ contents on the oxidation behaviour of Ni–CeO₂ nanocomposite coatings. The results show that the as-codeposited Ni–CeO₂ nanocomposite coatings have a superior oxidation resistance compared with the electrodeposited pure Ni coating at 800 °C due to the codeposited CeO₂ nanoparticles blocking the outward diffusion of nickel along the grain boundaries. However, the effects of CeO₂ particles on the oxidation resistance significantly decrease at 1050 °C and 1150 °C due to the outward-volume diffusion of nickel controlling the oxidation growth mechanism, and the content of CeO₂ has little influence on the oxidation.     

Characterization and Performance of Magnetron-Sputtered Zirconium Coatings Deposited on 9Cr-1Mo Steel

Zirconium coatings of different thicknesses have been deposited at 773 K on 9Cr-1Mo steel substrate using pulsed DC magnetron sputtering. These coatings were heat treated in vacuum at two different temperatures (1173 and 1273 K) for one hour. X-ray diffraction (XRD) analysis of Zr-coated samples revealed the formation of α-phase (HCP structure) of Zr. XRD analysis of heat-treated samples show the presence of Zr₃Fe and Zr₂Fe intermetallics. The lattice parameter of these coatings was calculated, and it matches with the bulk values when the thickness reached 2µm. In order to understand this, crystallite size and strain values of these coatings were calculated from XRD plots employing Williamson-Hall method. In order to assess the performance of the coatings, systematic corrosion tests were carried out. The corrosion current density calculated from the polarization behavior showed that the corrosion current density of the uncoated 9Cr-1Mo steel was higher than the coated sample before and after the heat treatment. Studies using electrochemical impedance spectroscopy confirmed that the coated steel has higher impedance than the uncoated steel. The corrosion resistance of 9Cr1Mo steel had improved after Zr coating. However, the corrosion resistance of the coating after heat treatment decreased when compared to the as-deposited coating. The microstructure and composition of the surface oxide film influence the corrosion resistance of the Zr-coated 9Cr1Mo steel.