Nonisothermal crystallization kinetics of flame‐sprayed polyamide 1010/nano‐ZrO2 composite coatings

Polyamide1010 (PA1010) and its composite with nanometer‐sized zirconia (PA1010/nano‐ZrO₂) coatings were deposited using a flame spray process. The kinetics of nonisothermal crystallization of PA1010/nano‐ZrO₂ composite coatings was investigated by differential scanning calorimetry (DSC) at various cooling rates. Several different analysis methods were used to describe the process of nonisothermal crystallization. The results showed that the modified Avrami equation and Mo's treatment could describe the nonisothermal crystallization of the composite coatings very well. The nano‐ZrO₂ particles have a remarkable heterogeneous nucleation effect in the PA1010 matrix. The values of halftime and Z_c showed that the crystallization rate increased with increasing cooling rates for both PA1010 and PA1010/nano‐ZrO₂ composite coating, but the crystallization rate of PA1010/nano‐ZrO₂ composite coating was faster than that of PA1010 at given cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

Adaptive Polymeric Coatings with Self‐Reporting and Self‐Healing Dual Functions from Porous Core–Shell Nanostructures

In biological system, early detection and treatment at the same moment is highly required. For synthetic materials, it is demanding to develop materials that possess self‐reporting of early damage and self‐healing simultaneously. This dual function is achieved in this work by introducing an intelligent pH‐responsive coatings based on poly(divinylbenzene)‐graft‐poly(divinylbenzene‐co‐methacrylic acid) (PDVB‐graft‐P(DVB‐co‐AA)) core–shell microspheres as smart components of the polymer coatings for corrosion protection. The key component, synthesized PDVB‐graft‐P(DVB‐co‐AA) core–shell microspheres are porous and pH responsive. The porosity allows for encapsulation of the corrosion inhibitor of benzotriazole and the fluorescent probe, coumarin. Both loading capacities can be up to about 15 wt%. The polymeric coatings doped with the synthesized microspheres can adapt immediately to the varied variation in pH value from the electrochemical corrosion reaction and release active molecules on demand onto the damaged cracks of the coatings on metal surfaces. It leads simultaneously to the dual functions of self‐healing and self‐reporting. The corrosion area can be self‐reported in 6 h, while the substrate can be protected at least for 1 month in 3.5 wt% NaCl solution. These pH‐responsive materials with self‐reporting and self‐healing dual functions are highly expected to have a bright future due to their smart, long‐lasting, recyclable, and multifunctional properties.     

Resistance of 2ZrO2·Y2O3 top coat in thermal/environmental barrier coatings to calcia‐magnesia‐aluminosilicate attack at 1500°C

Internally cooled, hollow SiC‐based ceramic matrix composites (CMCs) components that may replace metallic components in the hot section of future high‐efficiency gas‐turbine engines will require multilayered thermal/environmental barrier coatings (T/EBCs) for insulation and protection. In the T/EBC system, the thermally insulating outermost (top coat) ceramic layer must also provide resistance to attack by molten calcia‐magnesia‐aluminosilicate (CMAS) deposits. The interactions between a potential candidate for top coat made of air‐plasma‐sprayed (APS) 2ZrO₂·Y₂O₃ solid‐solution (ss) ceramic and two different CMASs (sand and fly ash) are investigated at a relevant high temperature of 1500°C. APS 2ZrO₂·Y₂O₃(ss) top coat was found to resist CMAS penetration at 1500°C for 24 hours via reaction products that block CMAS penetration pathways. In situ X‐ray diffraction (XRD) studies have identified the main reaction product to be an Ca‐Y‐Si apatite, and have helped elucidate the proposed mechanism for CMAS attack mitigation. Ex situ electron microscopy and analytical spectroscopy studies have identified the advantageous characteristics of the reaction products in helping the CMAS attack mitigation in the APS 2ZrO₂·Y₂O₃(ss) coating at 1500°C. Finally, the Y³⁺ solubility limit and transport behavior are identified as potential comparative tools for assessing the CMAS resistance ability of top‐coat ceramics.     

Heat‐resistant hydrophobic–oleophobic coatings

Thermally and chemically durable hydrophobic oleophobic coatings, containing different ceramic particles such as SiO₂, SiC, Al₂O₃, which can be alternative instead of Teflon, have been developed and applied on the aluminum substrates by spin‐coating method. Polyimides, which are high‐thermal resistant heteroaromatic polymers, were synthesized, and fluor oligomers were added to these polymers to obtain hydrophobic–oleophobic properties. After coating, Al surface was subjected to Taber‐abrasion, adhesion, corrosion, and thermal tests. The effects of the particle size of ceramic powders, organic matrix, and heat on the coating material were investigated. Coating material was characterized by FTIR spectrophotometer. Surface properties and thermal resistance of the coating materials were investigated by SEM and TGA analyses. After thermal curing, contact angles of these coatings with H₂O and n‐hexadecane were measured. It was observed that coatings like ceramic particles are more resistant against scratch and abrasion than the other coatings. Also, they are harder than coatings, which do not include ceramic particles. It was seen that coatings, containing Fluorolink D10H, have high‐contact angles with water and n‐hexadecane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2386–2392, 2006     

Effect of High‐Temperature Aging on the Fracture Toughness of 40 mol% Ceria‐Stabilized Zirconia

The 40 mol% CeO₂‐stabilized ZrO₂ ceramic was synthesized by the sol‐spray pyrolysis method and aged at 1400°C–1600°C. The effects of high‐temperature aging on its fracture toughness were investigated after heat treatments at 1500°C for 6–150 h in air. Characterization results indicated that the activation energy for grain growth of 40 mol% CeO₂‐stabilized ZrO₂ was 593 ± 47 kJ/mol. The average grain size of this ceramic varied from 1.4 to 5.6 μm within the aging condition of 1500°C for 6–150 h. The Ce‐lean tetragonal phase has a constant tetragonality (ratio of the c‐axis to a‐axis of the crystal lattice) of 1.0178 during the aging process. It was found that the fracture toughness of 40 mol% CeO₂‐stabilized ZrO₂ was determined to be 2.0 ± 0.1 MPa·m^1/2, which did not vary significantly with prolonging aging time. Since no monoclinic zirconia was detected in the regions around the indentation crack‐middle and crack‐tip, the high fracture toughness maintained after high‐temperature aging can be attributed to the remarkable stability of the tetragonal phase in 40 mol% CeO₂‐stabilized ZrO₂ composition.     

Oxygen‐ion conduction in scandia‐stabilized zirconia‐ceria solid electrolyte (xSc2O3–1CeO2–(99−x)ZrO2, 5 ≤ x ≤ 11)

Solid oxide fuel cells (SOFCs) operating at intermediate temperature (500°C‐700°C) provide advantages of better durability, lower cost, and wider target application market. In this work, we have studied Sc₂O₃ (5‐11 mol%) stabilized ZrO₂–CeO₂ as a potential solid electrolyte for application in IT‐SOFCs. Lower Sc₂O₃ doping range than the traditional 11 mol% Sc₂O₃‐stabilized ZrO₂ is an interesting research topic as it could potentially lead to an electrolyte with reduced oxygen vacancy ordering, lower cost, and higher mechanical strength. XRD and Raman spectroscopy was used to study the phase equilibrium in ZrO₂–CeO₂–Sc₂O₃ system and impedance spectroscopy was done to estimate the grain, grain boundary, and total ionic conductivities. Maximum for the grain and grain‐boundary conductivities as well as the tetragonal‐cubic phase boundary was found at 8‐9 Sc₂O₃ mol% in ZrO₂‐1 mol% CeO₂ system. It is suggested that the addition of 1 mol% CeO₂ in the ZrO₂ host lattice has improved the phase stability of high‐conductivity cubic and tetragonal phases at the expense of low‐conductivity t′‐ and β‐phases.     

Phase Evolution of SiO2–Al2O3–ZnO–CaO–ZrO2–TiO2‐Based Glass with Added Y‐PSZ Particles

Yttria partially stabilized zirconia Y‐PSZ/glass‐ceramic composites were prepared by reaction sintering using powder mixtures of a SiO₂–Al₂O₃–ZnO–CaO–ZrO₂–TiO₂‐based glass and yttria partially stabilized zirconia (Y‐PSZ). The glass crystallized during sintering at temperatures of 1173, 1273, and 1373 K to give a glass‐ceramic matrix for high‐temperature protecting coatings. With the increasing firing time, the added zirconia reacted with the base glass and a glass‐ceramic material with dispersed zircon particles was prepared in situ. Furthermore, the added zirconia changed the crystallization behavior of the base glass, affecting the shape, amount, and distribution of zircon in the microstructure. The bipyramid‐like zircon grains with imbedded residual zirconia particles turned out to have two growth mechanisms: the inward growth and the outward growth, and its rapid growth was mainly dominated by the later one. For comparison, the referenced glass‐ceramic was prepared by sintering using exclusive glass granules and its crystallization behavior at 1173–1373 K was examined as well. Scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) were used to characterize the crystallization behavior of the base glass and the phase evolution of the Y‐PSZ/glass‐ceramic composites.     

High catalytic efficiency in liquid‐phase oxidation of 1,4‐dioxane using a Pt/CeO2‐ZrO2‐SnO2/SBA‐16 catalyst

A Pt/CeO₂–ZrO₂–SnO₂/SBA‐16 (SBA‐16: Santa Barbara Amorphous No. 16) catalyst was developed for the efficient removal of 1,4‐dioxane. Because the catalyst showed synergistic action between the high catalytic activity of Pt and the high oxygen release and storage abilities of CeO₂–ZrO₂–SnO₂, high catalytic efficiency in the liquid phase was obtained in an air atmosphere without the supply of any strongly oxidizing additives or photoirradiation. After reaction at 80°C for 4 h, the residual percentage of 1,4‐dioxane reached 31%. Furthermore, the Pt/CeO₂–ZrO₂–SnO₂/SBA‐16 catalyst exhibited high reusability and durability and the rate of net decrease in 1,4‐dioxane reached 44% at 80°C.     

Potassium sodium niobate (KNN)‐based lead‐free piezoelectric ceramic coatings on steel structure by thermal spray method

For the first time, potassium sodium niobate (KNN)‐based lead‐free piezoelectric ceramic coating with strong piezoelectric response was fabricated on stainless steel substrates by thermal spray process, after introducing NiCrAlY and yttria‐stabilized zirconia (YSZ) intermediate layers. A large effective piezoelectric coefficient (d₃₃) of 125 pm/V was obtained with the thermal‐sprayed KNN‐based ceramic coating on the steel substrates. The mechanisms of improving the structure and enhancing the properties of the KNN‐based piezoelectric ceramic coatings by introducing the intermediate layers were analyzed. Ultrasonic transducers were designed and fabricated from the KNN‐based coatings directly formed on a steel plate structure, and the feasibility for generation and detection of ultrasonic waves for structural health monitoring using the thermal‐sprayed lead‐free piezoelectric ceramic coating was demonstrated.     

Effect of CeO2 and Al2O3 contents on Ce‐ZrO2/Al2O3 composites

Effect of CeO₂ and Al₂O₃ contents on phase composition, microstructures, and mechanical properties of Ce–ZrO₂/Al₂O₃ composites was studied. The CeO₂ content in CeO₂–ZrO₂ varied from 7 to 16 mol%, and the Al₂O₃ content in Ce‐ZrO₂/Al₂O₃ composites were 7 and 22 wt%. When CeO₂ content was ≤10 mol%, high Al₂O₃ content contributed to hinder the tetragonal‐to‐monoclinic ZrO₂ phase transformation during cooling and decrease the density of microcracks in the composites. Tetragonal ZrO₂ single‐phase was obtained in the composites with ≥12 mol% CeO₂, regardless of the Al₂O₃ content. Hardness, flexural strength, and toughness were dependent on CeO₂ and Al₂O₃ contents which were related to the microcracks, grain size, and phase transformation. The high flexural strength and toughness of the composites with 7wt% Al₂O₃ could be obtained at an optimum CeO₂ content of 12 mol%, whereas those of the composites with 22 wt% Al₂O₃ could be achieved in the wide CeO₂ content range of 8.5‐12 mol%.     

Cu/Ni‐Loaded CeO2‐ZrO2 Catalyst for the Water‐Gas Shift Reaction: Effects of Loaded Metals and CeO2 Addition

Two different types of metals (Cu and Ni) and the effect of CeO₂ addition to produce a CeO₂‐ZrO₂ co‐supporter were investigated through the water‐gas shift (WGS) reaction. It was found that the WGS activity could be enhanced with CeO₂ addition. At relatively high temperature, Ni‐loaded catalysts exhibited higher CO conversion while Cu‐loaded catalysts demonstrated better performance at low temperatures. The stability and yield of the CO₂ and H₂ products of the Cu catalysts were higher than those of the Ni catalysts. These results may be caused by an irreversible adsorption of CO on Ni and the reverse WGS reaction occurring on the Ni catalysts. In situ diffuse‐reflection infrared Fourier transform spectroscopy data suggests that the WGS mechanism likely proceeded via formate species.     

Study on thermal shock resistance of Sc2O3 and Y2O3 co-stabilized ZrO2 thermal barrier coatings

In order to reveal the effect of Sc₂O₃ and Y₂O₃ co-doping system on the thermal shock resistance of ZrO₂ thermal barrier coatings, Y₂O₃ stabilized ZrO₂ thermal barrier coatings (YSZ TBCs) and Sc₂O₃–Y₂O₃ co-stabilized ZrO₂ thermal barrier coatings (ScYSZ TBCs) were prepared by atmospheric plasma spraying technology. The surface and cross-section micromorphologies of YSZ ceramic coating and ScYSZ ceramic coatings were compared, and their phase composition before and after heat treatment at 1200 °C was analyzed. Whereupon, the thermal shock experiment of the two TBCs at 1100 °C was carried out. The results show that the micromorphologies of YSZ ceramic coating and ScYSZ ceramic coating were not much different, but the porosity of the latter was slightly higher. Before heat treatment, the phase composition of both YSZ ceramic coating and ScYSZ ceramic coating was a single T′ phase. After heat treatment, the phase composition of YSZ ceramic coating was a mixture of M phase, T phase, and C phase, while that of ScYSZ ceramic coating was still a single T′ phase, indicating ScYSZ ceramic coating had better T′ phase stability, which could be attributed to the co-doping system of Sc₂O₃ and Y₂O₃ facilitated the formation of defect clusters. In the thermal shock experiment, the thermal shock life of YSZ TBCs was 310 times, while that of ScYSZ TBCs was 370 times, indicating the latter had better thermal shock resistance. The difference in thermal shock resistance could be attributed to the different sintering resistance of ceramic coatings and the different growth rates of thermally grown oxide in the two TBCs. Furthermore, the thermal shock failure modes of YSZ TBCs and ScYSZ TBCs were different, the former was delamination, while the latter was delamination and shallow spallation.     

Self‐cleaning,titanium dioxide based,multilayer coating fabricated on polymer and glass surfaces

A photocatalytic self‐cleaning titanium dioxide (TiO₂) coating was prepared as a multilayer coating structure by the spin‐coating method. Three substrate materials (two thermoplastics and one ceramic) were used: (1) high‐density polyethylene (HDPE), (2) poly(vinyl chloride), and (3) borosilicate glass (BK7). The multilayer structure consisted of a polyurethane protective layer on the substrate, two layers of photocatalytic TiO₂ on the protective layer, and finally immobilized TiO₂ particles bound in a diluted polyurethane dispersion. Photocatalytically active surfaces were achieved by reactive oxygen‐plasma surface etching of the fabricated coatings. The structure and properties of the coating surfaces were characterized with scanning electron microscopy and contact‐angle measurements. The coatings on HDPE and BK7 were rendered superhydrophilic by an oxygen‐plasma treatment. The photocatalytic activity and self‐cleaning properties of the prepared surfaces were studied with palmitic acid (model soil), the degradation of which was confirmed by contact‐angle measurements and gas chromatography analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Development of Ce‐PSZ‐/Y‐PSZ‐Toughened Alumina Inserts for High‐Speed Machining Steel

The nanocomposite CeO₂/Y₂O₃ partially stabilized zirconia (Ce‐PSZ/Y‐PSZ)‐toughened alumina was prepared by wet chemical simultaneous coprecipitation process. The thermal stability of phases and morphology of powders were characterized by TG‐DTA, FTIR, and FESEM. The microstructure, stabilization of phases and compositional analysis with different mol% CeO₂/Y₂O₃‐doped zirconia in alumina are characterized by FESEM, XRD, and EDAX spectra. Significant improvement in fracture toughness and flexural strength has been observed in 10 vol% of partially stabilized zirconia (2.5 mol% Y₂O₃ in ZrO₂/9 mol% CeO₂ in ZrO₂)‐toughened alumina, which is suitable for high‐speed machining applications.     

Evaluation of Rare‐Earth Modified ZrB2–SiC Ablation Resistance Using an Oxyacetylene Torch

Rare‐earth modified ZrB₂–SiC coatings were prepared via mechanical mixing Sm₂O₃ or Tm₂O₃ powders with spray‐dried ZrB₂, or by chemically doping samarium ions into spray‐dried ZrB₂. In either approach, SiC powders were also added and coatings were fabricated via shrouded air plasma spray. An oxyacetylene torch was utilized to evaluate the coatings under high heat flux conditions for hold times of 30 and 60 s. The resulting phases and microstructures were evaluated as a function of rare‐earth type, modification approach, and ablation time. A brittle m‐ZrO₂ scale was observed in the ZrB₂/SiC‐only coating after ablative tests; during cooling this scale detached from the unreacted coating. In contrast, rare‐earth modified coatings formed a protective oxide scale consisting primarily of either Sm_0.2Zr_0.8O_1.9 or Tm_0.2Zr_0.8O_1.9, along with small amount of m‐ZrO₂. These rare‐earth oxide scales displayed high thermal stability and remained adhered to the unreacted coating during heating and cooling, offering additional oxidation protection.     

Effect of CMAS Deposits on MOCVD Coatings in the System Y2O3–ZrO2: Phase Relationships

Three metal‐organic chemical vapor deposition (MOCVD) coatings (ZrO₂, Y₂O₃·ZrO₂, Y₂O₃) were studied in contact with model CMAS to investigate the microstructural evolution and phase formation. The MOCVD coatings were covered with CMAS powder deposits and annealed for 1 h at 1250°C, respectively. The ZrO₂ coating was completely infiltrated by CMAS, whereas the yttria containing coatings show a higher resistance against CMAS infiltration. This is explained by the formation of a continuous oxyapatite layer in the reaction zone of the coating and the CMAS deposit. The Y₂O₃·ZrO₂ coating shows the best infiltration resistance despite the fact that the Y₂O₃–CMAS sample is the only completely crystallized. As crystallization products, oxyapatite, melilite, anorthite as well as new garnets bearing all available cations were formed. The garnet phase was confirmed by XRD and TEM. EDS measurements were used to calculate structural formula A₃B₂T₃O₁₂ (A = Ca, Y, Zr; B = Mg, Al; T = Al, Si).     

Properties and microstructural aspects of TiO2‐doped sintered Alumina‐Zirconia composite ceramics

The effect of titania content on the densification, the phase transformation, the microstructures, and mechanical properties of 50 wt% Al₂O₃‐50 wt% ZrO₂ (12 mol% CeO₂) was evaluated. Ceramic composites with different TiO₂ content (0.27, 5, 10 wt%) were prepared by pressureless sintering at low temperature (1400°C) for 2 hours in air. Dense ceramic was obtained by adding 5 wt% of TiO₂ loading to improved mechanical properties. The microstructure analysis provided lots of information about solid‐state reactivity in alumina‐zirconia‐titania ternary system. The content of TiO₂ strongly affected the phases evolution and the grain growth during sintering. Furthermore, a significant effect on mechanical properties and fracture behavior was also observed.     

Performance of mix‐impregnated CeO2‐Ni/YSZ Anodes for Direct Oxidation of Methane in Solid Oxide Fuel Cells

CeO₂‐Ni/YSZ anodes for methane direct oxidation were prepared by the vacuum mix‐impregnation method. By this method, NiO and CeO₂ are obtained from nitrate decomposition and high temperature sintering is avoided, which is different from the preparation of conventional Ni‐yttria‐stabilised zirconia(YSZ) anodes. Impregnating CeO₂ into the anode can improve the cell performance, especially, when CH₄ is used as fuel_. The investigation indicated that CeO₂‐Ni/YSZ anodes calcined at higher temperature exhibited better stability than those calcined at lower temperature. Under the testing temperature of 1,073 K, the anode calcined at 1,073 K exhibited the best performance. The maximum power density of a cell with a 10 wt.‐%CeO₂‐25 wt.‐%Ni anode calcined at 1,073 K reached 480 mW cm^–2 after running on CH₄ for 5 h. At the same time, high discharge current favoured cell operation on CH₄ when using these anodes. No obvious carbon was found on the CeO₂‐Ni anode after testing in CH₄ as revealed from SEM and corresponding linear EDS analysis. In addition, cell performance decreased at the beginning of discharge testing which was attributed to the anode microstructure change observed with SEM.     

Modified thick thermal barrier coatings: microstructural characterization

Thick thermal barrier coatings were modified with laser glazing and phosphate based sealing treatments. Surface porosity of the sealed coatings decreased significantly in all cases. Structural analysis showed a strong preferred crystal orientation of the t′ZrO₂ phase in direction [002] in laser-glazed 25CeO₂–2.5Y₂O₃–ZrO₂ coating. In laser-glazed 22MgO–ZrO₂ coating the major phase was rhombohedral Mg₂Zr₅O₁₂. In phosphate sealed 8Y₂O₃–ZrO₂ coating the strengthening mechanism was identified as adhesive binding without chemical bonding. Coating microstructures were determined by scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy and optical microscopy. Coatings were also characterized by X-ray diffraction, microhardness and porosity.