LZC/YSZ DCL TBCs by EB-PVD: Microstructure,low thermal conductivity and high thermal cycling life

Thermal barrier coatings (TBCs) with low thermal conductivity have triggered tremendous attention due to their promising application in the gas turbine engines. Albeit recent studies have investigated double ceramic layers (DCL) with pyrochlore (A₂B₂O₇) phase, it still remains a big challenge for controlling element content and investigating the relationship between the complex hierarchical architectures and their thermal performances. Here we describe a series of DCL La₂O₃-ZrO₂-CeO₂ (LZC)/Y₂O₃-stabilized ZrO₂ (YSZ) coating under different current of electron beam by electron beam-physical vapor deposition (EB-PVD). The formation of hierarchical architecture with feathery microstructure and intra-columnar have been investigated in detail. The DCL coatings achieve a high thermal cycling life and relatively low thermal conductivity at controlling current of electron beam from 1.0 A to 1.3 A. This work may open new opportunities to rationally design other promising TBCs.     

Controlling thermal cycling effect in phase separated manganites with high temperature thermal treatments

Several phase separated manganites present a peculiar effect each time they go through a phase transition within the range characterized by phase separation. The effect is known as the thermal cycling effect (TCE) and is characterized by monotonous changes in the relative content of the coexisting phases.In this work, we analyze a way to control the effects induced by TCE, performing thermal treatments at high temperature. Our results revealed a complex interplay between the dynamic and static characteristics of the phase separated state, which can be analyzed in terms of three simple parameters. One related to the static properties, another to the dynamic properties and a last one that acts as a link between both features.     

Effective thermal inertia in relation to normalized heat load

Normalized heart load, obtained by dividing heat absorption by thermal inertia, is a quantity useful in building design for relating fire severity in fully developed compartment fires to fire severity in standard fire resistance tests. Harmathy has shown how normalized heat load may be used for determining required fire resistance in projected buildings. The present work describes how effective values of thermal inertia can be calculated for such important materials as brick and concrete, both normal and lightweight, for which thermal properties depend strongly upon temperature.     

Rapid preparation of low thermal expansion transparent LAS nanocrystalline glass by one-step thermoelectric treatment

The Li₂O–Al₂O₃–SiO₂ (LAS) glass ceramics are prepared by one-step thermoelectric treatment. The influence of thermoelectric treatments on LAS glass-ceramics were studied. The crystal phase composition and microstructure of the LAS glass-ceramics were investigated by DSC, SEM, XRD and FTIR. Moreover, the thermal expansion performance and light transmittance of LAS nanocrystalline glass were characterized. The results show that low-expansion transparent LAS nanocrystalline glass can be produced in a short time by thermoelectric treatment. The free energy of nucleation and the degree of polymerization of the glass network are reduced by the electric field. The key is that the electric field polarizes Ti and Zr ions at the crystallization temperature, so that the crystal nuclei repel the same poles. This allows uniform crystal distribution, promotes crystallization and reduces one-step crystallization of crystal agglomeration. This proves that the rapid preparation of nanocrystalline glass by the one-step method is feasible, and provides a reference for the future one-step processing of glass-ceramics.     

Electrochemical capacitor thermal management issues at high-rate cycling

Electrochemical capacitors have attractive performance features for gas-electric hybrid vehicle applications, namely high-power density and essentially unlimited cycle life. A capacitor system can efficiently capture and store the 5-10 s of braking energy generated during vehicle stopping and then release it during subsequent vehicle acceleration. Even with their exceptional power performance, these types of capacitors have less than 100% cycle efficiency—some energy is always lost as heat. Thus, high-rate cycling of electrochemical capacitors may create thermal management problems, the magnitude increasing with cycle rate. This paper examines energy loss of capacitors undergoing periodic constant-current charge/discharge cycling from one-half rated voltage to rated voltage. Cycle efficiencies of five commercial, large-cell capacitors are reported as a function of cycle rate and compared with series-RC equivalent circuit model results. Three of the capacitors were well represented by such the simple model with good correlation over a span covering almost two orders of magnitude of charge/discharge times. The other two capacitors were not well represented by this simple model, which was due to their substantially greater porous electrode behavior. Consequently, the series-RC model appears adequate for investigating thermal management issues of some, but not all large ECs and demonstrates that caution is needed when selecting capacitor electrical models to perform thermal management engineering.     

Effect of thermal cycling and low pressure sandblasting on the bond strength of a self-adhesive cement to Y-TZP zirconia

The aim of this investigation was to assess the influence of several surface treatments on the shear bond strength (SBS) of a self-adhesive resin cement containing 10-methacryloxydecyl-dihydrogenphosphate monomer to densely sintered zirconia ceramic, before and after thermal cycles. Hundred densely sintered zirconia cylinders were divided into five groups (n = 20). Each of them received a different surface treatment: (1) control [No_T], with the zirconia surface unconditioned, (2) low pressure air abrasion [Sand_S], (50 μm, 1 bar), (3) standardized air abrasion [Sand_H], (50 μm, 2.8 bar), (4) standardized Rocatec? Plus (silica-coated alumina oxide) air abrasion (2.8 bar) and silanization [Roc_H], (5) low pressure Rocatec? Plus (silica-coated alumina oxide) air abrasion (1 bar) and silanization [Roc_S]. Five more surface-treated specimens were addressed to scanning electron microscope for qualitative observations. After specimen fabrication, subgroups of 10 bonded samples were stored in water either for 24 h (T1) or subjected to 5000 thermal cycles (T2); SBSs were determined with a universal testing machine at a crosshead speed of 1 mm/min. At T1, mean SBSs (MPa) obtained for the examined groups were: [Sand_H] 16.24 ± 2.95; [Sand_S] 16.01 ± 2.68; [Roc_H] 17.17 ± 1.64; [Roc_S] 15.92 ± 1.99. All surface treatments positively affected (p < 0.05) the initial self-adhesive cement adhesion to zirconia with respect to No_T (13.29 MPa). Artificial aging decreased the bond strength in all test groups significantly, but no spontaneous debonding was observed in [No_T]: at T2, SBS values ranged from 7.76 ± 2.37 (No_T) to 8.89 ± 1.74 (Sand_S), with no statistically significant difference between groups (p = 0.5293). Both air abrasion with alumina oxide and Rocatec? universal bonding system, used with hard or low air pressure, produced comparable effects on cement–zirconia interface before and after thermal cycles. After artificial aging, minimal differences in bond strength values between sandblasted and control groups were not of statistical significance.     

铜基金刚石工具中铬的快速测定

文章提出了采用硝酸溶样,高氯酸直接冒烟氧化Cr3+为Cr2O72-,硫酸亚铁铵氧化-还原快速滴定来测定铜基金刚石工具中铬的新方法.试验表明,该方法省时、操作简便,减少了环境污染,是一种有效的实用方法.     

融合C80数据的绝热加速量热法热惯量因子修正

受限于仪器原理,绝热加速量热法数据分析需进行热惯量因子修正。然而,现有的修正方法均违背由反应物比热及炉体温度动态追踪效果变化等引起热惯量因子动态变化的事实,导致动力学参数求取存在偏差。针对上述不足,提出一种基于C80与绝热加速量热数据联用的绝热加速量热热惯量因子修正及动力学计算方法。具体步骤如下：基于Friedman法分析C80数据获取无模型动力学参数,将其代入绝热数据求解反应体系比热容与等效热惯量因子乘积,并在绝热平衡方程中由上述乘积替代恒定热惯量因子及比热实现动力学计算。以过氧化二叔丁基(DTBP)和过氧化氢异丙苯(CHP)为实验对象进行实验验证。结果表明,基于两种量热模式联用的热惯量因子修正方法避免了热惯量动态变化对动力学分析的影响,从而获得更加准确的动力学参数。     

Stress development in supported polymer films during thermal cycling

A simple and in-situ bending-beam technique has been used to investigate the stress-temperature relationships for three different polymer coatings (viz, poly(methyl methacrylate), FR-4 epoxy resin, and an amide-imide polymer) during thermal cycling. With this technique, we were able to detect stress relaxation near the polymer's glass transition or caused by cracking of the polymer. Knowing the Poisson's ratio and Young's modulus for the polymer, this technique also allows calculation of the polymer's thermal expansion coefficient from measured thermal stress data. The calculated thermal expansion coefficient of poly(methyl methacrylate) (7 × 10^?5/°C) is in good agreement with literature values (5 to 9 × 10^?5/°C).     

金刚石工具粉末胎体热硬性问题探讨

文章阐明了红硬性与热硬性不同概念的界定,并讨论金刚石工具胎体与高速工具钢热硬性的不同差异。指出影响金刚石工具胎体性能的应该是热硬性而不是红硬性。胎体硬度高低的单一指标,不能表征粉末胎体的耐磨性。而在高温下表征的胎体热硬性是影响胎体耐磨性和金刚石包镶能力的重要因素。随着对胎体热硬性的深入研究和认知,热硬性有望成为业界公认的金刚石工具粉末胎体的重要性能指标。     

Atmospheric plasma sprayed 7%-YSZ thick thermal barrier coatings with controlled segmentation crack densities and its thermal cycling behavior

Yttria-stabilized zirconia (YSZ)-coatings are deposited on Ni-based superalloy IN738 by atmospheric plasma spraying (APS). For the first time, controlled segmentation crack densities are manually developed in the coatings, even after the APS deposition. This method allows to user to control segmentation densities as well as cracks depth, which could be designed as per coating thickness and required application. Thermal cycling test shows promising strain tolerance behavior for the segmented coatings, whereas coating without segmentation could not sustain even for its first thermal cycle period. Further, microstructural studies reveal that a very thin layer of TGO was formed and obvious no coating failure or spallation was observed after thermal cycling test at 1150 °C for 500 cycles.     

Microstructure and thermal cycling behavior of thermal barrier coating on near-α titanium alloy

Two kinds of thermal barrier coatings (TBCs), consisting of NiCoCrAlY bond coats (BCs) deposited by electron beam-physical vapor deposition (EB-PVD) and high velocity oxy-fuel (HVOF) thermal spraying, respectively, and top 8 wt%Y₂O₃–ZrO₂ (8YSZ) ceramic layers deposited by EB-PVD were prepared on near-α titanium alloys. The field emission scanning electronic microscopy and microhardness indentation are used to study the microstructure and microhardness. Different failure features including cracking patterns and the delamination degree of these two TBCs are discussed according to the thermal cycling tests in the atmosphere. It is found that the morphology of the two BCs deposited by different methods (EB-PVD and HVOF) determines the microstructure and microhardness of their corresponding top 8YSZ layers. The BC prepared by EB-PVD is dense and homogeneous, which leads to a dense and hard 8YSZ with clustered slim columnar grains. The BC prepared by HVOF, however, is porous and inhomogeneous in microstructure and, as a result, the top ceramic layer is loose with low microhardness and clustered coarse columnar grains.     

Evaluation of microstructural evolution in thermal barrier coatings during thermal cycling using impedance spectroscopy

Air plasma sprayed thermal barrier coatings are thermally cycled in air up to 1030 °C and evaluated using impedance spectroscopy in conjunction with scanning electron microscopy. When the number of cycles is less than 15, impedance measurements cannot be used to detect the thermally grown oxide (TGO, usually alumina) scale because it does not fully cover the top coat-bond coat interface and the YSZ (yttria-stabilised zirconia used as the top coat) is much more electrically conductive than the alumina, leading to most of the current passing through the YSZ rather than the alumina. After the specimens are subjected to 100 until 250 cycles, impedance measurements show that a continuous alumina scale is formed. In the impedance spectra, there are four relaxation processes, which correspond to the YSZ grains, the YSZ grain boundaries, the TGO, and the electrode effect. Impedance analyses demonstrate that the resistance of the alumina scale increases and the capacitance decreases with increasing cycling. When the specimen is subjected to 400 cycles, the impedance response to the continuous TGO vanishes due to the TGO degradation.     

Architecture designs for extending thermal cycling lifetime of suspension plasma sprayed thermal barrier coatings

Suspension plasma spraying (SPS) as a relatively new spraying technology has great potential on depositing high performance thermal barrier coatings (TBCs). In some cases, however, columnar SPS TBCs show premature failure in thermal cycling test. To explain the reasons of such failure, a failure mechanism for columnar SPS TBCs was proposed in this work. The premature failure of TBCs might be related to the radial stresses in the vicinity of top coat/bond coat interface. These radial stresses were introduced by the thermal misfit and the roughness of bond coat. According to this mechanism, two architecture designs of SPS TBCs were applied to improve the thermal cycling lifetime. One was a double layered top coat design with a lamellar atmospheric plasma sprayed (APS) sub-layer and a columnar SPS top-layer. The other one was a low roughness bond coat design with a columnar SPS top coat deposited on a low roughness bond coat which was grinded before the spraying. With both designs, lifetimes of SPS TBCs were significantly extended. Especially, a lifetime even better than conventional APS TBCs was achieved with the double layered design.     

低膨胀率堇青石陶瓷的研究

以粘土、滑石、氧化铝等为原料 ,经 1390～14 0 0℃烧结 ,制备了堇青石陶瓷。使用X射线荧光分析和X射线衍射分析确定了其化学组成和晶相组成 ,并测定了热膨胀率。根据堇青石的晶体结构和烧结机理 ,研究并讨论了陶瓷的化学组成、原料种类和质量对其晶相组成和热膨胀率的影响。     

Ester-type photosensitive polyimide precursor with low thermal expansion coefficient

For an ester-type photosensitive polyimide precursor of low thermal expansion coefficient, the oxygen concentration in the curing process and the molecular weight of the polyimide precursor were found to control the properties of the polyimide. The effects of these factors on the thermal expansion coefficient, tensile strength, and modulus of polyimide film were investigated. Based on these results, a photosensitive polyimide with low thermal expansion coefficient, called the PIMEL TL-series, was developed. Crack and delamination free multilayers were successfully achieved using this newly developed product.     

Assessment of protective properties of organic coatings by thermal cycling

Researchers’ efforts are focused on understanding how coatings can be tested in order to determine their real capabilities and selected for different purposes. Outdoor exposures are certainly reliable and offer a good representation of the actual service life. However, such tests cannot be considered quick.

On the other hand, a quick test, even if reliable, very often disagrees with the actual degradation mechanisms occurring under natural conditions. In fact, in order to determine an acceleration of the natural weathering, it is necessary to increase the effect of natural parameters affecting the protection properties of a coating.

The usual modern way to operate is to take advantage of ageing tests where temperature plays a big role in the ageing of the material, permitting to gather faster information for coating corrosion resistance evaluation.

Following the recent new experience realised by the Bierwagen group, we carried out different thermal cycling tests consisting in daily series of electrochemical measurements on coated samples, carried out using electrochemical impedance spectroscopy (EIS).

The cumulative effects of such a thermal cycling on the film, based on a large variety of theoretical explanations, should permit the ranking of a variety of materials, by constituents, characteristics and application purposes, in a short time while remaining objective and reliable.

The used ageing procedure and data evaluation allowed to quickly and precisely obtain information concerning both barrier properties and adhesion properties of the studied materials.     

Forced thermal cycling of catalytic reactions: Experiments and modelling

Recent studies of catalytic reactions subjected to fast forced temperature oscillations have revealed a rate enhancement increasing with temperature oscillation frequency. We present detailed studies of the rate enhancement up to frequencies of 2.5 Hz. A maximum in the rate enhancement is observed at about 1 Hz. A model for the rate enhancement that includes the surface kinetics and the dynamic partial pressure variations in the reactor is introduced. The model predicts a levelling off of the rate enhancement with frequency at about 1 Hz. The experimentally observed decrease above 1 Hz is explained by dynamic thermal limitations of the reactor.     

New approach to low thermal conductivity of thermal barrier protection with improved mechanical integrity

Layered ceramic systems with designed stacks of dense and porous layers were investigated as alternative for thermal barrier protection system (TBPs). This approach gives the possibility to obtain low thermal conductivity with the impact protection of dense external layers whilst maintaining the relatively high mechanical properties. Different stacking configurations have been proposed utilizing in total a combination of up to 30 dense/porous layers. Porous layers were produced with two different nominal porosities 20 vol% and 40 vol%. For comparison uni-axial pressed samples with the same porosity level have been prepared. Thermal and mechanical characterization was performed on samples of tape cast (with different stacking designs) and uni-axial pressed fully stabilized zirconia TBPs. The layered fully stabilized zirconia (8YSZ) has 15–30 % lower thermal conductivity in comparison with the uni-axial pressed samples, nevertheless by the same Young`s modulus value. The results of the thermal and mechanical observation shows, that such an approach can be beneficial as an alternative for future thermal barrier protection systems.     

Mechanical and fracture properties of cement-based bi-materials after thermal cycling

This study investigates the effect of thermal cycles on the fracture properties of the cement-based bi-materials. Sixty eight cubes were exposed to a varied number of 24-hour thermal cycles ranging from 0 to 90 and subsequently were tested in a wedge splitting configuration. The mechanical and fracture properties of normal strength and high strength concretes are substantially improved after 30 thermal cycles, but less so after 90 thermal cycles both in isolation and when bonded to an ultra high-performance fibre-reinforced cement-based composite.