Multilayer Coatings Research Articles

Nanostructured multilayer Cr/CrN coatings on 316L stainless steel for proton exchange membrane fuel cell bipolar plates

Nowadays, hybrid surface modification approaches offer tailored solutions for improving the corrosion resistance and electrical conductivity of the bipolar plates (BPPs) in proton exchange membrane fuel cells (PEMFCs). In the present study, a combination of plasma nitriding and physical vapor deposition (PVD) processes was used to apply a nanometric Cr/CrN multilayer coating onto 316L stainless steel (SS316L) bipolar plates. The performance of the resulting plasma nitrided, PVD-coated, and combined plasma nitriding/PVD-coated SS316L BPPs was examined by phase and morphological characterizations, surface wettability measurements, interfacial contact resistance (ICR), and electrochemical investigations. Potentiodynamic and potentiostatic polarization evaluations, electrochemical impedance spectroscopy (EIS) and Mott-Schottky asessments were conducted on the coated samples in a simulated PEMFC cathode environment at temperatures of 25 °C and 75 °C. Results indicated that the Cr/CrN multilayer coating deposited on the plasma-nitrided 316L BPP exhibited a remarkable 100-fold improvement in corrosion resistance compared to the uncoated substrate. Also, the combination of nitriding and PVD resulted in a significant reduction of the ICR from 186 mΩ cm2 for the uncoated SS316L to 10.2 mΩ cm2 for the coated sample. Multilayer coatings based on the combination of plasma nitriding and PVD treatment can identified as promise candidates for BPP applications.

Development of an advanced in-line multilayer deposition system at Diamond Light Source.

A state-of-the-art multilayer deposition system with a 4200 mm-long linear substrate translator housed within an ultra-high vacuum chamber has been developed. This instrument is engineered to produce single and multilayer coatings, accommodating mirrors up to 2000 mm in length through the utilization of eight rectangular cathodes. To ensure the quality and reliability of the coatings, the system incorporates various diagnostic tools for in situ thickness uniformity and stress measurement. Furthermore, the system features an annealing process capable of heating up to 700°C within the load-lock chamber. The entire operation, including pump down, deposition and venting processes, is automated through user-friendly software. In addition, all essential log data, power of sputtering source, working pressure and motion positions are automatically stored for comprehensive data analysis. Preliminary commissioning results demonstrate excellent lateral film thickness uniformity, achieving 0.26% along the translation direction over 1500 mm in dynamic mode. The multilayer deposition system is poised for use in fabricating periodic, lateral-graded and depth-graded multilayers, specifically catering to the beamlines for diverse scientific applications at Diamond Light Source.

Enhancing Solar Absorption with Double-Layered Nickel Coatings and WS2 Nanoparticles on Copper Substrates

This study focused on the development and characterization of multi-layered nickel coatings doped with WS2 nanoparticles and electrodeposited on copper substrates. To enhance the solar collector’s performance by improving the solar radiation conversion into heat, two distinct undercoatings were evaluated, along with the incorporation of WS2 nanoparticles in the black nickel layer. X-ray diffraction (XRD) analysis revealed that the bright and dull nickel undercoatings consisted of metallic nickel, whereas the black coatings comprised amorphous nickel oxide, inferred to be Ni2O3 based on energy-dispersive X-ray spectroscopy (EDS) analysis. Scanning electron microscopy (SEM) analysis of the undercoatings and black nickel morphology showed a compact surface with a relatively homogenous microstructure composed of polyhedric grains, which was free of visible cracks or pinholes. The undercoating influenced the brightness, the reflectivity and the reflectance of the black nickel films, with the dull undercoated sample showing the most promising results, with a total absorbance of 0.94. The incorporation of WS2 nanoparticles induced the formation of cracks and increased the porosity of the black nickel film. With an appropriate content of WS2 nanoparticles and the use of a dull undercoat, these drawbacks can be avoided. Concerning the integration of WS2 nanoparticles, a minor decrease in the brightness of the black films and a subsequent increase in the total absorbance ultimately led to an enhancement of the conversion of solar energy into thermal energy.

Microstructure, mechanical performance, thermal stability, and oxidation resistance of AlCrN/AlCrBN nano-multilayer coating

This study synthesized three different coatings using multi-arc ion coating technology: AlCrN, AlCrBN monolayer, and AlCrN/AlCrBN nano-multilayer coatings. A comparative investigation was conducted on the microstructure, mechanical performance, thermal stability, and oxidation properties of coatings. The results indicate the AlCrN, AlCrBN, and AlCrN/AlCrBN nano-multilayer coatings consist of face-centered cubic solid solution fcc-(Cr, Al)N phase. AlCrN/AlCrBN nano-multilayer coatings also exhibit better thermal stability and oxidation resistance than AlCrN and AlCrBN monolayer coatings. The AlCrN/AlCrBN nano-multilayer coatings have a dense, protective, Al2O3 layer formed during high-temperature oxidation. During high-temperature oxidation, the AM (amplitude modulation) decomposition of the AlCrN and AlCrBN monolayers in the AlCrN/AlCrBN nanolayers is inhibited by the structure of the multilayer coatings. The formation of dense oxides on the surface prevents the diffusion of Al and Cr atoms to the outside and prevents the diffusion of oxygen from the outside to the inside of the AlCrN/AlCrBN nanolayers.

Enhancing color tunability and corrosion resistance of ZrO2 hard coatings via embedding Si multilayer films

ZrO2 coatings are widely employed to protect metal substrates from corrosion. However, achieving anti-corrosive ZrO2 coatings that also exhibit the full color range remains a significant challenge. Using the magnetron sputtering, the present study applied a ZrO2/Si multilayer coating to the 304 stainless steel, incorporating Si interlayers within a ZrO2 monolayer coating. The influence of incorporated Si interlayers on the morphology, structure, hardness, optical properties, and corrosion resistance of the ZrO2 coatings was systematically investigated. Application of Si interlayers effectively mitigated the development of columnar structure and pinhole defects in the ZrO2 coatings. This led to a reduction in the surface cluster size from 300 to 50 nm and the average grain size of ZrO2 from 20.3 to 15.7 nm. As a result, ZrO2 coating exhibited significant improvement in corrosion resistance. After adding Si interlayers, the corrosion current density of the ZrO2 coating dropped from 3.76 × 10-6 to 4.69 × 10-8 A/cm2 in 1 mol/L H2SO4 solution, while it dropped from 6.81 × 10-8 to 2.57 × 10-10 A/cm2 in 3.5 wt.% NaCl solution. The ZrO2/Si multilayer coatings exhibited different colors, including red, orange, yellow, green, blue, indigo, and purple. These colors were achieved by varying the thickness of the ZrO2 top layer, which was set at 240, 220, 210, 190, 175, 160, and 150 nm, respectively. The present study provided detailed insights into the color tuning capability and the enhanced corrosion resistance of ZrO2/Si multilayer coatings.

Algorithm for accurate and efficient calculation of coating-induced effects

Multilayer coatings are widely used in reflective optical systems, particularly for short-wavelength applications. Such coatings, while playing a key role in enhancing the reflectance, may cause non-negligible aberrations, which are often omitted in the typical optical design and simulation. In this study, we investigate the effects induced by the multilayer coatings and present a practical computational algorithm that correctly considers the lateral shift, the phase change, and the amplitude modulation. Several examples are included to show the effectiveness of the algorithm.

Advances in optical coating uniformity of interference filters

We propose a method to obtain uniform multilayer coatings using vacuum assemblies with a linear ion source to manufacture narrow-band interference filters essential in astrophysical research for space object imaging in important spectral lines, and to provide multi-channel fiber-optic transmission of information. Interference filters and other optical systems, for example, high-reflective mirrors, steep-front beam splitters contain up to hundreds of film layers deposited onto a substrate. During the coating deposition, film thickness on the substrate must be strictly withstood and be uniform throughout the entire surface. This can be achieved by placing the linear source and target on the same platform and by conducting a test target sputtering on a fixed substrate. There is an inflection line on the coating thickness distribution on the substrate. By moving the platform, the inflection line midpoint is aligned with the center of the rotating working substrate, and in this position, the substrate is coated to a specified thickness, which is monitored during the deposition process.

Controllable stress-adsorbed layers in Ti/TiN/TiAlN coatings: Mechanical performance and micropillar compression

Solid particle erosion often compromises the durability of turbine engine blades, particularly those used in offshore and desert environments. Surface protective coatings have emerged as a promising solution to significantly enhance the erosion resistance of compressor blades. In this study, TiAlN multilayer coatings were deposited onto Ti-6Al-4V substrates using a vacuum arc deposition technique. The article explored the strategic incorporation of TiN-Ti-TiN stress-adsorbed layers (SALs) within TiAlN-based coatings. It also investigated the microscale mechanisms leading to coating failure under conditions of micropillar compression. The findings revealed that the presence of metal/ceramic interfaces significantly improved the adhesion strength, crack resistance, erosion resistance and fracture toughness of the coatings. The multilayer deformation behavior of the coatings was primarily determined by the plastic flow of the softer metal layers. The SALs played a crucial role in reducing the elastic strain energy by generating nanotwins, coherent interfaces, and high-density dislocations during deformation, thereby improving the coatings' plastic deformation capability. Moreover, the implementation of dual-cycle SALs successfully reduced radial crack propagation, facilitating a transition from brittle fracture to a combined brittle-ductile fracture mechanism. This study highlights the critical role of metal/ceramic interfaces and SALs in improving the erosion resistance and co-deformability of TiAlN-based hard coatings.

Achieving exceptional strain-hardening ability in nanocrystalline Ni–W coatings through compositionally modulated multilayer approach

Nanocrystalline Ni–W coatings show exceptional strength; however, they exhibit poor toughness due to limited ductility and high residual stresses which impede their use in practical applications as a potential hard chrome replacement. In the present study, compositionally modulated multilayer (CMM) coatings with alternate layers of Ni-1 at% W (soft) and Ni-15 at% W (hard) of three different layer thicknesses of 1, 0.5, and 0.1 μm are developed by pulse reverse electrodeposition to achieve the strength-ductility synergy, thereby enhanced wear resistance. Microcompression test results reveal that all the CMM coatings exhibit remarkably higher strain-hardening ability than the homogenous coatings. Significant fluctuations in the strain-hardening rate and a positive shift in the onset stress for the work-hardening stages were observed with the layer thickness. This suggests a strong interplay between the hard and soft layers on the deformation characteristics of multilayer coatings. Detailed electron microscopy of the cross-section of the deformed micropillars shows substantial evidence of co-deformation of both layers. A mechanism is proposed to explain the enhanced strain-hardening in multilayers involving the strength incompatibility arising in the layers leading to lateral constraints, resulting in strain gradient plasticity, stabilizing of local shear by the soft layers, and the barrier effect of the interfaces.

Lattice matching growth of high anti-corrosion TiCr/TiCrN coating for Ti bipolar plate

Designof suitable transition layer is of great importance for the preparation of high-performance multilayer coatings for metallic bipolar plate. In present work, complete lattice matching growth of TiCrN surface layer on the TiCr transition layer is demonstrated. The double-layer TiCr/TiCrN coating exhibits both excellent anti-corrosion performance and surface conductivity, i.e., a low corrosion current density (Icorr) of 0.070 μA/cm2 (0.5 M H2SO4 + 2 ppm HF, 80 °C with air) and a small interfacial contact resistance (ICR) of 2.3 mΩ cm2 at 140 N/cm2, respectively. Moreover, the TiCr/TiCrN coating shows excellent long-term stability under the conditions proposed by the U.S. Department of Energy (pH = 3, 0.1 ppm HF, 80 °C with air), i.e., the current density maintains at around 0.02 μA/cm2 during the 300 h potentiostatic test at 0.2 V (vs. Hg/Hg2SO4).

Cellulose Acetate and Polycaprolactone Fibre Coatings on Medical-Grade Metal Substrates for Controlled Drug Release.

This study explores a method that has the potential to be cost effective in inhibiting biofilm formation on metallic prostheses, thereby preventing rejection or the requirement for replacement. A cost-effective metal alloy used in biomedical implants was chosen as the substrate, and ibuprofen (Ibu), a well-known anti-inflammatory drug, was selected for drug release tests for its widespread availability and accessibility. Multilayer coatings consisting of cellulose acetate (CA), polycaprolactone (PCL), and chitosan (CHI), with or without ibuprofen (Ibu) content, were applied onto medical-grade stainless steel (SS-316 type) through electrospinning, electrospray, or blow spinning. The adhesion of the CA, PCL, and layered CA/PCL membranes, with thicknesses ranging from 20 to 100 μm, to SS substrates varied between 0.15 N and 0.22 N without CHI, which increased to 0.21 and 0.74 N, respectively, when a CHI interlayer was introduced by electrospraying between the SS and the coatings. Although drug release in a simulated body fluid (SBF) medium is predominantly governed by diffusion-driven mechanisms in all single- and multilayer coatings, a delayed release was noted in CA coatings containing Ibu when overlaid with a PCL coating produced by blow spinning. This suggests avenues for further investigations into combinations of multilayer coatings, both with and without drug-imbued layers.

Research, Development and Implementation of Methods for Determining Surface Density and Mass Fraction of Elements for Multilayer and Multicomponent Coatings by X-Ray Fluorescence Method

Metal coatings provide products with the necessary technical characteristics; in particular, they increase corrosion resistance and protect against mechanical abrasion. The application of metal coatings is a promising direction and is widely used in mechanical engineering, metallurgy, and other industries. Therefore, studying the properties and improving the technology of applying metal coatings is a significant and sought-after line of activity for metrology researchers. The needs of industry in the field of monitoring the parameters of single-layer and single-component coatings in the Russian Federation are fully satisfied. At the beginning of this study, the Federal Information Fund for Ensuring the Uniformity of Measurements provided a comprehensive list of reference materials of surface density and thickness of single-layer onecomponent coatings that were tested using the State Primary Standard for units of surface density and mass fraction of elements in coatings GET 168-2015. The needs for testing, verification, and calibration of instruments for measuring surface density, thickness, and chemical composition of multilayer and multicomponent coatings remained not fully met, which became the starting point for this research.The research presented in the article was carried out in order to develop methods for determining the surface density and mass fraction of elements for multilayer and multicomponent coatings on GET 168-2015. At the same time, the problem of developing a set of reference materials of surface density and mass fraction of elements in two-layer and two-component coatings for metrological support of the corresponding measuring instruments was solved.The article fully reveals the content of the work to improve metrological support for measuring surface density, thickness, and mass fraction of elements in coatings, taking into account the needs of industry in the field of monitoring coating parameters and the variety of measurement tasks that are constantly expanding.

Impact of carbon and platinum protective layers on EDS accuracy in FIB cross-sectional analysis of W/Hf/W thin-film multilayers

Achieving high-quality cross sections is essential for accurate analysis of multilayer coatings. One method of performing such cross sections is focused ion beam, where sample protection from ion damage in the form of protective layers applied by FEBID and FIBID methods is used. Due to the lack of comparative summaries of different layers applied by these methods, especially in the context of cross-sectional analysis and elemental analysis of the cross-section, it was decided to address the effect of the protective layer on the reliability of EDS analysis. This study compares the effectiveness of platinum and carbon protective layers in creating cross sections for W/Hf/W samples. The effect of protective layers on elemental mapping and elemental analysis accuracy was evaluated. This study highlights the importance of protective layer selection in providing reliable EDS analysis of cross sections.

Contrast Role of Third Body Layer and Hard Abrasives in the Wear Process of a TiAlSiN Hardness-Modulated Multilayer Coating: A Case Study on the Effect of Normal Load and Velocity

Working conditions exert an important influence on the tribological properties of protective coatings, thus affecting the wear resistance of workpieces. In this work, a TiAlSiN hardness-modulated multilayer coating with a good match of strength and toughness was deposited on WC-Co substrates. The adhesive wear played a predominant role under the condition of a larger normal load and lower velocity, leading to the formation of a third body layer composed of compressed and lubricating oxides. As a result, the wear rate of the coating tested at 20 N reduced by 23% of that tested at 5 N. Instead, abrasive wear was more manifest, leading to the formation of big-size abrasives, and thus the wear rate increased by 2.8 times while the velocity elevated from 4 mm/s to 16 mm/s. A full factorial analysis of the wear behaviors, including the nanohardness and roughness of the wear track, and the friction coefficient and wear rate of the coating, offered good guidance for the comprehension of the wear form of the TiAlSiN multilayer coating. The results demonstrated the optimization of multilayer structures for TiAlSiN coatings to attain better wear resistance under coupling conditions of normal load and velocity: harder or more lubricated sublayers.

Effect of TiN monolithic and Ti/TiN multilayer coating on the fatigue behavior of titanium alloy under tension-tension

This paper investigates the fatigue failure mechanism of mono- and multilayer coatings on the fatigue performance of TC11 titanium alloy under tension-tension. The morphology, phase composition, mechanical properties were measured by scanning electron microscope, X-ray diffractometer and nanoindentation. Electron back scatter diffraction was employed to investigated the failure mechanism. Fatigue limits obtained of uncoated TC11, TC11 with TiN coating, TiN/Ti multilayer (ML-6, ML-3, ML-1) and after 1 × 107 cycles are 855 MPa, 550 MPa, 525 MPa, 500 MPa and 400 MPa. Under fatigue loading, the hard-coating/TC11 substrate experiences fatigue failure through coating cracking hastens the substrate's fatigue failure. EBSD analysis results indicate that the main slip system of TC11 titanium alloy under tension-tension fatigue load is α phase (10-10)[-12-10]. After 1 × 107 cycles at fatigue limits, the average dislocation density on the surface of the TC11 with TiN coating is lower than that of TC11. Due to the surface defect induced by coating preparation and high crack propagation velocity, the hard coating significantly deteriorates fatigue property of TC11 by reducing fatigue crack initiation period. Therefore, instead of approaching from the perspective of coating structure design to increase the fatigue crack propagation cycles, it is more effective to reduce the surface roughness of the coating and enhance the fatigue crack initiation cycles.

Multi-layer structured AlN/Er2O3 coating: Enhanced thermal stability and hydrogen isotope permeation resistance

AlN/Er2O3 multi-layer coatings, as a novel hydrogen isotope permeation barrier for nuclear reactor and hydrogen energy field, were prepared by magnetron sputtering coupled with metal-organic decomposition on the surface of reduced activation ferrite/martensitic steel. The thickness of the Er2O3 layers was adjusted by spin coating several times, the adhesion of the layers was tested with a micron scratch tester, and the microstructure and surface composition of the layers were analyzed by TEM and XPS. The results indicate the absence of evident crack holes on the coating surface, uniform distribution of elements without segregation, and satisfactory densification. In comparison with the individual Er2O3 coating, the multi-layer coating incorporating AlN as the interlayer exhibits enhanced adhesion strength, which could effectively mitigate the thermal mismatch phenomenon of Er2O3 under high temperature conditions. Electrochemical hydrogen permeation and high temperature gas pressure driven deuterium permeation tests demonstrated that the permeability resistance of the AlN/Er2O3 coating does not linearly increase with its thickness. The hydrogen permeation reduced factor of the coating reaches its maximum value when the thickness of the Er2O3 coating is 1500 nm.

Corrosion behavior of TiN monolayer and CrN/TiN multilayer coatings: Impact of immersion time and saline solution type

AbstractThe corrosion behavior of the TiN monolayer and CrN/TiN multilayer coatings deposited via cathodic arc evaporation physical vapor deposition (CAE‐PVD) on the Ti–6Al–4V substrates were evaluated in Ringer's and Hank's physiological saline electrolytes. XRD (x‐ray diffractometry) and scanning electron microscopy (SEM) analysis were used to characterize the coatings. The corrosion behavior of coatings was assessed by impedance spectroscopy and potentiodynamic polarization techniques. The results showed that the corrosion resistance of coatings was increased in the order of TiN‐Ringer's < TiN‐Hank's < CrN/TiN‐Ringer's < CrN/TiN‐Hank's. Therefore, it can be concluded that the CrN/TiN coating, due to having a large number of interfaces and a smoother surface with fewer macroparticles and pinholes, is more efficient in raising the corrosion resistance properties of titanium than TiN monolayer coating. Moreover, it was observed that Ringer's solution is a more severe environment than Hank's solution. Both coatings, because of the precipitation of a protective corrosion products layer on their surface, showed an enhancement in corrosion resistance with increasing the immersion time from 1 to 14 days in Hank's. The results suggest TiN monolayer and CrN/TiN multilayer coatings as promising candidates for biomedical applications.

Stress, reflectance, and stability of Ru/Be multilayer coatings with Mo interlayers near the 11 nm wavelength.

The stress, reflectance, and temporal stability of Ru/Be multilayer mirrors, both with and without Mo interlayers, were studied. A Ru/Be MLM was found to have zero stress at a Ru layer thickness-to-period ratio of γ ∼ 0.4. By adding Mo interlayers to both interfaces, it is possible to achieve a record-high reflectance (R > 71%) at a wavelength close to 11 nm while maintaining near-zero stress levels. A Ru/Be MLM with Mo interlayers at both interfaces also demonstrates high temporal reflectance stability. Ru/Be MLMs may be of interest for the next-generation projection lithography at a wavelength of 11.2 nm.

Investigation of the structural and phase state of detonation multilayer coatings based on NiCr/NiCr–Al2O3/Al2O3 during high-temperature oxidation

This paper presents a study of the structural and phase state of detonation multilayer coatings under hightemperature oxidation. The experiment aimed to find out the effect of high temperatures on the structuralphase state of coatings and their effectiveness in preventing oxidative processes. As a result of the research, it was found that after high-temperature tests, protective phases such as NiCr2O4, Al2O3, and Cr2O3 are formed in the structure of multilayer coatings. These phases were identified to play a key role in preventing intensive oxidation of the metal surface. It was determined that NiCr2O4 provides stability to the metal layer, and Al2O3 and Cr2O3 are effective barriers protecting the surface from aggressive environmental influences. It is important to note that no signs of fracture or detachment were found in the multilayer coatings during the entire experiment. After the first cycle, the uncoated sample experienced peeling of its oxide film, resulting in a significant loss of mass. It was determined that the uncoated steel experiences significantly higher mass loss, indicating a faster formation of oxides on its surface. The experimental data confirm the effectiveness of coatings in protecting against oxidative processes at high temperatures, thereby maintaining the stability and durability of the material under extreme thermal influences.

Fabrication and characterization of MgF2 anti-reflective films comprising dual-layer prepared by physical vapor deposition technique for optoelectronic applications

Moth eye protuberances, for instance, exhibit highly developed and well-organized nanostructures that allow them to adapt to a wide range of environmental conditions and achieve remarkable antireflective performance, which has inspired and been emulated by scientific advancement. Innovative studies have focused on bioinspired and imitating moth-eye patterns to provide a textured surface in multilayer antireflective coatings (ARC) using nanomaterials, polymers, or composites to eliminate undesired reflection in standard optical components and optoelectronic industrial applications. Multilayer AR systems provide a number of advantages over single-layer designs. Still, their limited applicability is due to obstacles such as mismatched properties at interfaces, high costs, poor mechanical durability, and wetting concerns. Using MgF2 and polytetrafluoroethylene, we develop a technique for fabricating high-performance AR nanostructures on borosilicate crown glass and Fluorine-doped Tin Oxide substrates via the glancing angle deposition technique. By inducing porosity and changing the deposition angle (α) at 550 nm, the refractive index of MgF2 is reduced from 1.38 to 1.14. In agreement with optical modelling predictions, high-performance ARC has been successfully produced on different substrates. Besides this, introducing a thin layer of polytetrafluoroethylene on MgF2 ARC via vapor deposition having a refractive index of 1.21 deposited at α ∼80° results in inducing water-repellent properties in ARC. Hence, our fabricated ARC yields stable AR efficiency with outstanding directional uniformity, durability, and negative temperature stability, having hydrophobic characteristics.