Microstructure of oxides in thermal barrier coatings grown under dry/humid atmosphere

The microstructure of thermally grown oxide (TGO) in thermal barrier coatings (TBCs) oxidized under dry/humid atmosphere at 1100 °C has been characterized by transmission electron microscopy. A thin and continuous oxide layer is formed in the as-deposited TBCs produced by electron beam physical vapor deposition. The TGO formed in dry atmosphere consists of an outer layer of fine α-alumina, zirconia grains and an inner layer of columnar α-alumina grains. However, a small amount of spinel is observed in the TGO under humid atmosphere. The presence of water vapour promotes the formation of spinel.     

Characterization of reactively sputtered permeation barrier materials on polymer substrates

Transparent permeation barrier layers are not only used for food packaging but are also needed to encapsulate flexible electronic devices. Magnetron sputtering allows the deposition of high quality oxide barrier layers with a low water vapor and oxygen permeation. This paper compares different metal oxide layers which are deposited onto a polyethylene terephthalate (PET) film using a reactive dual magnetron sputtering process. The oxides of aluminum, silicon, titanium, zinc and a zinc-tin alloy are compared regarding their permeation barrier, structural and surface properties to determine the relationship between the layer structure and the gas permeation. Thereby, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology and surface structure of the layers and X-ray diffraction analysis (XRD) was used to determine the solid state phase.Cross-section images taken with SEM show a very compact structure for both aluminum oxide and zinc-tin oxide layers. These materials also have the lowest water vapor permeation compared to all other materials. Zinc oxide and titanium oxide layers both exhibit a columnar structure. Zinc oxide is polycrystalline and has a surprising low water vapor and oxygen permeation. In contrast to that the amorphous titanium oxide layers show a high water vapor and oxygen permeation which is not decreasing with an increasing layer thickness above 40 nm.     

Stability of Y-Ti-O nanoparticles during laser deposition of oxide dispersion strengthened steel powder

This study investigated the feasibility of a direct energy deposition process for fabrication of oxide dispersion strengthened steel cladding. The effect of the laser working power and scan speed on the microstructural stability of oxide nanoparticles in the deposition layer was examined. Y-Ti-O type oxide nanoparticles with a mean diameter of 45 nm were successfully dispersed by the laser deposition process. The laser working power significantly affected nanoparticle size and number density. A high laser power with a low scan speed seriously induced particle coarsening and agglomeration. Compared with bulk oxide dispersion strengthened steel, the hardness of the laser deposition layer was much lower because of a relatively coarse particle and grain size. Formation mechanism of nanoparticles during laser deposition was discussed.     

ALD沉积HfO_2薄膜生长行为及其调控

采用原子层沉积(ALD)的方法,选择四二乙基氨基铪(TDEAH)和水作为反应前驱体,在p型(100)单晶硅衬底上制备了HfO_2高介电质薄膜。系统研究了前驱体流量、反应气压、反应温度等工艺参数对HfO_2薄膜生长质量的影响。通过工艺调控,发现存在两种薄膜生长模式:类CVD(化学气相沉积)生长模式和ALD生长模式。发现薄膜的生长模式主要依赖于制备工艺参量:脉冲参量M和冲洗参量Q,通过优化工艺参数,可实现薄膜生长由类CVD生长模式向ALD生长模式的转变,并获得了0.1 nm/周次的最优薄膜生长速率。同时,薄膜微结构与表面形貌的表征结果表明:薄膜的非晶晶态转变受温度和膜厚两个因素共同控制。     

热壁CVD制备铂薄膜的沉积室内壁材料选择研究

选择合适的沉积室内壁材料是热壁化学气相沉积制备Pt薄膜过程中降低前驱体在沉积室内壁上大量消耗,进而保证沉积室内Pt前驱体分压的关键。本研究对比了Pt在镍基高温合金,备选沉积室内壁材料——有氧化层的Cu以及紫铜表面的沉积的难易程度,发现在有氧化层的Cu的表面Pt薄膜很难沉积,因此当镍基高温合金为沉积基体时有氧化层的Cu可以作为热壁CVD的沉积室内壁衬底材料,但是只能一次性使用。     

Bonding mechanism and interface characterisation during dissimilar friction stir welding of an aluminium/polymer bi-material joint

In the present study, detailed microstructural characterisation of a friction-stir-welded joint between AA5059 alloy and high-density polyethylene was carried out using field-emission scanning and high-resolution-transmission electron microscopy analysis. The structural features indicate large numbers of macro-, micro- and nano-mechanical interlocks between the Al-fragments and melted/re-solidified polymer matrix at the stir zone of the joint, with a 30-nm thick semi-crystalline aluminium structure layer elevated in levels of O, and traces of C at the interface. An ultrafine-grained structure with an average cell size of <100?nm was formed for the embedded Al-alloy fragments in the polymer matrix, as a result of low-temperature severe plastic deformation during friction-stir welding process. The interfacial chemical reactions assisted by generation of nano-scale pores inside the metal surface at the interface and secondary Van der Waals bonding are suggested as the main joining mechanisms, leading to significant improvements in the mechanical properties.     

Inhibition of molten droplet deposition by substrate surface hydroxides

Nickel or nickel-chrome molten droplets were plasma-sprayed onto aluminium substrates which were hydrothermally-treated to grow thick layers of hydroxide and oxide on the surface. The boiled samples were subsequently thermally-treated at different temperature conditions to test whether removal of water vapour released from the dehydration of the surface hydroxide affects the splat deposition. It was observed that there was a complete absence of splat deposition on substrates held at room temperature, regardless of the roughness of their surfaces. The absence of splat deposition on these surfaces was also independent of the spraying parameters and particle properties. In contrast, significant splat deposition was found on the substrates held at 350 °C during spraying. The obvious difference in splat deposition between non-heated and heated samples can be explained by their significant variation proportion of hydroxide in the substrate surface layers. It was also found that the oxide layers on the substrate surface remained intact across the entire interface between the splat and the substrate.     

The relationship between the corrosion resistance and impurity content of aluminium oxide layers

In the last few years there has been an increased production and application of aluminium foil of under 20 μm thickness all over the world. Household foil is often stored in a wet environment, where the surface is only protected against corrosion by an aluminium oxide layer produced during manufacturing. In this study it has been shown that the aluminium-water vapour reaction is greatly affected by the composition and structure of the amorphous oxide layer on the surface and this depends on the composition of base metal and on the annealing of the foil. The incubation period of aluminium hydroxide nucleation is shortened and its growth rate accelerated by alkali and alkaline earth metal cations incorporated in the oxide layer. In particular the corrosion resistance is decreased by the presence of alkali (Li) and alkaline earth metal (Mg) cations in the oxide layers.     

Restoring the tensile properties of PVD-TiN coated Al 7075-T6 using a post heat treatment

In this work, a post heat treatment cycle is proposed with the aim to recover the lost tensile properties of aluminium alloy 7075-T6 coated with a 3 μm thick titanium nitride (TiN) film by using a physical vapour deposition (PVD) process. First, it was found that the application of the PVD hot process with a high operating temperature of 450 °C significantly decreased the tensile properties of the coating-substrate system compared to those of Al 7075-T6. The yield and ultimate strength decreased by 78% and 54%, respectively. However, as a result of re-applying the T6 cycle (as the post heat treatment), substantial improvements of 243% and 77% were achieved in the yield and ultimate strength of the coated material, respectively. Fractography of the failed specimens indicated the TiN coating layer to be satisfactorily adhered to the substrate under tensile loading.     

Untersuchungen zur Morphologie von Aluminiumhydroxiden und anodischen Aluminiumoxiden mit dem Rasterelektronenmikroskop

Investigations on the morphology of aluminium hydroxides and anodic aluminium oxide films using scanning electron microscope Hydroxide films of spongy structure are originated on aluminium surfaces if aluminium is trated with hot water for short periods. By increasing the reaction time the hydroxide layers start to become more compact until films are growing coherent showing a porous surface. If the reaction time exceeds 4 hours at a reaction temperature of 98°C crystalline scales appear on the top of the films. During the anodic oxydation of hydroxide coated aluminium in citric acid solutions, thin hydroxide films transform into barrier layer type oxides. If the anodization occurs in aggressive electrolytes the existing hydroxide dissolves and oxide layers with porous structure are obtained. Oxide layers produced by anodizing in hot citric acid solutions in the absence of a hydroxide film show a current density dependent morphology. At higher current densities barrier layer type oxides are growing. Using low current densities oxide layers with a character are predominating.     

氧化锆基双陶瓷层热障涂层表层材料研究进展

双陶瓷层热障涂层是热障涂层技术的发展方向之一。等离子喷涂和电子束-物理气相沉积技术是目前最常用的双层涂层制备技术,但存在的固有缺点影响涂层性能的发挥。可实现非视线沉积的等离子-物理气相沉积技术效率高,能对涂层微观结构进行精准调控,发展潜力巨大。稀土氧化物掺杂ZrO2、A2B2O7型烧绿石和萤石结构化合物、钇铝石榴石、独居石结构的稀土磷酸盐、氧化铝等材料被作为表层陶瓷,分别与传统的6%~8%Y2O3部分稳定的ZrO2（(6~8)YSZ）层组合构成双陶瓷层,可有效降低涂层的热导率,极大地改善抗熔盐热腐蚀性能,提高耐热温度等。如YSZ/CeO2和TiO2共稳定的ZrO2双层涂层可大幅提高隔热性能,La2(Zr0.7Ce0.3)2O7能有效提高整个涂层的使用寿命,钇铝石榴石能阻隔氧渗入YSZ层并防止粘结层金属的氧化,GdPO4能与Na2SO4+V2O5熔盐反应形成稠密反应层并抑制熔盐的进一步渗入,纳米Al2O3可形成致密结构,并提高涂层的抗热腐蚀能力和抗高温氧化能力。但是,绝大部分材料的热膨胀系数较低、断裂韧性较差,限制了涂层整体性能的发挥。结合纳米技术和等离子-物理气相沉积等新的制备技术,改性修饰稀土锆酸盐等表层材料的热物理性能,引入稀土钽酸盐等热导率低、韧性强、阻氧性好的材料,被认为能提高双层涂层的隔热性能和使用寿命。     

T91钢高温水蒸汽氧化层形成机理研究

为了研究T91钢高温高压水蒸汽条件下锅炉管道内壁氧化层的形成机理,对T91钢锅炉再热器管内壁高温高压水蒸汽条件下的氧化层形貌进行观察,利用X-Ray物相分析仪测试氧化层的物相结构.结果表明:T91钢在高温高压水蒸汽环境下产生的氧化皮内层为极薄且含有大量阳离子空位的单相无晶界CrFe 2O 4(阳离子空位约为37%)非晶体结构:中层为较厚的单相CrFe 2O 4细等轴晶和在其上生长的粗柱状晶结构:外层为Fe 3O 4-Fe 2O 3的细等轴晶和在其上生长的粗柱状晶结构.     

Optimization of Cold Spray Deposition of High-Density Polyethylene Powders

When a solid, ductile particle impacts a substrate at sufficient velocity, the resulting heat, pressure and plastic deformation can produce bonding between the particle and the substrate. The use of a cool supersonic gas flow to accelerate these solid particles is known as cold spray deposition. The cold spray process has been commercialized for some metallic materials, but further research is required to unlock the exciting potential material properties possible with polymeric particles. In this work, a combined computational and experimental study was employed to study the cold spray deposition of high-density polyethylene powders over a wide range of particle temperatures and impact velocities. Cold spray deposition of polyethylene powders was demonstrated across a range broad range of substrate materials including several different polymer substrates with different moduli, glass and aluminum. A material-dependent window of successful deposition was determined for each substrate as a function of particle temperature and impact velocity. Additionally, a study of deposition efficiency revealed the optimal process parameters for high-density polyethylene powder deposition which yielded a deposition efficiency close to 10% and provided insights into the physical mechanics responsible for bonding while highlighting paths toward future process improvements.     

High temperature oxidation of FeCrAl‐alloys – influence of Al‐concentration on oxide layer characteristics

The superior high temperature oxidation resistance of FeCrAl alloys relies on the formation of a dense and continuous protective aluminium oxide layer on the alloy surface when exposed to high temperatures. Consequently, the aluminium content, i.e. the aluminium concentration at the alloy–oxide layer interface, must exceed a critical level in order to form a protective alumina layer. In the present study the oxidation behaviour of six different FeCrAl alloys with Al concentrations in the range of 1.2–5.0 wt% have been characterised after oxidation at 900 °C for 72 h with respect to oxide layer surface morphology, thickness and composition using scanning electron microscopy, energy dispersive X‐ray spectroscopy and Auger electron spectroscopy. The results show that a minimum of 3.2 wt% Al in the FeCrAl alloy is necessary for the formation of a continuous alumina layer. For Al concentrations in the range of 2.0–3.0 wt% a three‐layered oxide layer is formed, i.e. an oxide layer consisting of an inner alumina‐based layer, an intermediate chromia‐based layer and an outer iron oxide‐based layer. In contrast, the 1.2 wt% Al FeCrAl alloy is not able to form a protective oxide layer inhibiting extensive oxidation.     

Oxidation behaviour of cast aluminium matrix composites with Ce surface coatings

The oxidation behaviour of SiC-reinforced aluminium matrix composites (A3xx.x/SiCp) has been studied after Ce-based treatments. Kinetics data of oxidation process were obtained from gravimetric tests performed at different temperatures (350, 425 and 500 °C). The nature of the oxidation layer was analyzed by scanning electron and atomic force microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy and X-ray diffraction. The extent of oxidation degradation in untreated composites was preferentially localized in matrix/SiCp interfaces favouring the MgO formation. Ce coatings favoured a uniform oxidation of the composite surface with MgAl₂O₄ spinel formation. This oxide increased the surface hardness of the materials.     

Investigation of the Evolution of the Oxide Scale Formed on 310 Stainless Steel Oxidized at 600 °C in Oxygen with 40% Water Vapour Using FIB and TEM

Detailed microstructure investigations were performed on oxide scales formed on 310 stainless steel exposed isothermally at 600 °C to O₂ with 40% water vapour for 1–336 h. FIB microscopy was used to study the evolution of the surface morphology and to prepare cross-section TEM thin foils of the oxide scales. The foils were investigated by analytical transmission electron microscopy. The results showed that a thin protective base oxide scale had formed after 1 h. Due to Cr loss from the oxide scale through water vapour induced Cr evaporation, local breakaway oxidation occurs, resulting in the formation of oxide nodules. The development of these nodules depends on whether a new Cr-rich healing layer is formed or not. A model for the evolution of the oxide scale is proposed based on the results regarding the composition and distribution of various phases in the oxide scale and subjacent steel.     

Characterization of anodized and sealed aluminium by EIS

Anodized and sealed aluminium samples exposed to different atmospheres for up to three years have been studied by means of electrochemical impedance spectroscopy (EIS). EIS was used to obtain detailed information concerning the electrochemical properties of the porous and barrier layer of anodized aluminium. An equivalent circuit that reproduces the a.c. impedance results of porous aluminium oxide films is proposed. The results reveal that the EIS technique is a good tool for obtaining detailed information on the influence of autosealing and the ageing process on anodized aluminium. This research shows that porous layer sealing quality increases over months and years (especially in the first 24 months) as the ageing proceeds when exposed to the natural atmospheric conditions. The analysis was completed with the aid of the SEM technique.     

Impedance measurements on oxide films on aluminium obtained by pulsed tensions

We have performed this study on oxide films sealed or not in boiling water. The films are first obtained on type 1050 A aluminium substrat by pulsed tensions anodizing technique, in a sulfuric acid solution. Afterwards the, Electrochemical Impedance Spectroscopy (EIS) is employed to appreciate the films behaviour in a neutral solution of 3.5% K₂SO₄, in which the interface processes interest only the ageing phenomenon of the oxide films and not their corrosion. We have also attempted a correlation between pulse parameters of anodization and the electrical parameters characterizing these films. The sealing influence on ageing has been studied as well. For all films, ageing is appreciated using impedance diagrams evolution versus time. The results show: – the existence of two capacitive loops confirming the presence of two oxide layers characteristic of oxide films obtained in a sulfuric acid medium. The first loop, at high frequencies, is related to the external porous layer and the second one, at lower freqencies, is related to the internal barrier layer. – the thickness of the barrier layer varies between 25 and 40 nm in relation with the electrical pulse parameters. – the sealing acts favorably against anodic oxide films ageing.     

Friction stir lap joining of aluminium alloy to polypropylene sheets

Joining feasibility of aluminium alloy to polypropylene sheets via friction stir lap joining was examined. Effects of heat-input on microstructure and mechanical behaviour of the joints were investigated. A covering plate was used to confine flow of molten polymer. The results showed a distinctive interaction layer at polymer/aluminium interface, consisted mainly of C, O and Al. Shear strength of the joints decreased by enhancement of the heat-input due to increase in the thickness of the interaction layer as well as the gap width between this layer and both aluminium and polymer matrices. Maximum shear-tensile strength of 5.1?MPa (～20% of polymer shear strength) was obtained, which was higher than or comparable to that of the joints produced by other processes.     

Corrosion protection of a thin aluminium layer deposited on polyester

Organosilicon plasma polymer layers were deposited by surface dielectric barrier discharge (DBD) at atmospheric pressure, in an attempt to enhance the corrosion protection of a reflective aluminium (Al) layer applied on a polyester (PET) fabric. A number of tests were carried out to characterize the improvement of corrosion resistance - namely sodium carbonate (Na₂CO₃), water vapor and Kesternich tests - as a function of plasma treatment time, type of carrier gas, admixture of oxygen, amount of hexamethyldisiloxane (HMDSO) precursor supplied to plasma and post-plasma-treatment heating. Moreover, plasma-deposited protective films were characterized by the scanning electron microscopy (SEM), infrared spectroscopy (DRIFT FTIR), and X-ray photoelectron spectroscopy (XPS). While aluminium was consumed in the Na₂CO₃ corrosive solution within a few minutes for the untreated surface, the optimally performing plasma polymerized layers revealed an extraordinary corrosion resistance. Furthermore, the best protective organosilicon coatings showed only a 1-2% absolute reduction of reflection compared to the untreated fabric, over the complete solar spectrum (250-2500 nm).