Toughness evaluation of hard coatings and thin films

Enormous progress has been achieved over the past decade in evaluating the toughness of hard coatings and thin films. This paper reviews methodologies developed based on indentation, bending, and microtensile testing. In addition, we discuss a recent development in fracture toughness measurement which involves the application of macrotension to a substrate in order to induce microtension in a patterned thin film.     

Measuring the fracture toughness of ultra-thin films with application to AlTa coatings

An experimental technique is presented for measuring the fracture toughness of brittle thin films. In this technique, long rectangular membranes are fabricated from the film of interest using standard silicon micromachining techniques. A focused ion beam is then used to introduce pre-cracks of different lengths along the centerline of the membranes and the membranes are pressurized until rupture. The fracture stress of the membrane is measured as a function of pre-crack length and the fracture toughness of the film is determined from a simple fracture mechanics analysis. The technique is applicable to a wide range of materials and is especially suited for ultra-thin films. We have demonstrated the experimental procedure for a 150 nm AlTa intermetallic film and obtained a room-temperature fracture toughness of K _1c = 4.44 ± 0.21 MPam^1/2.     

Measurement of fracture toughness of anode used in Solid Oxide Fuel Cell

Reliability prediction and design of multi-layered structure necessitates the knowledge of the mechanical properties of the individual layers, in particular fracture toughness. To measure fracture toughness of typical anode, composed of 60 wt.% NiO and 40 wt.% 3YSZ (60:40 Ni-YSZ) used in Solid Oxide Fuel Cell (SOFC), controlled buckling test was used. A simple set-up was made where a compressive strain was applied on a thin substrate supporting the anode. Both curvature and film strength are calculated from the applied strain, elastic modulus and geometric dimension of the sample. The fracture toughness is calculated to be .     

Indentation-induced subsurface tunneling cracks as a means for evaluating fracture toughness of brittle coatings

When a plate glued to a compliant substrate is subject to indentation, cracks may initiate from its subsurface due to flexure. Upon increasing the load, the damage develops into a set of tunnel radial cracks which propagate stably under a diminishing stress field. This phenomenon is utilized here to extract fracture toughness K _C for brittle materials in the form of thin plates or films. Experiments show that the SIF at the tip of the subsurface radial cracks is well approximated as K ~ P/c ^3/2, where P is the indentation load and c the mean length of the crack fragments. Using a transparent substrate, c can be easily determined after unloading, from which K _C is found. This simple and economic concept is applied to a wide variety of thin ceramic coatings, yielding toughness data consistent with literature values. Because the tip of the tunneling cracks are well removed from the contact site, the method circumvents certain complications encountered in common top-surface radial cracking techniques such as the effect of plastic deformation, residual stresses and crack extension after unloading. Although the present tests are limited to coating thicknesses >150 μm, it is believed that thinner coatings may be studied as well provided that the indenter radius is kept sufficiently small to insure that subsurface radial cracking dominates over all other failure modes.     

Characterization of strain-softening behavior and failure mechanisms of composites under tension and compression

A methodology is presented to directly measure the damage properties and strain softening response of laminated composites by conducting over-height compact tension (OCT) and compact compression (CC) tests. Through the use of digital image correlation (DIC) technique, and analysis of the measured surface displacement/strain data, the strain-softening response of composites is constructed. This method leads to a direct determination of the Mode I translaminar fracture properties with the assumption that the shear stress is negligible around the damage zone and the crack growth occurs in the symmetric opening mode. Using this methodology, and by correlating the observed failure mechanisms with the strain-softening curves, the interaction of failure mechanisms leading to the final failure and also the distinction between the tensile and compressive failure mechanisms can be studied. The effectiveness of the method in accurate identification of the damage parameters is demonstrated through sectioning and deplying techniques. As a consistency check and further verification of the method, the obtained strain-softening curves are fed into a numerical damage mechanics model and successfully used to simulate the detailed response of the very same OCT and CC specimens from which the strain-softening curves were extracted.     

Size effect on fracture toughness of freestanding copper nano-films

We conducted fracture toughness experiments on freestanding copper films with thicknesses ranging from about 800 to 100 nm deposited by electron beam evaporation to elucidate the size effect on fracture toughness in the nano- or submicron-scale. It was found that initially, the crack propagated stably under loading, and then the crack propagation rate rapidly increased, resulting in unstable fracture. The fracture toughness K_C was estimated on the basis of the R-curve concept to be 7.81 ± 1.22 MPa m^1/2 for the 800-nm-thick film, 6.63 ± 1.05 MPa m^1/2 for the 500-nm-thick film and 2.34 ± 0.54 MPa m^1/2 for the 100-nm-thick film. Thus, a clear size effect was observed. The fracture surface suggested that the crack underwent large plastic deformation in the thicker 800-nm and 500-nm films, whereas it propagated with highly localized plastic deformation in the thinner 100-nm film. This size effect in fracture toughness might be related to a transition in deformation and fracture morphology near the crack tip.     

The thickness effect of Bi3.25La0.75Ti3O12 buffer layer in PbZr0.58Ti0.42O3/Bi3.25La0.75Ti3O12 (PZT/BLT) multilayered ferroelectric thin films

A series of PbZr_0.58Ti_0.42O₃ (PZT) thin films with various Bi_3.25La_0.75Ti₃O₁₂ (BLT) buffer layer thicknesses were deposited on Pt/TiO₂/SiO₂/p-Si(100) substrates by RF magnetron sputtering. The X-ray diffraction measurements of PZT film and PZT/BLT multilayered films illustrate that the pure PZT film shows (111) preferential orientation, and the PZT/BLT films show (110) preferential orientation with increasing thickness of the BLT layer. There are no obvious diffraction peaks for the BLT buffer layer in the multilayered films, for interaction effect between the bottom BLT and top PZT films during annealing at the same time. From the surface images of field-emission scanning electron microscope, there are the maximum number of largest-size grains in PZT/BLT(30 nm) film among all the samples. The growth direction and grain size have significant effects on ferroelectric properties of the multilayered films. The fatigue characteristics of PZT and PZT/BLT films suggest that 30-nm-thick BLT is just an effective buffer layer enough to alleviate the accumulation of oxygen vacancies near the PZT/BLT interface. The comparison of these results with that of PZT/Pt/TiO₂/SiO₂/p-Si(100) basic structured film suggests that the buffer layer with an appropriate thickness can improve the ferroelectric properties of multilayered films greatly.     

Fracture toughness measurement of thin films on compliant substrate using controlled buckling test

Thin films and multilayered structures are increasingly used in the industry. One of the important mechanical properties of these thin layers is the fracture toughness, which may be quite different from the known value of the bulk sample due to microstructural difference. In the design towards device flexibility and scratch resistance, for example, fracture toughness is an important parameter of consideration. This work presents a testing scheme using controlled buckling experiment to determine the fracture toughness of brittle thin films prepared on compliant substrates. When the film is under tension, steady-state channelling cracks form in parallel to each other. Critical fracture strain can be calculated by the measuring the displacement of the buckled plate. The fracture toughness can then be obtained with the help of finite element calculation. When the substrate experiences plastic deformation, the energy release rate is increased by the degree of plasticity. Fracture toughness measurement of two types of thin film Cu-Sn intermetallic compounds has been given to illustrate the merits of such a test scheme.     

Fracture behavior under mixed-mode loading of ceramic plasma-sprayed thermal barrier coatings at ambient and elevated temperatures

The fracture behavior under modes I and II loading of ceramic plasma-sprayed thermal barrier coatings was determined in air at 25 and 1316 °C in asymmetric four-point flexure. The mode I fracture toughness was found to be K_Ic = 1.15 ± 0.07 and 0.98 ± 0.13 MPa , respectively, at 25 and 1316 °C. The respective ‘nominal’ mode II fracture toughness values were K_IIc = 0.73 ± 0.10 and 0.65 ± 0.04 MPa . The empirical mixed-mode fracture criterion best described the coatings’ fracture behavior under mixed-mode loading. The angle of crack propagation was in reasonable agreement with the minimum strain energy density criterion.     

Fracture toughness of exponential layer-by-layer polyurethane/poly(acrylic acid) nanocomposite films

This paper characterizes the fracture toughness of layer-by-layer (LBL) manufactured thin films with elastic polyurethane, a tough polymer, and poly(acrylic acid) as a stiffening agent. A single-edge-notch tension (SENT) specimen is used to study mode I crack propagation as a function of applied loading. Experimental results for the full-field time histories of the strain maps in the fracturing film have been analyzed to obtain R-curve parameters for the nanocomposite. In particular, by using the strain maps, details of the traction law are measured. A validated finite strain phenomenological visco-plastic constitutive model is used to characterize the nanocomposite film while a discrete cohesive zone model (DCZM) is implemented to model the fracture behavior. The LBL manufactured nanocomposite is found to display a higher fracture toughness than the unstiffened base polymer.     

Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes,chitosan and cobalt (II) phthalocyanine

The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {Chit/CoTsPc}_n and {Chit-SWCNTs/CoTsPc}_n (n = 1–10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E_1/2 at −0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)]⁵⁻/[CoTsPc(II)]⁴⁻ and CoTsPc(II) to CoTsPc(III), respectively. The {Chit-SWCNTs/CoTsPc}₅ multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the electrode surface.     

Influence of substrate temperature on the materials properties of reactive DC magnetron sputtered Ti/TiN multilayered thin films

Ti/TiN multilayers were deposited by DC reactive magnetron sputtering method using a titanium target and an Ar-N₂ mixture discharge gas. XRD technique was employed to study the structure of the coatings and to observe the variations of structural parameters with substrate temperatures. An increase in grain size with increase of substrate temperature was observed. The components of Ti 2p doublet, related to TiN, TiON and TiO₂, were observed in the core-level spectra of the deposited multilayer films from XPS analysis. A microhardness value of 25.5 GPa was observed for Ti/TiN multilayers prepared at 400 °C. Electrical properties were found to depend on substrate temperature.     

Fracture toughness of polycrystalline tungsten under mode I and mixed mode I/II loading

The fracture toughness of swaged polycrystalline tungsten was tested parallel and perpendicular to the swaging direction and under mixed mode I/mode II loading. The fracture mode is dominated by the microstructure and changed from all-transgranular cleavage in mode I to almost all-intergranular fracture in mode II. The mixed mode results can be related to two common failure criteria, the maximum tensile stress criterion (Maximum σ) and the maximum energy release rate criterion (Maximum G), but the large scatter in the data prohibits a clear distinction between the two criteria. Tests at 77 K show that the polycrystal is significantly tougher than the single crystal at this temperature. This is a consequence of the deflection of the crack into the grain boundaries and the imperfect texture (as compared to a single crystal) of the polycrystalline material.     

Fracture toughness of austempered chilled ductile iron

The structure and properties of ductile iron are highly dependent on the solidification mechanism and chills are used to promote directional solidification to get sound castings. A series of fracture toughness experiments were carried out involving austempered chilled ductile iron containing 3.42% C, 1.8% Si and other alloying elements. By using copper chills of different thickness, the fracture toughness of varying the chill rate was also examined. The fracture toughness tests were carried out using three-point bend specimens, each with a chevron notch, as per ASTM E 399 1990 standards. It was found that austempered chilled ductile iron is highly dependent on the location on the casting from where the test samples are taken and also on the Ni and Mo content of the material. Chill thickness, however, also affects the fracture toughness of the material.     

Fracture toughness of Ti-15Al-8Nb alloy under mixed mode I/III loading

The effect of mixed mode I/III loading on fracture toughness of Ti-15 at.% Al-8 at.% Nb alloy, which undergoes stress-induced martensitic transformation, was investigated for four different grain sizes. The fracture toughness under mixed mode I/III loading was found to be significantly higher than that under mode I loading in all cases. The results were explained on the basis of the stress and strain fields ahead of a mixed mode crack and its influence on the martensitic transformation zone.     

On the Effect of Hydrogen on the Fracture Toughness of Steel

A model is developed to quantify the effect of hydrogen on the critical stress intensity factor or fracture toughness of steels. The stress-assisted hydrogen diffusion model proposed by Liu (1970) is assumed and combined with the elastic stress field around the crack tip for quantifying the hydrogen concentration at the crack tip. Introducing a fracture criterion as the critical hydrogen concentration at a critical distance ahead of the crack tip, this model is successfully applied to the interpretation of hydrogen embrittlement behavior in a piping material. Experimental data at constant temperature were used to validate the model. With further development, the model has the potential to predict fracture toughness values at temperatures other than the test temperature.     

Fracture behavior and toughening mechanism in Zanchor reinforced composites under mode II loading

The mode II interlaminar fracture behavior and the toughening mechanism of Zanchor reinforced composite laminates were investigated by using the End Notched Flexure (ENF) and Interlaminar Shear (ILS) specimens. The ENF test results demonstrated that the Zanchor process was highly effective to improve the mode II fracture toughness of composite laminates, where the fracture toughness increased almost linearly with the Zanchor density. The R-curves of Zanchor composites were roughly divided into the transition and stable regions, where the width of the transition region became larger as the Zanchor density increased. The macroscopic fracture behavior of the Zanchor composites was still brittle under mode II loading like that of the base composite, where the crack tip process zone was estimated to be rather small regardless of the Zanchor density. The ILS test results demonstrated that the square of the normalized shear strength increased linearly with the Zanchor density and agreed quantitatively with the normalized fracture toughness. The wedge effect was supposed to be the dominant toughening mechanism against the mode II fracture, where the entangled fiber bundles partly sustained the shear stress in the vicinity of the crack tip. The entangled fiber bundles played an important role to form the mode II fracture surface, where the microscopic fracture pattern of the entangled fiber bundles was mainly the breakage of the fiber bundles rather than the pull-out or debonding of the fiber bundles.     

Fracture toughness KIC analysis of Co-doped 7YSZ

Abstract

Co-doped samples of 7YSZ with Yb³⁺, Ce⁴⁺ and Nb⁵⁺ having high porosity are subject to Vickers hardness testing. Fracture toughness K_IC values are obtained by measuring linear and non-linear crack geometries. Three separate means are used to calculate the fracture toughness and to investigate the associated trends. It is confirmed that high amounts of retained tetragonal zirconia improve fracture toughness, while elevated amounts of monoclinic zirconia lower overall fracture toughness. The experimental trend for increasing K_IC is Nb:7YSZ<Yb:7YSZ<7YSZ<Ce:7YSZ; however, this trend is qualitative as the Young’s modulus values for different samples are corrected for porosity using an equation that does not generally apply to indentation techniques.