Quantifying adhesion energy of mechanical coatings at atomistic scale

Coatings of transition metal compounds find widespread technological applications where adhesion is known to influence or control functionality. Here, we, by first-principles calculations, propose a new way to assess adhesion in coatings and apply it to analyze the TiN coating. We find that the calculated adhesion energies of both the (1 1 1) and (0 0 1) orientations are small under no residual stress, yet increase linearly once the stress is imposed, suggesting that the residual stress is key to affecting adhesion. The strengthened adhesion is found to be attributed to the stress-induced shrinkage of neighbouring bonds, which results in stronger interactions between bonds in TiN coatings. Further finite elements simulation (FEM) based on calculated adhesion energy reproduces well the initial cracking process observed in nano-indentation experiments, thereby validating the application of this approach in quantifying adhesion energy of surface coating systems.     

Structure and mechanical properties of ceramic coatings fabricated by plasma electrolytic oxidation on aluminized steel

Ceramic coatings were formed by plasma electrolytic oxidation (PEO) on aluminized steel. Characteristics of the average anodic voltages versus treatment time were observed during the PEO process. The micrographs, compositions and mechanical properties of ceramic coatings were investigated. The results show that the anodic voltage profile for processing of aluminized steel is similar to that for processing bulk Al alloy during early PEO stages and that the thickness of ceramic coating increases approximately linearly with the Al layer consumption. Once the Al layer is completely transformed, the FeAl intermetallic layer begins to participate in the PEO process. At this point, the anodic voltage of aluminized steel descends, and the thickness of ceramic coating grows more slowly. At the same time, some micro-cracks are observed at the Al₂O₃/FeAl interface. The final ceramic coating mainly consists of γ-Al₂O₃, mullite, and α-Al₂O₃ phases. PEO ceramic coatings have excellent elastic recovery and high load supporting performance. Nanohardness of ceramic coating reaches about 19.6 GPa.     

Tribological properties of heat-treated electroless Ni-P coatings on AZ91 alloy

Influence of heat treatment regime on adhesion and wear resistance of Ni-P electroless coating on AZ91 magnesium alloy is investigated in this work. The pretreated substrate was plated using a bath containing nickel sulphate, sodium hypophosphite and sodium acetate as main constituents. The coated samples were heat treated at 400-450 °C for 1-8 h. Adhesion of coating was estimated from the scratch test with an initial load of 8.80 N. Wear resistance was studied using the pin-on-disc method. It was found that there is no significant dependence of the coating wear resistance on heat treatment regime, as the formation of Al-Ni intermetallic sub-layers that reduce coating adhesion is limited to regions where Al₁₇Mg₁₂ phase is present in the substrate. Moreover, the coating shows good sliding properties due to the formation of oxide glazes in the wear track.     

Adhesive and cohesive properties by indentation method of plasma-sprayed hydroxyapatite coatings

Adhesive and cohesive properties of the plasma-sprayed hydroxyapatite (HA) coatings, deposited on Ti-6Al-4V substrates by varying the plasma power level and spray distance (SD), were evaluated by an indentation method. The crystallinity and the porosity decreased with increasing both of these two parameters. The microhardness value, Young's modulus (E) and coating fracture toughness (K_C) were found to increase with a combinational increase in spray power and SD. The Knoop and Vickers indentation methods were used to estimate E and K_C, respectively. The critical point at which no crack appears at the interface was determined by the interface indentation test. This was used to define the apparent interfacial toughness (K_Ca) which is representative of the crack initiation resistance of the interface. It was found that K_Ca reaches to a maximum at a medium increase in both spray power and SD, while other mechanical properties of the coatings reaches to the highest value with further increase in these two plasma parameters. The tensile adhesion strength of the coatings, measure by the standard adhesion test, ISO 13779-4, was shown to alter in the same manner with K_Ca results. It was deduced that a combinational increase in spray power and SD which leads to a higher mechanical properties in the coatings, does not necessarily tends to a better mechanical properties at the interface.     

The effect of nitrogen and oxygen plasma on the wear properties and adhesion strength of the diamond-like carbon film coated on PTFE

Diamond-like carbon (DLC) films were deposited on polytetrafluoroethylene (PTFE) using a radiofrequency plasma chemical vapour deposition method. Prior to DLC coating, the PTFE substrates were modified with O₂ and N₂ plasma to enhance the adhesion strength of the DLC film to the substrate. The effect of the plasma pre-treatment on the chemical composition and the surface energy of the plasma pre-treated PTFE surface was investigated by X-ray photoelectron spectroscopy (XPS) and static water contact angle measurement, respectively. A pull-out test and a ball-on-disc test were carried out to evaluate the adhesion strength and the wear properties of the DLC-coated PTFE.In the N₂ plasma pre-treatment, the XPS result indicated that defluorination and the nitrogen grafting occurred on the plasma pre-treated PTFE surface, and the water contact angle decreased with increasing the plasma pre-treatment time. In the O₂ plasma pre-treatment, no grafting of the oxygen occurred, and the water contact angle slightly increased with the treatment time. In the pull-out test, the adhesion strength of the DLC film to the PTFE substrate was improved with the plasma pre-treatment to the PTFE substrate, and N₂ plasma pre-treatment was more effective than the O₂ plasma pre-treatment. In the ball-on-disc test, the DLC film with the N₂ plasma pre-treatment showed good wear resistance, compared with that with O₂ plasma pre-treatment.     

Plasma enhanced CVD of SiOxCyHz thin film on different textile fabrics: Influence of exposure time on the abrasion resistance and mechanical properties

In order to improve textile fabric abrasion resistance, in this work a SiO_xC_yH_z thin film was realized by low pressure plasma chemical vapour deposition (PCVD) at room temperature, using hexamethyldisiloxane (HMDSO) as precursor compound. To test changes in the performance properties of the surface finished samples as a function of the type of the substrate, the deposition was carried out on different textile fabrics. The polymerization processes were followed by weight measurements of textile fabrics. It was found that, after PCVD, a significantly lower fabric weight loss was observed on treated samples after rubbing than on the untreated samples. The morphology, elemental composition and type of chemical bonding present in the film applied on textile fabrics were also investigated using electron scanning microscopy (SEM), energy dispersive X-ray (EDX) and infrared spectroscopy techniques (FT-IR (ATR)). The results showed a substantial enhancement of wear resistance for the surfaces modified with the presented process, while tensile and tearing strength were adversely affected.     

Microstructure and mechanical properties of alumina coatings prepared by double glow plasma technique

Low-temperature growth (600 °C) of α-Al₂O₃ coatings on the stainless steel substrate by double glow plasma technique was achieved. The compositions and microstructures of the coatings prepared at different oxygen flow rates were characterized, respectively, by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectrometry. A phenomenological mechanism for the formation of the Al₂O₃ ceramic coatings during the oxidation process was proposed on the basis of the experimental results. It was obvious that the oxygen flow rates had a great effect on the surface structure of the prepared Al₂O₃ coatings. The dense and smooth Al₂O₃ coatings were prepared at the oxygen flow rate of 15 sccm. In addition, the correlations between the mechanical properties of Al₂O₃ coating and oxygen flow rates were also discussed. The coating prepared at 15 sccm oxygen flow rate exhibited the best mechanical properties with a maximum hardness of 31 GPa and elastic modulus of 321 GPa. The corresponding critical load of scratch adherence for this sample was 47 N.     

Effect of spraying power on the microstructure and mechanical properties of supersonic plasma-sprayed Ni-based alloy coatings

The aim of this paper was to investigate the microstructure and mechanical properties of the supersonic plasma-sprayed Ni-Cr-B-Si-C coatings prepared at different spraying powers. The microstructure, phase composition, porosity, Young's modulus, micro-hardness, and residual stresses of the coatings were investigated and determined. The variations of the porosity, Young's modulus and micro-hardness of the coatings were evaluated by using statistical method. Results showed that the variations of porosity, Young's modulus and micro-hardness of the coatings followed the Weibull distributions. With increasing the porosity, the micro-hardness and Young's modulus of the coating decreased. The mean value of the Young's modulus of the coating calculated from Weibull plot was almost proportional to the square root of the micro-hardness of the coating. With increasing the power, Young's modulus of the coating increased, which, in turn, resulted in the increment of the residual stress at the coating surface.     

Effect of feedstock powder characteristics on microstructure and mechanical properties of lanthanum silicate coatings deposited by atmospheric plasma spraying

Lanthanum silicate coatings were deposited onto stainless steel substrates by atmospheric plasma spraying (APS) using mechanically mixed (type A) and calcined feedstock (type B) powders. The phase composition, microstructure, density and porosity of coatings prepared from the two types of powder were compared.     

Silane effects on the surface morphology and abrasion resistance of transparent SiO2/UV-curable resin nano-composites

Transparent ultraviolet curable nano-composite coatings consisting of nano-sized SiO₂ and acrylate resin have been developed to improve the abrasion resistance of organic polymers. The nano-sized SiO₂ particles were surface-modified using various amounts of 3-methacryloxypropyltrimethoxysilane. The 3-methacryloxypropyltrimethoxysilane concentration effects on the surface morphology and abrasion resistance of the transparent SiO₂/ultraviolet-curable resin nano-composites were investigated using scanning electron microscopy, atomic force microscopy, and ultraviolet-visible spectrophotometer. The results showed that as the 3-methacryloxypropyltrimethoxysilane/SiO₂ weight ratio increased from 0.2 to 0.6, the dispersion, compatibility and cross-linking density between the 3-methacryloxypropyltrimethoxysilane-modified SiO₂ particles and acrylate resin were improved, leading to an increase in abrasion resistance. However, as the 3-methacryloxypropyltrimethoxysilane/SiO₂ weight ratio was increased to 1.5, the additional 3-methacryloxypropyltrimethoxysilane may exceed that needed to fill the pores with the probability of SiO₂ nano-particles existing on the coating surface was lower than that for samples with a 3-methacryloxypropyltrimethoxysilane/SiO₂ weight ratio of 0.6. This produced a decrease in abrasion resistance.     

Mechanism of adhesion between protein-based hydrogels and plasma treated polypropylene backing

We studied the mechanism of adhesion between N₂ plasma treated polypropylene (PP/N₂) backing and a hybrid hydrogel (HG) produced by chemical crosslinking between poly(ethylene glycol) and soy albumin. The work of adhesion, measured by peel testing, was found to be 25 times higher for PP/N₂ compared to untreated PP (≈5.0 J/m² versus ≈0.2 J/m²). In order to understand the adhesion mechanism, we performed a detailed analysis of the surface chemical composition of PP and PP/N₂ using X-ray photoelectron spectroscopy (XPS), chemical derivatization and attenuated total reflectance infra-red (ATR-IR) measurements. The results confirm incorporation of different nitrogen- (amine, amide,…) and oxygen- (hydroxyl, carboxyl,…) containing chemical groups on the PP/N₂ surface. The derivatized functions were primary amine, hydroxyl, carboxyl and carbonyl groups. Chemical derivatization reactions validated the XPS results (except for carbonyl groups), and they clearly underlined the essential role of primary amine groups in the adhesion process. In fact, after derivatization of the amine functions, the work of adhesion was found to be 0.41 ± 0.12 J/m². Participation of amine groups in the formation of covalent bonds at the interface between PP/N₂ and HG was directly confirmed by ATR-IR measurements.     

Porosity and effective mechanical properties of plasma-sprayed Ni-based alloy coatings

The aim of this paper was to address the relationship between the porosity and micro-mechanical properties of the Ni-based alloy coatings which were prepared by a novel plasma-spraying system. The porosity and the mechanical properties of the coatings varied through changing the spraying parameters. Experimental results showed that the measured data of porosity, Young’s modulus and micro-hardness of the coating exhibited high scattering and followed the Weibull distribution. From statistic trend, the micro-hardness and Young’s modulus of the coating decreased with increasing the porosity of the coating. Moreover, generally, with increasing the micro-hardness of the coating, Young’s modulus of the coating increased.     

Interface adhesion properties of functional coatings on titanium alloy formed by microarc oxidation method

Three functional coatings (namely Al-C, Si-P-Al and P-F-Al coating) were fabricated by microarc oxidation method on Ti6Al4V alloy in different aqueous solutions. The microstructure, phase and chemical composition of coatings were investigated using scanning electron microscope, X-ray diffraction and energy dispersive spectroscopy. The interface adhesion failure mode of the coating is revealed by shear, tensile and thermal shock methods. The coatings exhibit high adhesion strength by the quantitative shearing test, registering as 110, 70, and 40 MPa for Al-C, Si-P-Al and P-F-Al coating, respectively. The tensile test of the coated samples shows that microarc oxidation treatment does not significantly deteriorate mechanical properties of substrate titanium alloy. The observations of the coating failure after subjected to the identical tensile elongation of 3.0% are well in agreement with those results of the shear test. The thermal cycle test indicates that all the coatings have good anti-thermal shocking properties.     

Structure and mechanical properties of Ni-P electrodeposited coatings

The coatings with different phosphorus contents were obtained by varying the concentration of H₃PO₃ in the electroplating bath. With the increase of phosphorus content, the structure of the Ni-P electrodeposited coatings transformed from microcrystalline to a mixture of nanocrystalline and amorphous phases, then to amorphous phase. A high hardness value of 710 HV_0.1 of as-deposited Ni-P coating was obtained at 8.3 at.% phosphorus content, and high wear resistance was accordingly achieved. The refined nanocrystalline grains with average size of about 7 nm were found to be responsible for the high hardness and improved wear resistance of the as-deposited Ni-P electrodeposited coating.     

Formation of titania composite coatings on carbon steel by plasma electrolytic oxidation

Titania composite coatings were prepared on carbon steel by plasma electrolytic oxidation in silicate electrolyte and aluminate electrolyte with titania powers doping in the electrolytes. The microstructure of the coatings was characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The properties of the coatings including bond strength, thickness, thermal shock resistance and corrosion resistance varying with the quantities of titania powers in the electrolytes were studied. Investigation results revealed that the coating obtained in silicate electrolyte was composed of anatase-TiO₂, rutile-TiO₂ crystal phases and some Fe, Si, P elements; coating obtained in aluminate electrolyte consisted of anatase-TiO₂, Al₂TiO₅ and some Fe, P elements. Coatings obtained in two types of electrolytes show porous and rough surface. With increasing the concentration of titania powers in the electrolytes, the coating surface first became more compact and less porous and then became more porous and coarse. The bond strength and thickness were not strongly affected by concentration of titania powers in electrolytes. The valves were 23 MPa and for 66 μm for coatings obtained in aluminate electrolyte, and 21 MPa and 35 μm for coatings obtained in silicate electrolyte. Coatings obtained in silicate electrolyte showed a little better thermal shock resistance than those obtained in aluminate electrolyte and the best coatings were obtained with middle concentration of titania powers in the electrolytes. All coated samples showed better corrosion resistance than the substrate in 3.5 wt% NaCl solution. The best coatings were also obtained with middle concentration of titania powers doping in both electrolytes whose corrosion current density was decreased by 2 orders of magnitude compared with the substrate.     

Effect of pretreatment methods and chamber pressure on morphology, quality and adhesion of HFCVD diamond coating on cemented carbide inserts

In the present investigation, diamond coating was deposited on cemented carbide substrate by hot filament chemical vapour deposition. The effect of substrate pretreatment methods and chamber pressure on morphology, quality, and adhesion of the diamond film were studied. The carbide inserts were pretreated with acid, Murakami's solution, and Murakami's solution followed by acid, respectively. The chamber pressure was set at 6.6, 13.2, 26.4, 39.6 and 66 mbar. Deposition carried out at pressure of 26.4 and 39.6 mbar on inserts pretreated with acid exhibited uniform crystal habit and provided coating-substrate adhesion adequate for machining application. Good coating morphology was obtained when deposition was done at 6.6 mbar on carbide inserts treated with Murakami's solution. Pretreatment with Murakami's solution followed by acid and deposition at 6.6 mbar also resulted in good morphology of diamond film. Indentation (Rockwell C scale) was done on diamond-coated inserts to assess coating-substrate adhesion under three loads of 294, 588 and 980 N. The diameter of the indentation crack at the coating-substrate interface was observed under SEM. The results suggested that diamond coating deposited at medium pressure of 26.4 mbar on carbide substrate treated with acid not only exhibited best morphology but also highest coating-substrate adhesion and improved machining performance.     

The effects of organoclay on the morphology and mechanical properties of PAI/clay nanocomposites coatings prepared by the ultrasonication assisted process

In this research, solvent based polyamide – imide (PAI)/clay nanocomposites were prepared successfully using the solution dispersion technique. With the assistance of the ultrasonic wave, the effect of the ultrasonic wave time on the microstructure of 3 wt% PAI/C20A nanocomposite (NC) was investigated. Then, the best ultrasonic parameters were selected and the effects of the concentration of Cloisite 20A (C20A) (1, 3 and 5 wt% C20A) on the microstructure and mechanical properties (adhesion, hardness, flexibility, wear and impact) of NCs were investigated. The PAI, C20A and nanocomposites (NC)s were characterized by Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX), and Wide-angle X-ray diffraction (WAXD). The results showed that the sample with 1 and 3 wt% C20A had better mechanical properties, as compared to the pure PAI and the 5 wt% NC.     

Effect of particle size on the tribo-aero-electrostatic separation of plastics

Numerous research studies have been made on the electrostatic separation of granular insulating materials, with many industrial applications in the area of waste electric and electronic equipment (WEEE) recycling. However, very few investigators have studied the separation of finely-ground matter (i.e., granule diameter < 1 mm), in relation with applications in mineral processing, or in food industry. The aim of this work is to evaluate the effect of particle size on the selective sorting of fine particles in a two-rotating-disks-type tribo-aero-electrostatic separator. The experiments are carried out on a synthetic mixture composed of 50% Acrylonitrile Butadiene Styrene (ABS) and 50% Polystyrene (PS) particles of size 250 to 2000 microns. The performance of this separator is evaluated by setting up a measurement system that enables the continuous and simultaneous recording of the charges and the masses of the separated products. The conclusions of this study will serve at the optimum design of an industrial electrostatic separator for the recycling of micronized plastics from WEEE.     

The properties of copper films deposited on polyimide by nitrogen and oxygen plasma pre-treatment

Extensive studies on the relationship between a copper thin film and its polyimide substrate show that the adhesion strength is very weak. In this work, we show how to reduce Cu film resistivity and improve the adhesion strength between Cu and polyimide. After nitrogen and oxygen plasma treatment, polyimide substrates can substantially improve the resistivity and adhesion strength deposited Cu. It is found that the lowest resistivity is 4.22 μΩ cm and the maximum adhesion strength is 72.23 MPa for a polymide substrate treated in oxygen plasma for 5 min.     

Study on the surface properties of wood/polyethylene composites treated under plasma

Wood/polyethylene (PE) composites are widely used in many fields for its excellent properties, but they are hard to adhere for the surface lacking of polarity. So low-pressure glow discharge of air plasma was used to improve the adhesion properties of wood/PE composites. The composites were treated by plasma under different discharge power. And the changes on the surface properties of the treated and untreated composites were studied by contact angle, Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS) analysis. The measurement showed that the contact angle decreased after plasma treatment, and the contact angle decreased gradually with the increasing of discharge power. The FTIR analysis results showed that the polar groups such as hydroxyl, carbonyl and carboxyl were formed on the surface of the composites treated under plasma. SEM and AFM results showed that the roughness of plasma treated samples increased. XPS analysis results indicated that the content of carbon element decreased while the content of oxygen element in the composition of wood/PE composites surface element increased and it reached a balance in a higher power, meanwhile a lot of carboxyl groups were formed. The newly formed polar groups are benefit for the adhesion of composites. The shear bonding strength test showed that the adhesion properties of wood/PE composites improved effectively after plasma treatment.