Research Progress of Non-oxide and High Entropy Ceramic Coatings

Ceramic coatings play a keyrole in extending the service life of materials in aerospaceandenergy fields byprotectingmaterials from high temperature,oxidation,corrosion and thermal stress.Non-oxide and high entropy ceramics are new emerging coating materials which have been researched and developed in recent years.Compared with traditional oxide ceramics,non-oxide ceramics have better high temperature stability,oxidation resistance and erosion resistance.These characteristics make non-oxide ceramics perform well in extreme environments.It is particularly noteworthy that the non-oxide high entropy ceramic is a uniform solid solution composed of at least four or fiveatoms.Their unique structure and outstanding propertiesshow great potential application in the field of coating.In this paper,the researches aboutregulating microstructure,preparation technology and properties of nitride and its high entropy system,carbide and its high entropy system and boride and its high entropy system in coating field are summarized,and their future development and prospects are prospected.

Friction and Wear Properties of Amorphous Carbon Nitride Coatings in Water Lubrication

The friction and wear properties of amorphous carbon nitride(a-CN x)coatings in water lubrication were reviewed.The influences of mating materials and tribological variables such as normal load(W)and sliding speed(V)on the friction and wear properties of the a-CN x coatings were analyzed.It was indicated that the specific wear rate of the a-CN x coatings was related to the hydration reaction of mating materials with water.If the mating materials were easily hydrated,the specific wear rate of a-CN x coatings was low.The water-lubricated properties of the a-CN x coatings were better in comparison to the a-C coatings.The a-CN x/Si-based non-oxide ceramics tribo-pairs exhibited the lowest friction coefficient and wear rate.To describe their friction and wear properties at the normal loads of 3—15Nand the sliding speeds of 0.05—0.5m/s,the wear-mechanism maps for the a-CN x/SiC(Si3N4)tribo-pairs in water were developed.

Effect of process parameters on the microstructure and properties of laser-clad FeNiCoCrTi0.5 high-entropy alloy coating

FeNiCoCrTi0.5 coatings with different process parameters were fabricated by laser cladding. The macro-morphology, phase, microstructure, hardness, and wear resistance of each coating were studied. The smoothness and dilution rate of the FeNiCoCrTi0.5 coating generally increased with the increase of specific energy(Es), which is the laser irradiation energy received by a unit area. FeNiCoCrTi0.5 coatings at different parameters had bcc, fcc, and Ti-rich phases as well as equiaxed, dendritic, and columnar structures. When Es increased, the size of each structure increased and the distribution area of the columnar and dendritic structures changed. The prepared FeNiCoCrTi0.5 coating with the Es of 72.22 J·mm-2 had the highest hardness and the best wear resistance, the highest hardness of the coating reached HV 498.37, which is twice the substrate hardness. The average hardness of the FeNiCoCrTi0.5 coating with the Es of 72.22 J·mm-2 was 15.8% higher than the lowest average hardness of the coating with the Es of 108.33 J·mm-2. The worn surface morphologies indicate that the FeNiCoCrTi0.5 coatings exhibited abrasive wear.

Effects of substrate temperature and deposition time on the morphology and corrosion resistance of FeCoCrNiMo0.3 high-entropy alloy coating fabricated by magnetron sputtering

The effects of substrate temperature and deposition time on the morphology and corrosion resistance of FeCoCrNiMo0.3 coating fabricated by magnetron sputtering were investigated by scanning electron microscopy and electrochemical tests.The FeCoCrNiMo0.3 coating was mainly composed of the face-centered cubic phase.High substrate temperature promoted the densification of the coating,and the pitting resistance and protective ability of the coating in 3.5wt%NaCl solution was thus improved.When the deposition time was prolonged at 500℃,the thickness of the coating remarkably increased.Meanwhile,the pitting resistance improved as the deposition time increased from 1 to 3 h;however,further improvement could not be obtained for the coating sputtered for 5 h.Overall,the pitting resistance of the FeCoCrNiMo0.3 coating sputtered at 500℃for 3 h exceeds those of most of the reported high-entropy alloy coatings.

Microstructure and wear resistance of AlCrFeNiMo_(0.5)Si_(x) high-entropy alloy coatings prepared by laser cladding

In recent years,the coating prepared by laser cladding has attracted much attention in the field of wear research.In this work,AlCrFeNiMo_(0.5)Si_(x)(x=0,0.5,1.0,1.5,2.0)high-entropy alloy coatings were designed and prepared on Q235 steel by laser cladding.The effect of Si content on microstructure,microhardness and wear resistance of the coatings was studied in detail.The results indicate that the AlCrFeNiMo_(0.5)Si_(x) highentropy alloy coatings show an excellent bonding between substrate and the cladding layer.The AlCrFeNiMo_(0.5)Si_(x) coatings are composed of nano-precipitated phase with BCC structure and matrix with ordered B2 structure.With the addition of Si,the white phase(Cr,Mo)_(3)Si with cubic structure appears in the interdendritic,and the morphology of the coating(x=2.0)transforms into lamellar eutectic-like structures.The addition of Si enhances the microhardness and significantly improves the wear resistance of the coatings.As x increases from 0 to 2.0,the average hardness of the cladding zone increases from 632 HV to 835 HV,and the wear rate decreases from 1.64×10^(-5) mm^(3)·(N·m)^(-1) to 5.13×10^(-6) mm^(3)·(N·m)^(-1).When x≥1.5,the decreasing trend of the wear rate gradually slows down.The wear rates of Si1.5 and Si2.0 coatings are 5.85×10^(-6) mm^(3)·(N·m)^(-1) and 5.13×10^(-6) mm^(3)·(N·m)^(-1),respectively,which is an order of magnitude lower than that of Q235 steel.

Evaluation of 1031 primary titanium nitride coated mobile bearing total knee arthroplasties in an orthopedic clinic

AIM To evaluate the influence of the titanium nitride(TiN) coating on the results of a total knee arthroplasty(TKA). METHODS A total of 910 patients(338 men; 572 woman), with a mean age of 65(range 36-94) undergoing 1031 primary TKAs were assessed. Clinical evaluation and patientreported outcomes were gathered one year after surgery. The questionnaires included the Knee injury and Osteoarthritis Outcome Score(KOOS)-Dutch version, Visual Analogue Scale(VAS) pain scores in rest and during active knee movement, VAS-satisfaction scores, and EQ-5 D-3 L health scores. This was aimed to assess the overall knee function and patient satisfaction, and to enable us to make a gross comparison to other TKAs.RESULTS At a mean follow-up of 46 mo(range 1-92) the overall implant survival was 97.7% and 95.1% for any operative reason related to the implant. Twenty-three knees(2.2%) required revision surgery. Arthrofibrosis was the most common indication for a re-operation. The clinical evaluation and patient-reported outcomes revealed good to excellent patient satisfaction and function of the arthroplasty. The median postoperative VAS-pain scores on a scale of 0-100, at one year after surgery were 1 in rest and 2 during movement.CONCLUSION The Ti N coated, mobile bearing TKA results are excellent and similar to those of other widely used TKA designs. Residual pain of the knee remains a concern and the Ti N coating in combination with the mobile bearing does not seem to be the simple solution to this problem. Future research will have to show that the coating gives a better survival than the cobalt chrome version.

Effect of Laser Power on the Microstructure and Mechanical Properties of TiN/Ti_3Al Composite Coatings on Ti6Al4V

Laser nitriding is one of the effective techniques to improve the surface properties of titanium alloys and has potential application in the life extension of last-stage steam turbine blades. However, cracking of surface coating is a common problem due to heat concentration in laser nitriding process. Conventionally, the cracks can be avoided through heat treatment, which may have an important influence on the mechanical properties of coating. Crack-free TiN/Ti3Al IMC coatings on Ti6Al4V are prepared by plasma spraying and laser nitriding. The microstructures, phase constitutes and compositions of the coating are observed and analyzed with scanning electron microscopy(SEM), X-ray diffraction(XRD) and X-ray energy-dispersive spectroscopy(EDS). Microhardness, elastic modulus, fracture toughness of the coating are measured. The results show that the crackand pore-free IMC coatings can be made through the proposed method; with increasing laser power, the amount and density of TiN phase in the coating first increased and then decreased, leading to the similar trend of microhardness and elastic modulus and the reverse trend of fracture toughness of the coating. Both the average microhardness and elastic modulus of the coating increase three times higher than those of the substrate. The volume fraction of the TiN reinforced phase in composite can be controlled by varying the laser power and the cracking problem in laser nitriding process is successfully solved.

Extended Anode Effect for Tube Inner Coating of Non-Conductive Ceramics by Pulsed Coaxial Magnetron Plasma

For uniform tube inner coating of non-conductive thin films, the double-ended coaxial magnetron pulsed plasma (DCMPP) method was investigated. In this study, coating of TiN and TiO2 was performed. It was clearly shown that the extended anode effect was strongly influenced by the electric resistance of the coated thin films on the inner surface of an insulator tube. Additionally, high frequency (100 kHz) was better for relatively high plasma density. On the other hand, in the case of titanium oxide deposition, negative ion productions drastically decrease the deposition rate and the shifting velocity of plasma main position for coated TiO2 films.

Microstructure and Properties of A IN Coating/Graphite Fabricated via In-situ Reaction

A novel method was used to fabricate AlN coating on graphite substrate. This approach included two steps： firstly, the emulsion composed of BN and anhydrous ethanol was sprayed on the surface of the graphite substrate; secondly, AlN coating was formed through the in-situ reaction of Al with the sprayed BN. The reaction was investigated by thermogravimetric-differential thermal analysis （TG-DTA）, and the phase composition in the synthetic process was characterized by X-ray diffraction （XRD）. Scanning electronic microscopy （SEM） was used to observe the morphology, and electron probe microanalysis （EPMA） was used to observe the distribution of the elements. The experimental results show that the AlN coating is dense and bonded with graphite tightly.

Formation Conditions of TiN Coatings by Reactive Magnetron Sputtering and Its Characteristics

The TiN coatings on the surfaces of various cemented carbides were performed by use of reactive magnetron sputtering. The highest microhardness which was obtained in our experiment was 49 GPa. The order of effects of deposition parameters is resulted from the L16 experiments according to orthogonal design. The pole density analysis indicated that there were a few of the textureless samples. The crystal orientation of TiN exhibited clear regularity and affected microhardness and other properties of films remarkably. A concept relating to structure factor was proposed. A layer-like structure was found. SAES showed that a transition layer exists between substrate and coating and its thickness is of a micron. The formation mechanism of film was discussed.

Solid Particle Erosion Behaviour of TiN Coating on AISI 4140 Steel

In this study, the performance against erosive wear of PVD TiN (titanium nitride) coating was evaluated using an erosion test rig similar to that described in the standard ASTM G76-95. This coating normally has various industrial applications such as tapping, drilling, dry machining and punching. Angular silicon carbide (SiC) was used as an abrasive particle with a grain size of 350-450 μm. Erosion tests were carried out using different incident angles, 30°, 45°, 60° and 90° with a particle velocity of 24 ± 2 m/s, an abrasive flow rate of 0.7 ± 0.5 g/min, and the test temperature was between 35°C and 40°C. The particle velocity and the abrasive flow rate were low in all of the tests to reduce the interaction between the incident and the rebounding particles in the system. The surfaces were examined with a scanning electron microscope (SEM) to characterize the erosive damage. The wear mechanisms identified were brittle fracture characterized by radial cracks on the surface by multiple impact and a few pits at 30°, while a few cracks and the formation of craters in random positions were observed at angles near or at 90°. Elliptical scars were observed at 30° and 45°, which are a characteristic feature when the specimens are impacted at low-incident angles (α ≤ 45°) whereas a roughly circular scar was seen at 60° and 90°. In addition, roughness variations were analyzed using atomic force microscopy (AFM), before and after the erosion tests, and the results exhibited an increase in the roughness as the TiN samples were impacted at angles near or at 90°.

Microtribology of Nitrogen-doped Amorphous Carbon Coatings

The friction, wear and lubrication of carbon nitride coatings on silicon substrates are studied using a spherical diamond counter-face with nano-scale asperities. The first part of this paper clarifies the coating thickness effect on factional behavior of carbon nitride coatings. The second part of this paper reports empirical data on wear properties in repeated sliding contacts through in situ examination and post-sliding observation. The third part will concentrate on wear mechanisms for the transition from "No observable wear particles" to "Wear particle generation." In light of the above tribological study, the application of carbon nitride coatings to MicroElectroMechanical system (MEMS) is therefore discussed from view points of both microtribology and micromachining.

In Situ Synthesis of Titanium Nickel Intermetallic Compounds Layer and TiN Coating By Laser Cladding

Laser cladding,together with laser nitriding was used to synthesize a titanium nickel intermetallic compound layer on the nickel substrate and a TiN coating on the cladding layer. During the laser cladding, Ti and Ni powders were blown into the melting pool by a six-hole coaxial nozzle powder injection system. Exothermic reactions between Ti and Ni took place in the melting pool, and a cladding layer of titanium nickel intermetallic compounds was produced. Laser nitriding in a nitrogen-rich atmosphere followed the production of the cladding layer, and formed a golden yellow TiN layer over it. An optical and a scanning electron microscope were used to investigate the microstructures and measure the thicknesses of the cladding layer and the TiN layer. Phase identification was carried out by XRD. For the nitriding sample, the microhardness profile of the clad layer was tested. The optimal process parameters of the in situ synthesis of titanium nickel intermetallic compounds were obtained.

2Cr13钢离子渗氮和WCrAlTiSiN离子镀复合处理及电化学行为

马氏体不锈钢的常规表面改性方法基本局限在单一化学热处理或镀膜,对表面性能的提升有限。对2Cr13不锈钢进行离子渗氮与多弧离子镀WCrAlTiSiN纳米多层涂层复合强化处理,研究其在天然海水环境中的耐腐蚀性能。采用不同的表面强化工艺,即未处理(Untreated)、低温渗氮处理(LPN)、高温渗氮处理(HPN)、单一镀膜处理(Coating)、低温渗氮+镀膜处理(LPN+C)和高温渗氮+镀膜处理(HPN+C)。采用X射线衍射、光学显微镜、透射电子显微镜和维氏硬度计对不同样品的组织结构、化学成分和硬度等进行表征。采用电化学阻抗法和动态电位极化法对2Cr13在天然黄海海水中的电化学行为进行测试。试验结果表明:WCrAlTiSiN涂层可在一定程度上提升腐蚀性能,但是溶液中的Cl^(−)通过较薄单一涂层的缺陷侵入基体。LPN样品因渗氮层的存在提升了一定的耐腐蚀性能,而HPN样品因为渗氮温度过高而导致CrN大量析出,使得样品表面出现“贫Cr”现象,耐腐蚀性能下降。复合处理样品的渗氮层-WCrAlTiSiN涂层可形成保护屏障,有效阻止电荷转移和电流从阳极流向阴极,提高2Cr13钢在海水环境中的耐腐蚀性能。通过离子渗氮-多弧离子镀WCrAlTiSiN纳米涂层复合强化方法可有效提升马氏体不锈钢在海水中的耐腐蚀性能。

聚苯胺-氮化硼纳米颗粒复合水性环氧涂层的制备与防腐性能研究

为了提升水性环氧涂层在高盐、高湿海洋环境中的防腐性能和耐久性能,在羟基化的六方氮化硼表面通过原位聚合生长聚苯胺(PANI)得到聚苯胺/氮化硼纳米颗粒(PBN),将PBN作为防腐填料来增强水性环氧涂层的防腐性能。通过傅里叶变换红外光谱(FT-IR)和电子扫描电镜(SEM)对纳米颗粒的结构与微观形貌进行表征,采用电化学测试和中性盐雾试验(NSS)探究氮化硼、PANI改性水性环氧涂层和PBN添加量对水性环氧涂层的防腐性能的影响。结果表明:PANI在BN纳米片表面原位生长形成珊瑚状结构,向水性环氧涂层中添加0.50%(质量分数,下同)PBN后的粘结强度达到6.05 MPa,在3.5%NaCl溶液中浸泡120 h后的腐蚀电流密度(1.99×10^(-9) A/cm^(2))比纯环氧涂层(1.01×10^(-6) A/cm^(2))降低约3个数量级。这归因于添加的0.50%PBN能均匀分散在环氧树脂中,填补涂层的微小空隙并提升对腐蚀介质的阻隔作用,同时PANI具有缓蚀作用,二者协同提高纯环氧涂层的防腐性能。

轴承钢表面电弧离子镀氮化物涂层的抗冲击性能和耐磨性能

采用电弧离子镀工艺在GCr15轴承钢表面分别沉积了TiN和TiAlN 2种氮化物涂层,对比研究了涂层的微观结构、硬度、结合性能、抗冲击性能和耐磨性能。结果表明:制备的TiN涂层和TiAlN涂层表面平整,均以(200)晶面择优生长;TiN涂层和TiAlN涂层的硬度分别为2060.3,3390.8 HV,为基体(689.5 HV)的3.0倍和4.9倍。TiN和TiAlN涂层与轴承钢的结合性能良好,结合等级为HF1~HF2,40次冲击试验后TiN和TiAlN涂层表面均未发生剥落和开裂,抗冲击性能良好。TiN涂层和TiAlN涂层与轴承钢对磨时的平均摩擦因数分别为0.42,0.36,体积磨损量分别为1.26×10^(-3),0.54×10^(-3 )mm^(3),均低于基体,涂层表面均形成了较浅的犁沟,磨损机制为磨粒磨损,其中TiAlN涂层表面犁沟更浅,磨损程度更轻。TiAlN涂层的结合性能和抗冲击性能与TiN涂层相当,硬度和耐磨性能均高于TiN涂层,更适用于改善轴承钢的表面耐磨性能。

Cycling performance of layered oxide cathode materials for sodium-ion batteries

Layered oxide is a promising cathode material for sodium-ion batteries because of its high-capacity,high operating voltage,and simple synthesis.Cycling performance is an important criterion for evaluating the application prospects of batteries.However,facing challenges,including phase transitions,ambient stability,side reactions,and irreversible anionic oxygen activity,the cycling performance of layered oxide cathode materials still cannot meet the application requirements.Therefore,this review proposes several strategies to address these challenges.First,bulk doping is introduced from three aspects:cationic single doping,anionic single doping,and multi-ion doping.Second,homogeneous surface coating and concentration gradient modification are reviewed.In addition,methods such as mixed structure design,particle engineering,high-entropy material construction,and integrated modification are proposed.Finally,a summary and outlook provide a new horizon for developing and modifying layered oxide cathode materials.

Online preparation of high-quality BN coatings with atomic diffusion based on carbon-free water-soluble precursor

Efficient and environmentally friendly production of high-quality continuous fiber coatings using current preparation methods is highly challenging due to issues such as scale and batch processing restrictions,low deposition rate,high energy consumption,and utilization of multiple environmentally hazardous steps.To address these challenges,we propose a stable and efficient wet chemical deposition coating method for high-throughput online continuous preparation of boron nitride(BN)coatings on ceramic fibers under an ambient environment.Our process involves surface modification,in-situ wet chemical deposition,and heat treatment,and all seamlessly connecting with the ceramic fiber preparation process through continuous stretching.Hydrophilic groups were introduced via surface modification enhancing wettability of the fiber surface with impregnating solution.An in-situ reaction and atom migration improve uniformity and binding of the coating.As a result,outstanding impregnation and adhesion properties are achieved.A comprehensive analysis to evaluate the impact of the BN coatings was conducted,which demonstrates that the BN-coated fibers exhibit a remarkable 36%increase in tensile strength,a 133%increase in fracture toughness,and enhanced temperature resistance of up to 1600℃.It provides a secure and efficient platform for cost-effective production of functional and high-quality coatings through targeted surface modification and rapid stretching impregnation.

High-entropy(La_(0.2)Nd_(0.2)Sm_(0.2)Gd_(0.2)Yb_(0.2))_(2)(Zr_(0.75)Ce_(0.25))_(2)O_(7)thermal barrier coating material with significantly enhanced fracture toughness

Poor fracture toughness leads to premature failure of La_(2)(Zr_(0.75)Ce_(0.25))_(2)O_(7)(LCZ)ther-mal barrier coatings in an elevated temperature service environment.A novel coating material,namely(La_(0.2)Nd_(0.2)Sm_(0.2)Gd_(0.2)Yb_(0.2))_(2)(Zr_(0.75)Ce_(0.25))_(2)O_(7)(LNSGY)based on the high-entropy con-cept,was successfully fabricated by solid-state sintering.The microstructure of LCZ and LNSGY was investigated by X-Ray Diffraction(XRD),Raman Spectrometer(RS),Transmission Electronic Microscopy(TEM)and Scanning Electron Microscopy(SEM).The fracture toughness of the LCZ and LNSGY ceramics was evaluated.The LNSGY has excellent high-temperature phase stability,and the grain size of LNSGY ceramic is smaller than that of LCZ ceramic at an elevated temper-ature due to the sluggish diffusion effect.Compared with LCZ(fracture toughness is(1.4±0.1)MPa·m^(1/2)),the fracture toughness of LNSGY is significantly enhanced(fracture toughness is(2.0±0.3)MPa·m^(1/2)).Therefore,the LNSGY can be a promising advanced thermal barrier coat-ing material in the future.