Microstructural,mechanical and thermal shock properties of triple-layer TBCs with different thicknesses of bond coat and ceramic top coat deposited onto polyimide matrix composite

In this study, a triple-layer thermal barrier coating (TBC) of Cu-6Sn/NiCrAlY/YSZ was deposited onto a carbon-fiber reinforced polyimide matrix composite. Effects of different thicknesses of YSZ ceramic top coat and NiCrAlY intermediate layer on microstructural, mechanical and thermal shock properties of the coated samples were examined. The results revealed that the TBC systems with up to 300 µm top coat thicknesses have clean and adhesive coating/substrate interfaces whereas cracks exist along coating/substrate interface of the TBC system with 400 µm thick YSZ. Tensile adhesion test (TAT) indicated that adhesion strength values of the coated samples are inversely proportional to the ceramic top coat thickness. Contrarily, thermal shock resistance of the coated samples enhanced with increase in thickness of the ceramic coating. Investigation of the TBCs with different thicknesses of NiCrAlY and 300 µm thick YSZ layers revealed that the TBC system with 100 µm thick NiCrAlY layer exhibited the best adhesion strength and thermal shock resistance. It was inferred that thermal mismatch stresses and oxidation of the bond coats were the main factors causing failure in the thermal shock test.     

Characterisation of the microstructure and thermal properties of Nd2Zr2O7 and Nd2Zr2O7/YSZ thermal barrier coatings

The microstructure of following thermal barrier coatings (TBC) was characterised in this paper: monolayer coatings Nd₂Zr₂O₇ and 8YSZ; a double ceramic layered (DCL) coating. Coatings were characterised by thicknesses that did not exceed 300 μm and porosities of approx. 5%. The chemical and phase composition analysis of the DCL layers revealed an external Nd₂Zr₂O₇ ceramic layer approx. 80 μm thick, a transitional zone approx. 120 μm thick and an internal 8YSZ layer 100 μm thick. For the case of the monolayer coating, the Nd₂Zr₂O₇ pyrochlore phase was the only one-phase component. The surface topography of both TBC systems was typical for plasma sprayed coatings, and compressive stress state had a value of approx. 5–10 MPa. Measurements of the thermal parameters, i.e., thermal diffusivity, point to considerably better insulative properties for both new types of layers when compared to the standard 8YSZ layers.     

Effect of interface roughness and coating thickness on interfacial shear mechanical properties of EB-PVD yttria-partially stabilized zirconia thermal barrier coating systems

The effect of interface roughness and thickness of thermal barrier coating (TBC) on the interfacial shear mechanical properties of electron beam-physical vapor deposited (EB-PVD)-TBC was examined using as-sprayed and polished bond coats (BC) 200 μm and 500 μm TBC thickness systems, by using a barb test method. The residual compressive stress in the TBC layer from the interface to the top surface was measured, by using Raman spectroscopy. The interface toughness related to the interface roughness and the thickness of the TBC. The interface toughness was larger for the BC as-sprayed TBC system than for the BC polished TBC system. The delamination of the TBC propagated within the TBC layer adjacent to the interface for the BC as-sprayed TBC; for the BC polished TBC, this occurred at the interface between the TGO and the BC. Moreover, the interface toughness was larger in the 500 μm thickness TBC than in the 200 μm thickness TBC. The relation of interface toughness to interface roughness and thickness of the TBC was associated with the interface residual compressive stress and with the interface sliding friction during the delamination of TBC.     

Tailoring the EB-PVD columnar microstructure to mitigate the infiltration of CMAS in 7YSZ thermal barrier coatings

The CMAS associated degradation of 7YSZ TBC layers is one of the serious problems in the aero engines that operate in dusty environments. CMAS infiltrates into TBC at high temperatures and stiffens the TBC which ultimately loses its strain tolerance and gets delaminated. The EB-PVD technique is used to coat TBCs exhibiting a columnar microstructure on parts such as blades and on vanes. By varying the EB-PVD process parameters, columnar morphology and porosity of the 7YSZ coating is changed and its effect on the CMAS infiltration behaviour is studied in detail. Two different TBC pore geometries were created and infiltration experiments were carried out at 1250 °C and 1225 °C for different time intervals. The 7YSZ coating with more ‘feathery’ features has resulted in higher CMAS resistance by at least by a factor of 2 than its less ‘feathery’ counterpart. These results are explained on the basis of a proposed physical model.     

Influences of interface morphology and thermally grown oxide thickness on residual stress distribution in thermal barrier coating system

Calculation of residual stress with finite element method is a basic work in failure mechanism investigation in thermal barrier coating (TBC) system because the residual stress is main driving force for crack nucleation and propagation. In this work, a complicated cosine curve with gradually increasing amplitude was used to simulate interface morphologies between layers so as to study the residual stress behavior during the cooling process in air plasma spraying TBC system by finite element method. The substrate, thermally grown oxide (TGO) and top coat (TC) are considered to be elastic and bond coat (BC) elastic-perfectly plastic. The material properties are all temperature dependent. The stress result comparison between models with and without substrate shows the effect of substrate on the residual stress distribution around layers interfaces should not be ignored as the substrate influences the value of normal residual stress as well as the stress distribution along undulating interfaces. Then the model with substrate was used to study the residual stress evolution along interfaces during cooling down from the temperature of 1000 °C to room temperature. The influences of the thickness of TGO and the amplitude and wavelength of interface on the residual stress distributions near interfaces were considered. The results show that these influences are very complicated. Meanwhile, it's found that the hybrid roughness parameter containing information for height and spacing is more suitable to describe the interface complicacy. The results facilitate understanding the failure mechanism relevant to interface morphology and TGO thickness.     

Plasma spray deposition of tri-layer environmental barrier coatings

An air plasma spray process has been used to deposit tri-layer environmental barrier coatings consisting of a silicon bond coat, a mullite inter-diffusion barrier, and a Yb₂SiO₅ top coat on SiC substrates. Solidified droplets in as-deposited Yb₂SiO₅ and mullite layers were discovered to be depleted in silicon. This led to the formation of an Yb₂SiO₅ + Yb₂O₃ two-phase top coat and 2:1 mullite (2Al₂O₃*SiO₂) coat deposited from 3:2 mullite powder. The compositions were consistent with preferential silicon evaporation during transient plasma heating; a consequence of the high vapor pressure of silicon species at plasma temperatures. Annealing at 1300 °C resulted in internal bond coat oxidation of pore and splat surfaces, precipitation of Yb₂O₃ in the top coat, and transformation of 2:1 mullite to 3:2 mullite + Al₂O₃. Mud-cracks were found in the Yb₂SiO₅ layer and in precipitated Al₂O₃ due to the thermal expansion mismatch between these coating phases and the substrate.     

Hardmetal woodcutting tool tips coated with tetrahedral amorphous carbon

Woodcutting tools with hardmetal (WC–Co) tool tips were coated with a high-quality (80% sp³ bonding fraction) tetrahedral amorphous carbon (ta-C) film. The coatings were produced by filtered cathodic vacuum-arc (FCVA) deposition. The problem with poor adhesion between the ta-C film and cobalt was solved by using an intermediate chromium layer structure. The adhesion was tested with a conventional scratch tester. In the case of a 1.2 μm thick ta-C film with intermediate layer structure the critical load value was 31.6 N; without the intermediate layer it was 16.2 N. The lifetime of the ta-C-coated woodcutting tool was tested under normal production conditions with a computer numerical control (CNC) woodcutting machine. The lifetime of the woodcutting tool tip improved by a factor of three in the case of a 2.1 μm thick multilayer (ta-C/Cr) film coating and by a factor of 1.5 in the case of a 1.0 μm thick ta-C film coating with an 0.5 μm thick intermediate chromium layer.     

Effect of diamond surface orientation on the thermal boundary conductance between diamond and aluminum

[100] and [111] oriented diamond substrates were treated using Ar:H and Ar:O plasma treatments, and 1:1 HNO₃:H₂SO₄ heated at 200 °C. Subsequent to these treatments, an aluminum layer was either evaporated or sputteredon the substrates. The thermal boundary conductance (TBC) as well as the interfacial acoustical reflection coefficient between this layer and the diamond substrate was then measured using a Time Domain ThermoReflectance (TDTR) experiment. For the Ar:H plasma treated surfaces the [111] oriented faces exhibited conductances 40% lower than the [100] oriented ones with the lowest measured TBC at 32 ± 5 MWm^− 2 K^− 1. The treatments that led to oxygen-terminated diamond surfaces (extiti.e. acid or Ar:O plasma treatments) showed no TBC anisotropy and the highest measured value was 230 ± 25 MWm^− 2 K^− 1 for samples treated with Ar:O plasma with a sputtered Al layer on top. Sputtered layers on oxygen-terminated surfaces showed systematically higher TBC than their evaporated counterparts. The interfacial acoustic reflection coefficient correlated qualitatively with TBC when comparing samples with the same type of surface terminations (O or H) but this correlation failed when comparing H and O terminated interfaces with each other.     

Mechanisms governing the thermal shock and tensile fracture of PS-PVD 7YSZ TBC

Thermal barrier coating (TBC) system including NiCoCrAlYTa metallic bond coating and 7YSZ (7 wt%Y₂O₃-ZrO₂) ceramic top coating was deposited on nickel-based superalloy by plasma spray-physical vapor deposition (PS-PVD). Thermal shock property of 7YSZ TBC was characterized by water-quenching test at 1100 ℃ and its failure behaviors were investigated in detail. Besides, tensile test was performed for TBC sample and its cross-sectional fracture microstructure was studied as well. The results showed that after water-quenching test lots of pitting spallation took place in TBC surface, but no obvious microcracks were observed. Additionally, the tensile test indicated that fracture occurred in 7YSZ coating near the interface of ceramic-bond coating. After conduction of water-quenching and tensile testing, a lot of spherical particles and nano-sized agglomerated clusters were observed in the quasi-columnar structured 7YSZ coating. These lead to the formation of weak inter-column bonding and the failure of PS-PVD 7YSZ TBC. Moreover, in order to better understand the failure process, a deposition mechanism of coating was proposed.     

An evaluation of plasma-sprayed coatings based on Al2O3 and Al2O3–13 wt.% TiO2 with bond coat on pure titanium substrate

In this study, the effects of bond coat on the properties of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ coatings, which is plasma sprayed onto a commercial pure titanium substrate with and without Ni–5 wt.% Al (METCO 450 NS) as bond coating layer were investigated in terms of microhardness, bonding strength and surface roughness. Optical and scanning electron microscopy (SEM) examinations revealed that there is a uniform coating layer with no spalling and delamination. However, there is a little amount of porosity. The results indicated that the application of bond coat layer in the plasma spraying of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ on pure titanium substrate has increased the hardness and bonding strength of coatings. While the adhesive bonding is dominant without bond coat, the cohesive bonding is dominant with the application of the bond coating layer. It has been observed that percentage of cohesion strength was about three times higher than that of adhesion strength.     

A study of damage evolution in high purity nano TBCs during thermal cycling: A fracture mechanics based modelling approach

This work concerns the study of damage evolution in a newly developed high purity nano 8YSZ thermal barrier coating during thermal cyclic fatigue tests (TCF). TCF tests were conducted between 100 °C–1100 °C with a hold time of 1 h at 1100 °C, first till failure and later for interrupted tests. Cross section analysis along the diameter of the interrupted test samples revealed a mixed-type failure and that the most of the damage occurred towards the end of the coating’s life. To understand the most likely crack growth mechanism leading to failure, different crack growth paths have been modelled using finite element analysis. Crack growing from an existing defect in the top coat towards the top coat/TGO interface has been identified as the most likely mechanism. Estimated damage by the model could predict the rapid increase in the damage towards the end of the coating’s life.     

Processing of graded anode-supported micro-tubular SOFCs based on samaria-doped ceria via gel-casting and spray-coating

A simple gel-casting method was successfully combined with the spray-coating technique to manufacture graded anode-supported micro-tubular solid oxide fuel cells (MT-SOFCs) based on samaria-doped ceria (SDC) as an electrolyte. Micro-tubular anodes were shaped by a gel-casting method based on a new and simple forming technique that operates as a syringe. The aqueous slurry formulation of the NiO–SDC substrate using agarose as a gelling agent, and the effect of spray-coating parameters used to deposit the anode functional layers (AFLs) and electrolyte were investigated. Furthermore, pre-sintering temperature of anode substrates was systematically studied to avoid the anode–electrolyte delamination and obtain a dense electrolyte without cracks, after co-sintering process at 1450 °C. Despite the high shrinkage of substrate (～70%), an anode porosity of ～37% was achieved. MT-SOFCs with ～2.5 mm of outer diameter, 370 μm thick substrate, 20 μm thick AFLs and 15 μm thick electrolyte were successfully obtained. The use of AFLs with 30:70 and 50:50 wt% NiO–SDC allowed to obtain a continuous gradation of composition and porosity in the anode–electrolyte interface.     

Evaluation of the bond strength of different bonding agents to porcelain and metal alloy

This study was carried out with the purpose of testing the bond strength of different bonding agents bonded to different substrates.Substrates consisted of cylindrical specimens of three different materials: porcelain, metal, and a porcelain–metal combination. Specimens were all 10 mm in diameter and 4 mm thick. Surfaces to be bonded were air-abraded with Al₂O₃ and cleaned ultrasonically in distilled water for 10 min. After the preparation of the surface was complete, three different bonding agents were applied to the central region of the substrates. Composite resin of a 3.5 mm diameter and 2 mm thick was applied. All specimens were thermocycled between 5 and 55 °C for 200 cycles with a 30-s dwell time. After thermocycling, specimens were stored at 37 °C in distilled water for an additional 7 days before being subjected to a shear load. Shear testing was conducted Hounsfield test machine.The univariate analysis of variance and the Duncan multiple comparison test were used for statistical assessment. It was found that both type of bonding agents and of substrate led to statistically significant differences in bond strength (p<0.01).It was found that the highest bond strength was produced by Clearfil and on pure alloy substrate (33.36 MPa) and the lowest bond strength in Single Bond and porcelain–alloy substrate (4.25 MPa).     

Electrical fatigue behavior of lead zirconate titanate ceramic under elevated temperatures

The electrical fatigue behavior of lead zirconate titanate (PZT) ceramics is investigated under different temperatures. A bipolar triangular electric field with the amplitude of ±1.5 kV/mm and the frequency of 50 Hz is applied to samples up to 1 × 10⁶ cycles. The fatigue rate is found to be temperature dependent, and the fatigue degradation is represented by the loss of remnant polarization, dielectric constant, and piezoelectric constant increased with loading cycle numbers. The degradation, involving surface damage and crack propagation, is more pronounced in samples cycled at lower temperatures, and increases with increasing number of cycles. The temperature effect on fatigue degradation of the properties is described based on the field shielding effect caused by surface damage and fatigue-induced cracks. The effect is more dominant in case of higher cycling numbers and lower temperature fatigue due to higher strain mismatch between switchable and non-switchable domains. Moreover, Raman spectroscopy is used to determine the influence of fatigue on the ferroelectric domains in different areas of the specimens.     

UV-polymerisable,phosphorus-containing,flame-retardant surface coatings for glass fibre-reinforced epoxy composites

A vinyl phosphonic acid based flame retardant coating has been applied on the surface of a glass-fibre reinforced epoxy (GRE) composite substrate using a UV polymerisation technique. On exposure to heat the poly (vinyl phosphonic acid) (PVPA) coating thus obtained, intumesces and acts as a thermal insulator, providing active fire protection to the composite structure. Samples with ∼300 and 500 μm thick coatings were prepared. The fire performance of the coated GRE composite was studied by cone calorimetry at 35 and 50 kW/m² heat fluxes. While the sample with ∼500 μm thick coating did not ignite at both heat fluxes, the one with the ∼300 μm thick coating ignited at 50 kW/m², however the time-to-ignition was delayed from 60 s in the uncoated sample to 195 s and the peak heat release rate reduced from 572 kW/m² to 86 kW/m². The coatings did not peel off when subjected to a tape pull test and resisted cracking/debonding during an impact drop test of up to 5 J energy. However, the coatings are hydrophilic, showing significant mass loss in a water soak test. The improvement of the hydrophobicity of these coatings is a focus of our future research.     

Characterization of silicon carbide joints fabricated using SiC particulate-reinforced Ag–Cu–Ti alloys

CVD silicon carbide was brazed to itself using two Ag–Cu–Ti braze alloys reinforced with SiC particulates to control braze thermal expansion and enhance joint strength. Powders of the braze alloys, Ticusil (composition in wt%: Ag–26.7Cu–4.5Ti, T_L: 900 °C) and Cusil-ABA (Ag–35.3Cu–1.75Ti, T_L: 815 °C) were pre-mixed with 5, 10 and 15 wt% SiC particulates (～20–30 μm) using glycerin to create braze pastes that were applied to the surfaces to be joined. Joints were vacuum brazed and examined using optical microscopy (OM), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) and the Knoop hardness test. The SiC particles were randomly distributed in the braze matrix and bonded to it via reaction with the titanium from the braze alloy. Titanium together with Si and C segregated at the particle/braze interface, and promoted nucleation and precipitation of the Cu-rich secondary phase on particle surfaces. The Si–Ti–C-rich reaction layers also formed at the interface between CVD SiC substrate and the braze alloy. The loss of Ti in the reaction with SiC particulates did not impair either the bond quality or the thickness of the reaction layer on the CVD SiC substrate. Microhardness measurements showed that the dispersed SiC particulates lowered the braze hardness by depleting the braze matrix of Ti. Theoretical calculations indicated the CTE of the braze to decrease by nearly 45–60% with the incorporation of about 45 vol% SiC.     

Electron beam physical vapour deposition and mechanical properties of c-ZrO2-ZTA-coatings on alloy 617 substrates

Multilayered zirconia toughened alumina (ZTA) and c-zirconia coatings were prepared using electron beam physical vapour deposition (EB-PVD). Characterizations of the morphology and chemical composition of the deposited coatings were performed using scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). Scratch resistance, nano-indentation and bending strength were used for the evaluation of the mechanical properties. X-ray diffraction of the top ceramic TBC surface showed that it consists entirely of cubic ZrO₂ phase. The energy-dispersive X-ray spectroscopy analysis (EDS) showed that α-Al₂O₃ is the only oxide phase present at the interface, while SEM indicated the presence of columnar c-ZrO₂ as the only phase of the top coat. Delamination over a large region was observed in the case of double layer (ZTA) coating. In contrast, the multilayered (ZTA1 + ZTA2 + c-Z) coating showed neither delamination nor cracking. The hardness and scratch measurements showed that the top coat c-ZrO₂ layer is harder than the ZTA layers. The thermal conductivity of the multilayer coatings was estimated using the theoretical density and thermal conductivity values of zirconia toughened alumina (ZTA) and cubic-zirconia (c-ZrO₂) together with their experimentally measured data.     

Electrolytic deposition of fluorine-doped hydroxyapatite/ZrO2 films on titanium for biomedical applications

A novel method of electrolytic fluorine-doped hydroxyapatite/ZrO₂ double-layer coating was conducted on medical titanium in ZrO(NO₃)₂ aqueous solution and subsequently in the mixed solution of Ca(NO₃)₂, NH₄H₂PO₄ and NaF. The microstructure, phase composition, bond strength, dissolution rate and corrosion resistance of the films were studied. Results revealed that the additions of F^? reduced the crystallite and increased the crystallinity of hydroxyapatite, structure of apatite was changed from micro-petal-like crystals to nano-needle-like crystals, which aligned vertically to the substrate. The approximately 10 μm thick layers was much denser and uniform. Addition of ZrO₂ buffer layer could improve the bond strength between the fluorine-doped hydroxyapatite layer and the substrate. The bond strength of the double-layer coating was found to be significantly higher than that of pure hydroxyapatite coating even after soaking in normal saline for two weeks. In physiological solution, the double-layer coating showed lower dissolution rate and stronger corrosion resistance than pure hydroxyapatite coating.     

Effect of functionally graded structure design on durability and thermal insulation capacity of plasma-sprayed thick thermal barrier coating

This paper aimed to design and optimize the structure of a thick thermal barrier coating by adding graded layers to achieve a balance between high thermal insulation capacity and durability. To this end, conventional TBC, conventional TTBC, and functionally graded TTBCs were deposited on the superalloy substrate by air plasma spraying. To determine the quality of the bond strength of the coatings, the bonding strength was measured. The durability of coatings was evaluated by isothermal oxidation and thermal shock tests. Then, at a temperature of 1000 °C, the thermal insulation capacity of the coatings was carried out. The microstructure of the coatings was characterized by a scanning electron microscope. The results showed that the thickness of the TGO layer formed on the bond coat in the conventional TBC and TTBC under the oxidation test at 1000 °C after 150 h was 2.79 and 2.11 μm, respectively, whereas, in the functionally graded TTBC samples, no continuous TGO layer was observed as a result of internal oxidation. The functionally graded TTBC presented higher durability than conventional TTBC due to improved bonding strength, thermal shock resistance, and the lack of a TGO layer at the bond/top coat interface. Also, the thermal insulation capacity of the functionally graded TTBC (with 1000 μm thickness of YSZ coating) was better than TTBC.     

Thermal shock behavior of 8YSZ and double-ceramic-layer La2Zr2O7/8YSZ thermal barrier coatings fabricated by atmospheric plasma spraying

The single-ceramic-layer (SCL) 8YSZ (conventional and nanostructured 8YSZ) and double-ceramic-layer (DCL) La₂Zr₂O₇ (LZ)/8YSZ thermal barrier coatings (TBCs) were fabricated by plasma spraying on nickel-based superalloy substrates with NiCrAlY as the bond coat. The thermal shock behavior of the three as-sprayed TBCs at 1000 °C and 1200 °C was investigated. The results indicate that the thermal cycling lifetime of LZ/8YSZ TBCs is longer than that of SCL 8YSZ TBCs due to the fact that the DCL LZ/8YSZ TBCs further enhance the thermal insulation effect, improve the sintering resistance ability and relieve the thermal mismatch between the ceramic layer and the metallic layer at high temperature. The nanostructured 8YSZ has higher thermal shock resistance ability than that of the conventional 8YSZ TBC which is attributed to the lower tensile stress in plane and higher fracture toughness of the nanostructured 8YSZ layer. The pre-existed cracks in the surface propagate toward the interface vertically under the thermal activation. The nucleation and growth of the horizontal crack along the interface eventually lead to the failure of the coating. The crack propagation modes have been established, and the failure patterns of the three as-sprayed coatings during thermal shock have been discussed in detail.