The role of ion-induced substrate damage in thin film adhesion strength

Variable-energy positrons are combined with Auger electron spectroscopy, scanning electron microscopy, and scratch test critical load measurements to study interfacial properties in thin film adhesion. This work complements an earlier investigation of the adhesion strength enhancement produced by ion bombardment of the substrate surface before deposition. In this study, we have investigated SiO₂ films deposited by radio-frequency (RF) sputtering onto stainless steel substrates. Extended ion bombardment etching leads to three related effects: the scratch test critical load is increased significantly, Auger electron spectroscopy shows a greater penetration of the film material into the substrate; and the interfacial positron annihilation signal is dominated by large, open-volume defects. These results are interpreted as confirmation that ion bombardment leads to the formation of microvoids in the interface layer and, consequently, to an increased adhesion strength by allowing mechanical interlocking between the coating and the substrate.     

Interfacial adhesion measurement of a ceramic coating on metal substrate

The interfacial adhesion measurement of a ceramic coating on a metal substrate is studied by three-point bending (3PB) technique. In the measurement, interfacial cracks are induced during the 3PB test, and the interfacial energy release rate is calculated from the released energy per unit crack surface area during crack extension under the fixed displacement conditions. A finite element analysis (FEA) model encompassing the plastic behavior of the metal substrate is developed to simulate the 3PB test and extract the energy data. The inputs to the FEA model include the crack length, the maximum and critical loads corresponding to crack initiation, and the mechanical properties of the coating and substrate. A MoB/CoCr ceramic coating/stainless steel substrate system is investigated by the technique for demonstrating the utility of the technique.     

Micro-scratch test for adhesion evaluation of thin films

In tribological applications, surface properties govern performance, and hence the utilization of coatings to tailor properties has become an essential component of materials technology. The most critical requirement for such coatings is adequate adhesion. Therefore, the need to measure coating/substrate interfacial strength and to characterize the factors influencing it is critical. However, the most common method currently used to characterize adhesion-the scratch test-is inadequate because it does not really measure adhesion. It is indicative of a relative measure of coating durability, which can be useful, at best, for quality control purposes. Consequently, the need for a test that can more accurately determine the adhesion characteristics of thin films is imperative. The development of a micro-scratch test and how it addresses some of the deficiencies of the conventional scratch test are discussed.     

On the evaluation of adhesion of coatings by automatic scratch testing

Automatic scratch testing is an expedient technique for comparatively evaluating the cohesive failure load and adhesion failure load of thin coatings on various substrates. In combination with SEM examination of the scratch track, this technique has been used herein to detect and evaluate various effects on coating strength and adhesion. For soft Triballoy T-800 and Stellite SF-6 cobalt-base coatings on 4340 low alloy steel, adhesion was found to be strong and failure was found to be cohesive in the coating. In the presence of a plated chromium interlayer, pre-existing cracks lowered substantially the cohesive failure load, which was also lowered by an increase in the coating deposition pressure. The spacing of transverse cracks within the coating was found in all cases to decrease with increasing applied normal load. In soft aluminum coatings on depleted uranium (DU)-0.75% Ti alloy specimens, alloying aluminum with magnesium or zinc enhanced the coating strength and adhesion. In (Al-Mg) coatings on this substrate, a smoother surface led to a lower friction coefficient and a higher adhesion failure load. In hard, thin TiN coatings on 17-4 PH steel, a lower bias voltage applied to the substrate yielded higher cohesive and adhesion failure loads. In hydrogenated amorphous SiC thin coatings on 4340 steel, loss of hydrogen by annealing converted the residual compressive stresses into tensile stresses and lowered both the cohesive and the adhesion failure loads. Finally, automatic scratch testing proved helpful in determining delamination loads in multilayer TiN/Ti/TiN coatings on DU-0.75% Ti alloy.     

Adhesion studies of radio-frequency sputtered SiO2 films on Ti,stainless steel,Ni and Inconel substrates. Effects of substrate surface ion bombardment etching

The scratch test was applied to determine the adhesion strength of radio-frequency (RF) sputtered SiO₂ films to Ti, stainless steel, Ni and Inconel substrates. The effect of substrate ion bombardment etching was investigated by using a mean critical load derived from a Weibull-like statistical analysis. It was found that the mean critical load values obtained on substrates etched by ion bombardment for a sufficiently long time were two to three times those obtained on mechanically polished substrates. Scratch tracks were observed by scanning electron microscopy and some X-ray spectra were measured after the electron beam of the scanning electron microscope was focused inside the scratch channel. Depth composition profiles were also recorded by Auger electron spectroscopy. No important presence of contamination was observed in the interfacial domain even after mechanical polishing, but the width of this interfacial domain was higher after ion bombardment than after mechanical polishing. This difference in width could result from the formation of microcavities and vacancies at the substrate surface during ion bombardment. In such a case, the significant adhesion improvement should principally occur from an enhanced interlocking of the coating to its substrate.     

Influence of 27Al+ ion mixing on the adhesion and interfacial chemistry of Ni films on polyimide and polyester

In order to evaluate the influence of ion chemistry on ion-induced interfacial chemistry and thin film adhesion, 30 nm Ni films on polyester (PET) and polyimide (PI) substrates were implanted with various doses (1-10 x 10¹⁶ Al/cm²) of 50 keV ²⁷Al⁺. The ion-induced interfacial chemistry and adhesion were then examined using X-ray photoelectron spectroscopy (XPS) and scratch testing, respectively. The implantation induced extensive interfacial mixing in both types of specimens. In addition, the implanted Al reacted with oxygen in the polymer substrates to form interfacial Al₂O₃ and Al-O-C layers in the Ni/PET and Ni/PI specimens, respectively. Despite the ion-induced interfacial mixing and compound formation, the scratch testing indicated that no significant adhesion enhancement was produced by the ²⁷ Al⁺ ion mixing. The absence of adhesion enhancement was attributed to the absence of complete chemical bonding between the Ni films and the polymer substrates. Criteria for the selection of an effective reactive ion for adhesion enhancement in a given film/substrate system are discussed.     

Internal stresses and adhesion of thin silicon oxide coatings on poly(ethylene terephthalate)

The effect of internal stresses on the cohesion and adhesion of a thin silicon oxide (SiO_x) oxygen-barrier coating, evaporated on a poly(ethylene terephthalate) (PET) film substrate was studied. Internal stresses were generated during annealing in the temperature range for recrystallization of the PET,during calendering in a multilayer structure where two SiO_x /PET films were laminated together with a polypropylene film, and during long-term thermal aging below the glass transition temperature of the polymer. The cohesion of the coating and its adhesion to the polymer substrate were derived from fragmentation tests, in which the failure of the oxide coating was analyzed as a function of the applied stress during uniaxial tensile loading of the substrate. The intrinsic coating strength at critical length and the interfacial shear strength were found to be equal to 1350 MPa and 73 MPa, respectively. It was found that none of the thermal treatments investigated altered the interfacial interactions. Rather, these treatments induced shrinkage of the PET substrate, which increased the coating internal compressive stress and the SiO_x /PET interfacial shear strength. A linear relationship between the SiO_x /PET interfacial shear strength and the coating internal stress was determined from a stress transfer analysis. The coefficient of this linear relationship, equal to-1.34 · h _c/l _c, where h _c is coating thickness and l _c is the critical stress transfer length, reproduces the experimental data with good accuracy.     

An ASTM Standard for Quantitative Scratch Adhesion Testing of Thin, Hard Ceramic Coatings

Thin, hard ceramic coatings on metals and ceramics are extensively used for wear and abrasion resistance, friction control, corrosion resistance, and tailored functional (electrical, optical, and magnetic) properties across a wide range of high-performance applications. Coating producers and users have to measure and control the coating-substrate adhesion strength, because adhesion failure is often the primary failure mechanism of the coating, limiting its performance and life. The quantitative test method of choice for thin hard coatings is scratch adhesion testing. In this technique, a diamond stylus is drawn across the coating on the surface under increasing normal load and the damage to the coating is assessed against the applied load. With DOE funding and in coordination with the ASTM Committees C28, G08, and B02, a new scratch adhesion test standard has been researched and written and has been published. The ASTM C1624 test standard (Adhesion Strength and Mechanical Failure Modes of Ceramic Coatings by Quantitative Scratch Testing) provides comprehensive and detailed guidance and instructions on scratch adhesion testing of thin, hard ceramic coatings—the principles, terminology, applications, limitations, equipment, specimen preparation and characterization, critical experimental factors, calibration, procedures, calculations, and reporting requirements.     

Adhesion of diamond coatings on steel and copper with a titanium interlayer

Adherent diamond coatings on steel and copper were obtained by using a titanium interlayer. The adhesion of the coatings was evaluated by scratch tests and micro-indentation tests. The diamond coating on steel exhibited a much higher critical load than on copper, as revealed by the scratch tests. However, an observation on the back of the scratch-delaminated film and on the corresponding substrate surface showed that the detachment occurred between the diamond film and the titanium interlayer. Therefore, the difference in the critical scratch load is due mainly to a substrate effect, making it difficult to compare the adhesion of different coatings.On the other hand, Knoop indentation tests showed interesting results: a small indentation load causes round spallation in the film with no observable crack. An exponential sink-in deformation under the indentation is proposed, y=−a exp(−bx). The coating adhesion is considered to be equivalent to the deformation stress at the edge of the spallation zone. The adhesion of diamond coatings on steel and copper with a titanium interlayer is evaluated quantitatively using this model. Furthermore, a thermal quench method is proposed to estimate the coating adhesion. The results found are in agreement with the indentation model.     

Particle Cleaning of EUV Reticles

The practical adhesion, characterized by either ultimate parameters (F _max or d _max) or the critical strain energy release rate (G _Ic) using the three-point flexure test (ISO 14679-1997), and the residual stress (σ ) profiles within systems of organic layers made of DGEBA epoxy monomer and IPDA diamine hardener were determined. The prepolymer (DGEBA-IPDA) was deposited as thin and thick coatings onto degreased or chemically etched aluminum alloy (5754). To understand the role of the interphase, either a tri-layer (bulk coating/interphase/substrate) or a bi-layer model (bulk coating/substrate) were used for quantitative determination of the critical strain energy release rate. Indeed, as the interphase formation results from both dissolution and diffusion phenomena, we were able to control the interphase formation within coated systems by controlling the liquid-solid contact time and then to make tri- or bi-layered systems. In the three-point flexure test used to determine the practical adhesion, the failure may be regarded as a special case of crack propagation. The model considers residual stresses developed within the entire system leading to an intrinsic parameter representing the practical adhesion between the polymer and the metallic substrate. Moreover, to determine the profiles of residual stresses generated in such systems, the Young's modulus gradient of the interphase was also considered. The maxima in residual stress intensities were found at the interphase/substrate interface for a tri-layer system and at the coating/substrate interface for a bilayer system leading for all systems to an adhesional (interfacial) failure as experimentally observed. A comparison between the results obtained from the three-point flexure test and the Tapered Double Cantilever Beam (TDCB) was made. The determination of the critical strain energy release rate shows that residual stresses cannot be neglected. G _Ic depends on the substrate surface treatment when the residual stresses were neglected. Moreover, we have determined the role of the interphase formation on the practical adhesion before and after hydrothermal aging. The results obtained emphasize that the epoxy/metal interphase affects significantly the initial practical adhesion. However, organo-metallic complex formation improves considerably the hydrothermal durability, as these complexes act as corrosion inhibitors.     

Photocurable epoxy/cubic silsesquioxane hybrid materials for polythiourethane: Failure mechanism of adhesion under weathering

A new inorganic–organic hybrid coating containing epoxy‐functionalized cubic silsesquioxane (CSSQ) has been developed, which can be polymerized cationically by UV radiation. This solvent‐free solution can be used as hybrid coating for polythiourethane (PTU) substrate. The surface properties of the coating film were determined by adhesion and scratch resistance. The excellent adhesion of coating films on the substrate was observed at the initial stage before weathering, but deteriorated after exposure to the sunshine. The low viscosity of hybrid coating solution (～ 15 mPa s) leads to fast curing and the formation of hybrid coating film during the photopolymerization reaction. The adhesion failure was evaluated by atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), and X‐ray photoelectron spectroscopy (XPS) analyses. AFM images showed that the surface is smooth at the initial stage, but a texture surface was developed after weathering. The shrinkage of the hybrid film due to the increase in crosslinking density by postpolymerization would affect the surface roughness after weathering. XPS analysis indicated that the adhesion failure occurred by photodegradation of the PTU substrate during weathering. The weathering resistance was significantly improved by adding UV absorbers, which protected the polymer substrate from the photodegradation. The advantages of the hybrid coating include fast cure speed, solvent‐free formulation, and improved surface properties of the coating film. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The Role of the Residual Stresses of the Epoxy-Aluminum Interphase on the Interfacial Fracture Toughness

When an epoxy-diamine system (DGEBA-IPDA) is applied onto aluminum alloy (5754) and cured, an interphase having chemical, physical, and mechanical properties quite different from those of the bulk polymer is created between the substrate and the part of the polymer having bulk properties. To get a better understanding of the role of the interphase on the interfacial fracture toughness either a tri-layer (bulk coating/interphase/substrate) or a bi-layer model (bulk coating/substrate) were used for quantitative determination of the critical strain energy release rate (noted G_c). Indeed, as the interphase formation results from both dissolution and diffusion phenomena, we were able to control the interphase formation within coated systems by controlling the liquid-solid contact time and then to make tri- or bi-layered systems. The particularity of models used is to consider residual stress profiles developed within the entire system leading to an intrinsic parameter representing the work of adhesion between the polymer and the metallic substrate. The aim of this publication is to clearly establish the role of the interphase mechanical properties, such as Young's modulus and residual stress on the interfacial fracture toughness. Results are presented and discussed for three different aluminum surface treatments (chemical etching, degreasing and anodizing).     

Synergistic Toughening of Epoxy–Copper Interface Using a Thiol-Based Coupling Layer

A novel concept of tuning the fracture properties of the interface through the treatment process of the coupling layer according to the cohesive critical strain energy release rate of the epoxy is proposed for optimizing the joint strength between epoxy and copper substrate. In most coupling agent application recipes, the treatment condition design has omitted the influence of the fracture properties of the corresponding adhesive. Conceivably, excessive strengthening of the adhesive–substrate interface may not lead to optimal interfacial strength. Synergistic toughening of the interface takes place when there is simultaneous interfacial debonding and failure of adhesive under a comparable critical stress state. Under critical applied load, energy is concurrently dissipated through the fracture of the interface, the fracture in the adhesive, and possible non-reversible failure processes such as shear yielding or micro-cracking of the adhesive. These combined energy dissipation processes result in extensive energy absorption around the crack tip. The adhesive joint, therefore, becomes more crack resistant. In this study, the interfacial adhesion promotion concept with synergistic toughening was demonstrated using three different epoxy systems bonded to copper substrates modified by a thiol-based coupling layer. The coupling layer was formed by treating the copper substrate with a thiol-based coupling agent. Critical strain energy release rate of the treated tapered double cantilever beam samples in different treatment conditions was measured for each of the epoxy systems. From the failure path analysis, mixed interfacial and cohesive failure was observed. This observation indicated that extensive energy dissipation occurs around the crack tip that results in synergistic toughening of the interface. This work shows the significance of matching the fracture property of the coupling layer with the adhesive. Up to 2.3 times improvement in the critical strain energy release rate was achieved with optimized thiol treatment compared to non-optimized treatment.     

The Role of the Residual Stresses of the Epoxy-Aluminum Interphase on the Interfacial Fracture Toughness

When an epoxy-diamine system (DGEBA-IPDA) is applied onto aluminum alloy (5754) and cured, an interphase having chemical, physical, and mechanical properties quite different from those of the bulk polymer is created between the substrate and the part of the polymer having bulk properties. To get a better understanding of the role of the interphase on the interfacial fracture toughness either a tri-layer (bulk coating/interphase/substrate) or a bi-layer model (bulk coating/substrate) were used for quantitative determination of the critical strain energy release rate (noted G_c). Indeed, as the interphase formation results from both dissolution and diffusion phenomena, we were able to control the interphase formation within coated systems by controlling the liquid-solid contact time and then to make tri- or bi-layered systems. The particularity of models used is to consider residual stress profiles developed within the entire system leading to an intrinsic parameter representing the work of adhesion between the polymer and the metallic substrate. The aim of this publication is to clearly establish the role of the interphase mechanical properties, such as Young's modulus and residual stress on the interfacial fracture toughness. Results are presented and discussed for three different aluminum surface treatments (chemical etching, degreasing and anodizing).     

Adhesion characteristics of nano- and micro-crystalline diamond coatings: Raman stress mapping of the scratch tracks

Interfacial adhesion characteristics of nanocrystalline and microcrystalline diamond coatings deposited on tungsten carbide (WC–Co) substrates were studied and analysed using a scratch tester. Coating failure events and critical point loads were identified by acoustic emission, tangential force measurement and image analysis carried out on the scratch track. In this respect, enhanced scratch resistance properties were observed in microcrystalline diamond (MCD) coating in comparison to nanocrystalline diamond (NCD) coating. Significant difference in critical loads for adhesive failure was observed for MCD and NCD coatings. These loads were 42 N and 20 N for MCD and NCD coatings, respectively. The reason for these two distinctly different adhesive characteristics was attributed to the microstructure of the respective coatings. The surface morphologies at critical failure point and wedge spallation regions of the scratch tracks were completely different for NCD and MCD coatings. Critical point regions were analysed by Raman stress mapping to study the scratch induced residual stresses in the strained diamond flakes and deformed coating of the scratch track. In this respect, high tensile stresses were observed in the regions of critical failure. This behaviour is strongly dependent on magnitude of stress and nature of deformation during the scratch test of NCD and MCD coatings.     

Prediction of coating adhesion loss due to stretching

Polymer coated sheet metals are widely used for part fabrication in industry. To ensure that the manufactured products can meet the service life requirement, the effect of plastic deformation on coating adhesion is a critical concern. This paper presents an investigation of coating adhesion loss in forming polymer-coated sheet metals. A set of experiments were conducted to evaluate the pull-off strength of coatings before and after uniaxial stretching. The experiments show that axial plastic deformation can cause adhesion to deteriorate. An analytical method based on a virtual interface crack model was developed to evaluate the adhesion potential and was used to quantitatively predict the adhesion loss of two polymer coated sheet metals. The prediction results are in good agreement with the experimental measurements. A parametric study was also conducted to investigate the effects of material properties and coating/substrate thickness on adhesion loss. The results of this study can be used to attain better product design and application development for polymer coated sheet metals.     

Adhesion measurement of interfaces between gelatin and poly(ethylene terephthalate) using microscratch technique

A microscratch technique was used to evaluate the adhesion between interfaces of a gelatin coating and poly(ethylene terephthalate) (PET) film. The interface was reinforced by nitrogen plasma treatment on the PET surface and subsequently by heat treatment of each gelatin/PET sample to promote interactions at the interface. In the microscratch test, a normal load controlled conical stylus with 50‐μm radius tip was drawn over the gelatin coating surface under a continuously increasing normal load until failure occurred in the sample. Optical microscopy and depth profiling of the scratch track were used to detect failure and the failure mechanism. The critical normal load (F_c) was defined as when gelatin detached from the PET substrate or when a complete removal or plowing of the gelatin coating on the PET substrate occurred. With increasing plasma treatment time and heating treatment temperature, the F_c for both debonding and coating removal increased, which showed that both failure mechanisms are related to the adhesion. Different thicknesses of the gelatin coatings were also prepared under the same plasma and heat treatment conditions. It was found that the F_c increased with increasing coating thickness. The result demonstrated that both failure mechanisms depended on the plastic deformation of the coating and substrate. The F_c for coating detachment increased linearly with increasing coating thickness whereas the F_c for coating removal increased sharply with increasing thickness. Annealing temperatures ranging from 20 to 80°C exhibited a strong effect on the F_c, which increased with increasing annealing temperature. These results demonstrate that the microscratch technique can be used to access interfacial adhesion and that the F_c is a qualitative parameter for the evaluation of adhesion strengths. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1960–1974, 2006     

Analysis of the Notched Coating Adhesion Test

An analysis of the notched coating adhesion (NCA) test is presented. This simple adhesion test method is appropriate for measuring the interfacial fracture toughness of some classes of coatings and open-faced adhesive bonds. The NCA specimen consists of a single substrate coated with a thin layer of adhesive. The coating is notched to sever the coating and induce sharp interfacial debonds, and the specimen is then loaded in tension. The substrate strain at which coating debonding occurs is recorded and used to determine the critical strain energy release rate. Yielding of the substrate is permitted, and does not significantly affect the calculation of the strain energy release rate. Analytical and finite element analysis are used to quantify the available strain energy release rate for both steady state and laterally-constrained cases. The available strain energy release rate is shown to be quite insensitive to the initial debond length. The specimen geometry results in a mode mix which causes the adhesive to debond along the interface.     

Scratch and wear resistance of hydrophobic CeO2-x coatings synthesized by reactive magnetron sputtering

CeO_2-x coatings were deposited under variable oxygen flow ratios (%f_O2) onto Si substrates by reactive magnetron sputtering. Nanoindentation testing revealed an increase in the hardness, elastic modulus, H/E and H³/E² ratio with increasing oxygen flow ratio, which in turn increased the adhesion and tribological performance of the coatings. Scratch testing yielded the highest critical load (L_C2 = 28.8 N) and CPR_S = 103 for the coating deposited with the highest oxygen flow ratio (57 %f_O2). Cracking events during scratch testing were initiated by tensile forces behind the scratch stylus, which led to the formation of semi-circular ring cracks. As the normal load increased, transverse cracks emerged extending outwards from the scratch track towards the edge causing the exposure of substrate. Beyond L_C2, severe spallation of the CeO_2-x coatings led to coating failure. Furthermore, the specific wear rates of the CeO_2-x coatings were determined to be within the ~10⁻¹⁵ m³/Nm range influenced by three-body abrasive wear. In-depth analyses from scratch and wear data indicates that these coatings possess good adhesion and durability.     

Adhesion of diamond-like carbon films on polymers: an assessment of the validity of the scratch test technique applied to flexible substrates

The validity of the scratch test as a method of assessing the adhesion of diamond-like carbon (DLC) on polymers has been studied. Sheets of 12 μm thick polyethylene terephthalate (PET) and 100 μm thick polypropylene (PP) were adhesively bonded to glass slides in order to perform the scratch tests. The critical load is defined as the load at which tensile cracks occur in the coating homogeneously throughout the scratch. It is shown that the type and the thickness of the adhesive used have an influence on the critical load value. However, the calculated values of the interfacial shear strength do not depend on the adhesive thickness, and qualitative results in agreement with the literature have thus been obtained. The influence of a nitrogen plasma pretreatment on the adhesion of DLC films on PET and PP has been determined by both scratch test and tensile test techniques. The results follow the same trend and show that the scratch test technique is a good tool for semi-quantitative comparisons.