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Innovative manufacturing of nanostructured solid state electrolyte using suspension plasma spray
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-04-02 DOI: 10.1016/j.surfcoat.2025.132112
Surinder Singh , Nonthapat Nawbuntud , Kritkasem Khantisopon , Ashok Meghwal , Jirasak Tharajak , Poomirat Nawarat , Christopher C. Berndt , Andrew S.M. Ang
The conventional vacuum-based methods used to fabricate all-solid-state lithium-ion battery (ASSLIB) components are typically expensive, characterized by slow deposition rates and yield mostly amorphous coatings that demand postprocessing to enhance performance. This research explores the advanced fabrication of Li6.5La3Zr1.5Ta0.5O12 (LLZTO) solid electrolyte coatings using suspension plasma spray (SPS) for ASSLIBs. The LLZTO feedstock suspension was stabilised by identifying most suitable suspension parameters such as zeta potential, particle size, and pH values to obtain uniform flowability. Coatings with thicknesses ranging from 15 to 30 μm were developed by varying stand-off-distance (SOD) and torch surface speed. X-ray diffraction (XRD) reveals the retention of high amounts of 68 % of the cubic-LLZTO phase content in the coatings compared to the raw materials used for making the suspension. Coatings exhibit around 75 % of crystallinity and 7 % porosity, which is favourable for better phase stability at high operating temperatures and restrict the dendritic formation respectively. Moreover, the coatings retained around 4.5 wt% of Li content from an initial 5 wt% in the powder. Furthermore, SPS'ed. LLZTO coatings resulted in ion-conductivity of the order of 10−8 S cm−1, which is five times the conductivity of the same material obtained by magnetron sputtering, hence, demonstrating the potential of SPS to fabricate ASSLIB components.
{"title":"Innovative manufacturing of nanostructured solid state electrolyte using suspension plasma spray","authors":"Surinder Singh ,&nbsp;Nonthapat Nawbuntud ,&nbsp;Kritkasem Khantisopon ,&nbsp;Ashok Meghwal ,&nbsp;Jirasak Tharajak ,&nbsp;Poomirat Nawarat ,&nbsp;Christopher C. Berndt ,&nbsp;Andrew S.M. Ang","doi":"10.1016/j.surfcoat.2025.132112","DOIUrl":"10.1016/j.surfcoat.2025.132112","url":null,"abstract":"<div><div>The conventional vacuum-based methods used to fabricate all-solid-state lithium-ion battery (ASSLIB) components are typically expensive, characterized by slow deposition rates and yield mostly amorphous coatings that demand postprocessing to enhance performance. This research explores the advanced fabrication of Li<sub>6.5</sub>La<sub>3</sub>Zr<sub>1.5</sub>Ta<sub>0.5</sub>O<sub>12</sub> (LLZTO) solid electrolyte coatings using suspension plasma spray (SPS) for ASSLIBs. The LLZTO feedstock suspension was stabilised by identifying most suitable suspension parameters such as zeta potential, particle size, and pH values to obtain uniform flowability. Coatings with thicknesses ranging from 15 to 30 μm were developed by varying stand-off-distance (SOD) and torch surface speed. X-ray diffraction (XRD) reveals the retention of high amounts of 68 % of the cubic-LLZTO phase content in the coatings compared to the raw materials used for making the suspension. Coatings exhibit around 75 % of crystallinity and 7 % porosity, which is favourable for better phase stability at high operating temperatures and restrict the dendritic formation respectively. Moreover, the coatings retained around 4.5 wt% of Li content from an initial 5 wt% in the powder. Furthermore, SPS'ed. LLZTO coatings resulted in ion-conductivity of the order of 10<sup>−8</sup> S cm<sup>−1</sup>, which is five times the conductivity of the same material obtained by magnetron sputtering, hence, demonstrating the potential of SPS to fabricate ASSLIB components.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"507 ","pages":"Article 132112"},"PeriodicalIF":5.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143815229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enhancing interfacial strength of DLC films on plasma-nitrided stainless steel
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-04-02 DOI: 10.1016/j.surfcoat.2025.132106
Abdelrahman Farghali , Tatsuhiko Aizawa , Junho Choi
An interfacial toughness of diamond-like carbon (DLC) films onto the stainless steel substrates is of progressive importance due to the countless tribological advantages of DLC in recent industries. The purpose of this article is to enhance the adhesion strength of DLC amorphous film on martensite stainless steel by introducing two different layers. A combination of nitrogen supersaturation layer and SiCx:H interlayer film were utilized to achieve this purpose. The nanograined, hard nitrogen-supersaturated layer, acted as a transition zone, having more homogenous load-bearing capacity than all coatings onto the non-nitrided substrate. Moreover, SiCx:H interlayer attains SiN and CN bonds between the nitrogen-supersaturated layer and SiCx:H interlayer. These bonds have a direct influence in increasing the number of stable sp3 hybridization bonds between these two layers which ultimately further improve the interfacial strength.
{"title":"Enhancing interfacial strength of DLC films on plasma-nitrided stainless steel","authors":"Abdelrahman Farghali ,&nbsp;Tatsuhiko Aizawa ,&nbsp;Junho Choi","doi":"10.1016/j.surfcoat.2025.132106","DOIUrl":"10.1016/j.surfcoat.2025.132106","url":null,"abstract":"<div><div>An interfacial toughness of diamond-like carbon (DLC) films onto the stainless steel substrates is of progressive importance due to the countless tribological advantages of DLC in recent industries. The purpose of this article is to enhance the adhesion strength of DLC amorphous film on martensite stainless steel by introducing two different layers. A combination of nitrogen supersaturation layer and SiC<sub>x</sub>:H interlayer film were utilized to achieve this purpose. The nanograined, hard nitrogen-supersaturated layer, acted as a transition zone, having more homogenous load-bearing capacity than all coatings onto the non-nitrided substrate. Moreover, SiC<sub>x</sub>:H interlayer attains Si<img>N and C<img>N bonds between the nitrogen-supersaturated layer and SiC<sub>x</sub>:H interlayer. These bonds have a direct influence in increasing the number of stable sp<sup>3</sup> hybridization bonds between these two layers which ultimately further improve the interfacial strength.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"507 ","pages":"Article 132106"},"PeriodicalIF":5.3,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143815230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Reverse pulse strategies for silicon dioxide thin films deposition by high power impulse magnetron sputtering
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-04-01 DOI: 10.1016/j.surfcoat.2025.132117
A.W. Oniszczuk , D.S. Owen , D.A.L. Loch , P.Eh. Hovsepian , A.P. Ehiasarian
High density transparent oxide layers on polymers and glass can improve the environmental viability of photovoltaics‚ displays‚ and low emissivity layers in glazing as well as aid the design of optical filters. High Power Impulse Magnetron Sputtering (HIPIMS) produces high density microstructures and high hardness due to the delivery of an ionised metal and dissociated Oxygen deposition flux to the substrates. Silicon dioxide (SiOx) films were deposited by reactive HIPIMS of a metallic target in an Argon-Oxygen atmosphere. Single-target HIPIMS sputtering with reverse voltage operation was evaluated. The HIPIMS process was carried out by controlling the current within the pulse. This resulted in the elimination of stability issues associated with runaway currents for all target poisoning states from metallic to compound. SiOx was deposited at a peak current density of 0.5 Acm−2 in a plasma dominated by Si1+ ions as shown by energy- and mass- resolved spectrometry. The measured signal of atomic Oxygen was twice the amount of molecular Oxygen. The pulse duration was 20 microseconds. Plasma persisted to >150 μs after the pulse switch off as evidenced by the Ar neutral (Ar I) optical emission intensity. Arcing rates were significantly reduced when reverse pulsing was used due to the discharging of the target surface. The key attributes of the reverse voltage which influenced the extent of film defects caused by arcing events and deposition conditions were the amplitude and the delay between the switch-off of the pulse and the application of the reverse voltage. Applying a reverse voltage immediately after the end of the pulse utilised the undispersed high-density plasma still present in the racetrack at the point of switch off to neutralise the target surface and reduce arc energy. Reverse voltages of +25 V coupled with short delay times resulted in enhancing the flux and augmenting the energy of metal ions to the substrate. The gains in adatom mobility afforded by this approach promoted the formation of smooth and dense films with microscopic roughness of Ra = 3 nm as observed by AFM and high optical transmittivity of up to 97 % at a wavelength of 800 nm for 200 nm thick films. The high density supported a high nanohardness of 1 μm thick films of 10 ± 1 GPa and Young's modulus 77 ± 9 GPa, representing a 10 % increase over a glass substrate. Reverse voltages of +75 V and beyond were detrimental due to the production of ions of process and contaminant gases near the chamber walls and the target, which disrupted the lateral growth of film grains and induced the formation of globular morphology with a high microscopic surface roughness.
{"title":"Reverse pulse strategies for silicon dioxide thin films deposition by high power impulse magnetron sputtering","authors":"A.W. Oniszczuk ,&nbsp;D.S. Owen ,&nbsp;D.A.L. Loch ,&nbsp;P.Eh. Hovsepian ,&nbsp;A.P. Ehiasarian","doi":"10.1016/j.surfcoat.2025.132117","DOIUrl":"10.1016/j.surfcoat.2025.132117","url":null,"abstract":"<div><div>High density transparent oxide layers on polymers and glass can improve the environmental viability of photovoltaics‚ displays‚ and low emissivity layers in glazing as well as aid the design of optical filters. High Power Impulse Magnetron Sputtering (HIPIMS) produces high density microstructures and high hardness due to the delivery of an ionised metal and dissociated Oxygen deposition flux to the substrates. Silicon dioxide (SiO<sub>x</sub>) films were deposited by reactive HIPIMS of a metallic target in an Argon-Oxygen atmosphere. Single-target HIPIMS sputtering with reverse voltage operation was evaluated. The HIPIMS process was carried out by controlling the current within the pulse. This resulted in the elimination of stability issues associated with runaway currents for all target poisoning states from metallic to compound. SiO<sub>x</sub> was deposited at a peak current density of 0.5 Acm<sup>−2</sup> in a plasma dominated by Si<sup>1+</sup> ions as shown by energy- and mass- resolved spectrometry. The measured signal of atomic Oxygen was twice the amount of molecular Oxygen. The pulse duration was 20 microseconds. Plasma persisted to &gt;150 μs after the pulse switch off as evidenced by the Ar neutral (Ar I) optical emission intensity. Arcing rates were significantly reduced when reverse pulsing was used due to the discharging of the target surface. The key attributes of the reverse voltage which influenced the extent of film defects caused by arcing events and deposition conditions were the amplitude and the delay between the switch-off of the pulse and the application of the reverse voltage. Applying a reverse voltage immediately after the end of the pulse utilised the undispersed high-density plasma still present in the racetrack at the point of switch off to neutralise the target surface and reduce arc energy. Reverse voltages of +25 V coupled with short delay times resulted in enhancing the flux and augmenting the energy of metal ions to the substrate. The gains in adatom mobility afforded by this approach promoted the formation of smooth and dense films with microscopic roughness of R<sub>a</sub> = 3 nm as observed by AFM and high optical transmittivity of up to 97 % at a wavelength of 800 nm for 200 nm thick films. The high density supported a high nanohardness of 1 μm thick films of 10 ± 1 GPa and Young's modulus 77 ± 9 GPa, representing a 10 % increase over a glass substrate. Reverse voltages of +75 V and beyond were detrimental due to the production of ions of process and contaminant gases near the chamber walls and the target, which disrupted the lateral growth of film grains and induced the formation of globular morphology with a high microscopic surface roughness.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"505 ","pages":"Article 132117"},"PeriodicalIF":5.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Microstructure and properties of laser-cladded CoCrMoNb(TiC)x high entropy alloy coatings with various TiC contents
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-04-01 DOI: 10.1016/j.surfcoat.2025.132116
Peng Gao , Kai Wang , Yinghang Sheng , Tong Cui , Fuli Li , Zhiquan Wang , Yingying Fu , Fei Dai , Siying Chen , Bo Li , Hongjian Guo
In this work, CoCrMoNb(TiC)x high entropy alloy coatings with various TiC contents were fabricated by using the laser cladding technology. The effect of TiC content on the microstructure and mechanical properties of the coatings was investigated. The tribological properties of the CoCrMoNb(TiC)7.5% coatings were investigated in the temperature range from room temperature (RT) to 800 °C. The results showed that the CoCrMoNb(TiC)x coatings were mainly composed of BCC, FCC phases, and a small amount of Laves phases. The addition of TiC introduced new compounds such as Cr3C2 and NbC into the coatings. As the TiC content increased, the skeletal-like structure progressively bonded and fused in the coating, resulted in a denser structure. The CoCrMoNb(TiC) 7.5 % coating exhibited the largest microhardness of 938HV0.3 and best wear resistance (1.6 × 10−5 mm3/Nm) at RT, which was mainly attributed to the synergistic effect of solid solution strengthening, fine grain strengthening, and dispersion strengthening by hard phases such as TiC, Cr3C2 and NbC. The CoCrMoNb(TiC)7.5% coating demonstrated the best tribological property at 800 °C, primarily due to the formation of a dense enamel layer composed of Cr2O3, Co3O4, Nb2O5, and other oxides on the worn surface, which effectively reduced the friction and enhanced the anti-wear resistant of the coating.
{"title":"Microstructure and properties of laser-cladded CoCrMoNb(TiC)x high entropy alloy coatings with various TiC contents","authors":"Peng Gao ,&nbsp;Kai Wang ,&nbsp;Yinghang Sheng ,&nbsp;Tong Cui ,&nbsp;Fuli Li ,&nbsp;Zhiquan Wang ,&nbsp;Yingying Fu ,&nbsp;Fei Dai ,&nbsp;Siying Chen ,&nbsp;Bo Li ,&nbsp;Hongjian Guo","doi":"10.1016/j.surfcoat.2025.132116","DOIUrl":"10.1016/j.surfcoat.2025.132116","url":null,"abstract":"<div><div>In this work, CoCrMoNb(<em>TiC</em>)<sub>x</sub> high entropy alloy coatings with various TiC contents were fabricated by using the laser cladding technology. The effect of TiC content on the microstructure and mechanical properties of the coatings was investigated. The tribological properties of the CoCrMoNb(TiC)<sub>7.5%</sub> coatings were investigated in the temperature range from room temperature (RT) to 800 °C. The results showed that the CoCrMoNb(<em>TiC</em>)<sub>x</sub> coatings were mainly composed of BCC, FCC phases, and a small amount of Laves phases. The addition of TiC introduced new compounds such as Cr<sub>3</sub>C<sub>2</sub> and NbC into the coatings. As the TiC content increased, the skeletal-like structure progressively bonded and fused in the coating, resulted in a denser structure. The CoCrMoNb(TiC) 7.5 % coating exhibited the largest microhardness of 938HV<sub>0.3</sub> and best wear resistance (1.6 × 10<sup>−5</sup> mm<sup>3</sup>/Nm) at RT, which was mainly attributed to the synergistic effect of solid solution strengthening, fine grain strengthening, and dispersion strengthening by hard phases such as TiC, Cr<sub>3</sub>C<sub>2</sub> and NbC. The CoCrMoNb(TiC)<sub>7.5%</sub> coating demonstrated the best tribological property at 800 °C, primarily due to the formation of a dense enamel layer composed of Cr<sub>2</sub>O<sub>3</sub>, Co<sub>3</sub>O<sub>4</sub>, Nb<sub>2</sub>O<sub>5</sub>, and other oxides on the worn surface, which effectively reduced the friction and enhanced the anti-wear resistant of the coating.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"505 ","pages":"Article 132116"},"PeriodicalIF":5.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Effect of C content on the microstructural evolution and wear resistance of AlCoCrFeNiTiW high-entropy alloy coatings
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-04-01 DOI: 10.1016/j.surfcoat.2025.132115
Kedong Yu , Zhen Li , Fujie Zhou , Yingzhe Li , Jinglong Tang , Zhen Luo
Laser cladding was used to fabricate AlCoCrFeNiTiWCx high-entropy alloy (HEA) coatings (x = 0, 0.5, 1, 1.5, 2) reinforced with μ-phase and in-situ (Ti, W)C carbides. The influence of carbon content on the coatings' microstructure, microhardness, and wear resistance was examined. Results showed that all coatings exhibited a dominant BCC phase. With increasing carbon content, the μ-phase evolved from a blocky to a network-like structure, while its volume fraction decreased. Simultaneously, the carbides transformed from near-spherical to flower-like and dendritic morphologies, with their volume fraction increasing. Wear resistance initially improved and then declined, with the C1 coating demonstrating the highest resistance. The primary wear mechanisms were abrasive and oxidative wear. Strengthening mechanisms included solid solution strengthening, secondary phase strengthening by μ-phase and in-situ carbides, and grain refinement strengthening.
{"title":"Effect of C content on the microstructural evolution and wear resistance of AlCoCrFeNiTiW high-entropy alloy coatings","authors":"Kedong Yu ,&nbsp;Zhen Li ,&nbsp;Fujie Zhou ,&nbsp;Yingzhe Li ,&nbsp;Jinglong Tang ,&nbsp;Zhen Luo","doi":"10.1016/j.surfcoat.2025.132115","DOIUrl":"10.1016/j.surfcoat.2025.132115","url":null,"abstract":"<div><div>Laser cladding was used to fabricate AlCoCrFeNiTiWC<sub>x</sub> high-entropy alloy (HEA) coatings (x = 0, 0.5, 1, 1.5, 2) reinforced with μ-phase and in-situ (Ti, W)C carbides. The influence of carbon content on the coatings' microstructure, microhardness, and wear resistance was examined. Results showed that all coatings exhibited a dominant BCC phase. With increasing carbon content, the μ-phase evolved from a blocky to a network-like structure, while its volume fraction decreased. Simultaneously, the carbides transformed from near-spherical to flower-like and dendritic morphologies, with their volume fraction increasing. Wear resistance initially improved and then declined, with the C<sub>1</sub> coating demonstrating the highest resistance. The primary wear mechanisms were abrasive and oxidative wear. Strengthening mechanisms included solid solution strengthening, secondary phase strengthening by μ-phase and in-situ carbides, and grain refinement strengthening.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"505 ","pages":"Article 132115"},"PeriodicalIF":5.3,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143748501","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Unravelling the potential of non-reactively sputtered (Ti,Al)N coatings
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-03-31 DOI: 10.1016/j.surfcoat.2025.132093
Balint Istvan Hajas , Sarah Christine Bermanschläger , Alexander Kirnbauer , Tomasz Wojcik , Szilard Kolozsvári , Paul Heinz Mayrhofer
Non-reactive magnetron sputtering was used to synthesize (Ti,Al)N coatings from a TiN/AlN (50 % AlN) composite target, with a detailed investigation into how process parameters influence phase formation, hardness, and thermal stability. Optimizing pulse parameters, such as increasing reverse pulse on-time (ton-r) to 8016 ns or pulse frequency (fp) to 250 kHz, effectively suppressed the hcp phase observed under reference conditions (fp = 50 kHz, ton-r = 496 ns, substrate temperatures Ts = 600 °C, sputter power density Pt = 8.6 W/cm2, substrate bias Ub = −50 V). Lower Ts (≤ 450 °C) or Pt (3.4 W/cm2) also mitigate hcp phase formation, while higher Ts or Pt (up to 18.6 W/cm2) amplified it.
Similarly, increasing Ub to −100 V allows to prepare single-phase fcc structured (Ti,Al)N with H up to 39.8 ± 2.1 GPa. By adding 5–10 % N2 to the Ar working gas, the hcp phase formation can be avoided, achieving coatings with H = 38.3 ± 1.4 GPa.
Detailed in-situ XRD as well as TEM studies reveal that coatings with a single-phase fcc structure provide a superior thermal stability during vacuum annealing treatments, particularly those deposited with Ub = −100 V. These retain their fcc structure up to 1100 °C and reach 44.7 ± 2.3 GPa through age hardening.
This study underscores the critical role of suppressing hcp phase formation to enhance both hardness and thermal stability. Optimizing deposition parameters enables the tailoring of (Ti,Al)N coatings for demanding high-temperature applications.
{"title":"Unravelling the potential of non-reactively sputtered (Ti,Al)N coatings","authors":"Balint Istvan Hajas ,&nbsp;Sarah Christine Bermanschläger ,&nbsp;Alexander Kirnbauer ,&nbsp;Tomasz Wojcik ,&nbsp;Szilard Kolozsvári ,&nbsp;Paul Heinz Mayrhofer","doi":"10.1016/j.surfcoat.2025.132093","DOIUrl":"10.1016/j.surfcoat.2025.132093","url":null,"abstract":"<div><div>Non-reactive magnetron sputtering was used to synthesize (Ti,Al)N coatings from a TiN/AlN (50 % AlN) composite target, with a detailed investigation into how process parameters influence phase formation, hardness, and thermal stability. Optimizing pulse parameters, such as increasing reverse pulse on-time (<em>t</em><sub>on-r</sub>) to 8016 ns or pulse frequency (<em>f</em><sub>p</sub>) to 250 kHz, effectively suppressed the hcp phase observed under reference conditions (<em>f</em><sub>p</sub> = 50 kHz, <em>t</em><sub>on-<em>r</em></sub> = 496 ns, substrate temperatures <em>T</em><sub>s</sub> = 600 °C, sputter power density <em>P</em><sub>t</sub> = 8.6 W/cm<sup>2</sup>, substrate bias <em>U</em><sub>b</sub> = −50 V). Lower <em>T</em><sub>s</sub> (≤ 450 °C) or <em>P</em><sub>t</sub> (3.4 W/cm<sup>2</sup>) also mitigate hcp phase formation, while higher <em>T</em><sub>s</sub> or <em>P</em><sub>t</sub> (up to 18.6 W/cm<sup>2</sup>) amplified it.</div><div>Similarly, increasing <em>U</em><sub>b</sub> to −100 V allows to prepare single-phase fcc structured (Ti,Al)N with <em>H</em> up to 39.8 ± 2.1 GPa. By adding 5–10 % N<sub>2</sub> to the Ar working gas, the hcp phase formation can be avoided, achieving coatings with <em>H</em> = 38.3 ± 1.4 GPa.</div><div>Detailed in-situ XRD as well as TEM studies reveal that coatings with a single-phase fcc structure provide a superior thermal stability during vacuum annealing treatments, particularly those deposited with <em>U</em><sub>b</sub> = −100 V. These retain their fcc structure up to 1100 °C and reach 44.7 ± 2.3 GPa through age hardening.</div><div>This study underscores the critical role of suppressing hcp phase formation to enhance both hardness and thermal stability. Optimizing deposition parameters enables the tailoring of (Ti,Al)N coatings for demanding high-temperature applications.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"506 ","pages":"Article 132093"},"PeriodicalIF":5.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A thermal mechanical coupled damage accumulation model for rare earth-doped EB-PVD TBCs under isothermal oxidation, cyclic oxidation and creep conditions
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-03-31 DOI: 10.1016/j.surfcoat.2025.132088
Ziang Li , Kun Xiong , Dongxu Li , Cheng Hou , Xueling Fan
Thermal barrier coatings (TBCs), a key thermal protection technology, can effectively improve the service temperature and life of aircraft engineturbine blades. It is crucial to accurately predict the damage and life of TBCs under service environments for ensuring the safe and stable operation of engines. In this work, the isothermal oxidation, cyclic oxidation and creep tests of EB-PVD TBCs were carried out at 980 °C. The microstructure evolution of the TBCs was observed to reveal the failure mechanism of TBCs. The vertical compressive strain and compressive stress of TBCs were determined to characterize TBCs damage based on room-temperature compression tests and three-dimensional digital image correlation technology. In addition, a nonlinear coupled damage accumulation model of TBCs was developed, considering high-temperature oxidation, cyclic oxidation and creep conditions at 980 °C. Results show that the TBCs damage during service can be attributed to factors including the thermally grown oxide (TGO) growth, thermal mismatch stress and plastic deformation accumulation. The error between predicted damage and experimental results is <15 %.
{"title":"A thermal mechanical coupled damage accumulation model for rare earth-doped EB-PVD TBCs under isothermal oxidation, cyclic oxidation and creep conditions","authors":"Ziang Li ,&nbsp;Kun Xiong ,&nbsp;Dongxu Li ,&nbsp;Cheng Hou ,&nbsp;Xueling Fan","doi":"10.1016/j.surfcoat.2025.132088","DOIUrl":"10.1016/j.surfcoat.2025.132088","url":null,"abstract":"<div><div>Thermal barrier coatings (TBCs), a key thermal protection technology, can effectively improve the service temperature and life of aircraft engineturbine blades. It is crucial to accurately predict the damage and life of TBCs under service environments for ensuring the safe and stable operation of engines. In this work, the isothermal oxidation, cyclic oxidation and creep tests of EB-PVD TBCs were carried out at 980 °C. The microstructure evolution of the TBCs was observed to reveal the failure mechanism of TBCs. The vertical compressive strain and compressive stress of TBCs were determined to characterize TBCs damage based on room-temperature compression tests and three-dimensional digital image correlation technology. In addition, a nonlinear coupled damage accumulation model of TBCs was developed, considering high-temperature oxidation, cyclic oxidation and creep conditions at 980 °C. Results show that the TBCs damage during service can be attributed to factors including the thermally grown oxide (TGO) growth, thermal mismatch stress and plastic deformation accumulation. The error between predicted damage and experimental results is &lt;15 %.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"505 ","pages":"Article 132088"},"PeriodicalIF":5.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143748502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Vapor- and impurity-controlled growth regimes during deposition of thin noble metal films on weakly-interacting substrates
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-03-30 DOI: 10.1016/j.surfcoat.2025.132111
K. Sarakinos , S. Kirjonen , B. Sanzone , F.L. Nadji Adjim , A. Ashraf , N.J. Tanzum , S. Moraes , S. Korkos , K. Mizohata
We study the effect of impurities on the morphological evolution of thin silver (Ag) and copper (Cu) films deposited by direct current and high-power impulse magnetron sputtering on weakly-interacting silicon dioxide and amorphous carbon substrates. We systematically vary the ratio of impurity-to-metal particle flux JimpJmetal arriving at the substrate in the range 10410 and assess the character of film morphological evolution and the overall growth dynamics by means of real-time in-situ diagnostic tools and ex-situ analyses. We find that both thin-film materials exhibit a three-dimensional morphological evolution, which for the case of Ag is governed by the effect of metal vapor flux magnitude on the dynamic competition among island nucleation, growth, and coalescence (vapor-controlled growth regime). At all deposition conditions, small amounts (of the order of 1at.%) of impurities (comprising oxygen, carbon, and hydrogen) are incorporated in the Ag films, while an increase of JimpJmetal suppresses three-dimensional growth for layers deposited on silicon dioxide. Cu exhibits a similar (vis-à-vis Ag) behavior with respect to the overall morphology and impurity incorporation for JimpJmetal below a critical value of 1. For JimpJmetal above 1, the impurity content in the Cu layers increases sharply (reaching 10at.% for JimpJmetal10) and film morphological evolution is seemingly determined by the effect of impurities on the fundamental structure-forming process of island nucleation, grain growth, and crystal growth (impurity-controlled growth regime).
{"title":"Vapor- and impurity-controlled growth regimes during deposition of thin noble metal films on weakly-interacting substrates","authors":"K. Sarakinos ,&nbsp;S. Kirjonen ,&nbsp;B. Sanzone ,&nbsp;F.L. Nadji Adjim ,&nbsp;A. Ashraf ,&nbsp;N.J. Tanzum ,&nbsp;S. Moraes ,&nbsp;S. Korkos ,&nbsp;K. Mizohata","doi":"10.1016/j.surfcoat.2025.132111","DOIUrl":"10.1016/j.surfcoat.2025.132111","url":null,"abstract":"<div><div>We study the effect of impurities on the morphological evolution of thin silver (Ag) and copper (Cu) films deposited by direct current and high-power impulse magnetron sputtering on weakly-interacting silicon dioxide and amorphous carbon substrates. We systematically vary the ratio of impurity-to-metal particle flux <span><math><mfrac><msub><mi>J</mi><mi>imp</mi></msub><msub><mi>J</mi><mtext>metal</mtext></msub></mfrac></math></span> arriving at the substrate in the range <span><math><mo>∼</mo><msup><mn>10</mn><mrow><mo>−</mo><mn>4</mn></mrow></msup><mo>−</mo><mn>10</mn></math></span> and assess the character of film morphological evolution and the overall growth dynamics by means of real-time in-situ diagnostic tools and ex-situ analyses. We find that both thin-film materials exhibit a three-dimensional morphological evolution, which for the case of Ag is governed by the effect of metal vapor flux magnitude on the dynamic competition among island nucleation, growth, and coalescence (<em>vapor-controlled growth regime</em>). At all deposition conditions, small amounts (of the order of <span><math><mn>1</mn><mspace></mspace><mi>at</mi><mo>.</mo><mo>%</mo></math></span>) of impurities (comprising oxygen, carbon, and hydrogen) are incorporated in the Ag films, while an increase of <span><math><mfrac><msub><mi>J</mi><mi>imp</mi></msub><msub><mi>J</mi><mtext>metal</mtext></msub></mfrac></math></span> suppresses three-dimensional growth for layers deposited on silicon dioxide. Cu exhibits a similar (<em>vis-à-vis</em> Ag) behavior with respect to the overall morphology and impurity incorporation for <span><math><mfrac><msub><mi>J</mi><mi>imp</mi></msub><msub><mi>J</mi><mtext>metal</mtext></msub></mfrac></math></span> below a critical value of <span><math><mo>∼</mo><mn>1</mn></math></span>. For <span><math><mfrac><msub><mi>J</mi><mi>imp</mi></msub><msub><mi>J</mi><mtext>metal</mtext></msub></mfrac></math></span> above <span><math><mo>∼</mo><mn>1</mn></math></span>, the impurity content in the Cu layers increases sharply (reaching <span><math><mo>∼</mo><mn>10</mn><mspace></mspace><mi>at</mi><mo>.</mo><mo>%</mo></math></span> for <span><math><mfrac><msub><mi>J</mi><mi>imp</mi></msub><msub><mi>J</mi><mtext>metal</mtext></msub></mfrac><mo>∼</mo><mn>10</mn></math></span>) and film morphological evolution is seemingly determined by the effect of impurities on the fundamental structure-forming process of island nucleation, grain growth, and crystal growth (<em>impurity-controlled growth regime</em>).</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"505 ","pages":"Article 132111"},"PeriodicalIF":5.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143748503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Microstructural evolution and mechanism of a gradient multilayer CrN coating during isothermal oxidation
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-03-30 DOI: 10.1016/j.surfcoat.2025.132109
Shupeng Xu , Yu Xia , Jian Peng , Qiang Shen , Chuanbin Wang
The isothermal oxidation behavior, kinetics, and microstructural evolution of a gradient multilayer CrN coating deposited on 304 stainless steel were systematically investigated. The CrN coating demonstrated superior oxidation resistance compared to conventional Cr and CrN coatings, as evidenced by a lower weight gain over prolonged oxidation. The gradient structure of the coating evolved into a homogeneous multilayer, which effectively delayed the oxidation by hindering the diffusion of oxygen. Additionally, the introduction of a Cr bonding layer not only facilitated the formation of a robust interdiffusion zone with the substrate but also enhanced the coating's adhesion, contributing to its long-term stability.
{"title":"Microstructural evolution and mechanism of a gradient multilayer CrN coating during isothermal oxidation","authors":"Shupeng Xu ,&nbsp;Yu Xia ,&nbsp;Jian Peng ,&nbsp;Qiang Shen ,&nbsp;Chuanbin Wang","doi":"10.1016/j.surfcoat.2025.132109","DOIUrl":"10.1016/j.surfcoat.2025.132109","url":null,"abstract":"<div><div>The isothermal oxidation behavior, kinetics, and microstructural evolution of a gradient multilayer Cr<img>N coating deposited on 304 stainless steel were systematically investigated. The Cr<img>N coating demonstrated superior oxidation resistance compared to conventional Cr and CrN coatings, as evidenced by a lower weight gain over prolonged oxidation. The gradient structure of the coating evolved into a homogeneous multilayer, which effectively delayed the oxidation by hindering the diffusion of oxygen. Additionally, the introduction of a Cr bonding layer not only facilitated the formation of a robust interdiffusion zone with the substrate but also enhanced the coating's adhesion, contributing to its long-term stability.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"505 ","pages":"Article 132109"},"PeriodicalIF":5.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A new low infrared emissivity Ag-YCrO3 composite coating for high-temperature infrared stealth applications
IF 5.3 2区 材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Pub Date : 2025-03-30 DOI: 10.1016/j.surfcoat.2025.132107
Rifei Han , Naeem ul Haq Tariq , Jiqiang Wang , Tianying Xiong , Deming Zhang , Tianjie Shi , Xiaoxiao Pang , Xinyu Cui
The rise in temperatures in the hot-end components of aircraft engines underscores the need for the development of infrared stealth coatings capable of withstanding high-temperature conditions, thereby improving aircraft survivability. However, creating a high-performance infrared stealth coating for such environments presents a significant challenge due to the extreme thermal stresses and stringent material requirements. In this study, we design and fabricate a novel YCrO₃-reinforced Ag matrix composite coating with low infrared emissivity, high temperature resistance, and strong adhesion. The coating is characterized under simulated aircraft service conditions. Results reveal that the as-sprayed coating exhibits a low infrared emissivity of 0.376 (3–5 μm, 900 °C) and an adhesion strength of 17.58 ± 0.58 MPa. Furthermore, the coating demonstrates exceptional durability in high-temperature marine environments, as confirmed by a salt spray-thermal exposure cycle test. After 20 cycles, the coating shows no structural failure, with emissivity decreasing to 0.279 (3–5 μm, 900 °C) and bond strength increasing to 33.90 ± 1.10 MPa. This study demonstrates the potential for achieving high-temperature infrared stealth using a low-emissivity perovskite-reinforced noble metal composite coating.
{"title":"A new low infrared emissivity Ag-YCrO3 composite coating for high-temperature infrared stealth applications","authors":"Rifei Han ,&nbsp;Naeem ul Haq Tariq ,&nbsp;Jiqiang Wang ,&nbsp;Tianying Xiong ,&nbsp;Deming Zhang ,&nbsp;Tianjie Shi ,&nbsp;Xiaoxiao Pang ,&nbsp;Xinyu Cui","doi":"10.1016/j.surfcoat.2025.132107","DOIUrl":"10.1016/j.surfcoat.2025.132107","url":null,"abstract":"<div><div>The rise in temperatures in the hot-end components of aircraft engines underscores the need for the development of infrared stealth coatings capable of withstanding high-temperature conditions, thereby improving aircraft survivability. However, creating a high-performance infrared stealth coating for such environments presents a significant challenge due to the extreme thermal stresses and stringent material requirements. In this study, we design and fabricate a novel YCrO₃-reinforced Ag matrix composite coating with low infrared emissivity, high temperature resistance, and strong adhesion. The coating is characterized under simulated aircraft service conditions. Results reveal that the as-sprayed coating exhibits a low infrared emissivity of 0.376 (3–5 μm, 900 °C) and an adhesion strength of 17.58 ± 0.58 MPa. Furthermore, the coating demonstrates exceptional durability in high-temperature marine environments, as confirmed by a salt spray-thermal exposure cycle test. After 20 cycles, the coating shows no structural failure, with emissivity decreasing to 0.279 (3–5 μm, 900 °C) and bond strength increasing to 33.90 ± 1.10 MPa. This study demonstrates the potential for achieving high-temperature infrared stealth using a low-emissivity perovskite-reinforced noble metal composite coating.</div></div>","PeriodicalId":22009,"journal":{"name":"Surface & Coatings Technology","volume":"505 ","pages":"Article 132107"},"PeriodicalIF":5.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143759448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Surface & Coatings Technology
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