The application of small angle scattering techniques to porosity characterization in carbons

Small angle scattering (SAS) techniques offer a number of advantages for the investigation of the nature and behavior of porous materials. In particular, with respect to carbons, the essentially non-intrusive nature of SAS means that along with the more traditional, pre- and post-treatment characterization of carbons, in principle, characterization can also be performed in situ during adsorption and activation processes. In the current communication, the application of the techniques of small angle X-ray (SAXS) and neutron (SANS) scattering is reviewed specifically with respect to porosity characterization in carbons. First, the basis of these techniques is presented. More recent applications of SAXS and SANS to carbon porosity are presented, and their relative attributes are contrasted, including the related technique of contrast matching with SANS to distinguish “closed” from “open” porosity, and its application to elucidation of pore development mechanisms. Applications of other related techniques, such as μSAXS and TGA/SAXS, to carbon characterization and porosity development are also discussed.     

Microstructural,mechanical and tribological properties of suspension plasma sprayed YSZ/h-BN composite coating

Brittleness, relative high friction coefficient and wear rate limit the applications of ceramic coatings as wear-resistant layers. However, because embedding additives with ceramic matrix has demonstrated to be an effective way to improve coating performances, different contents and size of h-BN were added into an YSZ suspension. Afterwards, the YSZ/h-BN composite coatings were manufactured by suspension plasma spray and their tribological analysis indicated that: i) the reduction of the friction coefficient and wear rate can be achieved by incorporating h-BN into YSZ coating. ii) finer h-BN particle is more helpful to enhance the tribological properties of the coating. iii) the optimum content is dependent on h-BN particle sizes. iv) when the contents and the size of the h-BN inclusion increase, the probability distribution of the micro-hardness can become bi-modal. Three worn surface conditions were summarized and their wear mechanisms were discussed as well.     

Effect of environmental pressure on the microstructure of YSZ thermal barrier coating via suspension plasma spraying

Suspension plasma spraying (SPS) as a potential technique to prepare thermal barrier coatings (TBCs) has been attracting more and more attention. However, most reports on SPS were carried out in the atmosphere. Given the unique features of in-flight particles and plasma jets under low pressure, the resulting coatings are expected to be different from those under atmospheric pressure. In this article, yttria-stabilized zirconia (YSZ) thermal barrier coatings were prepared using suspension plasma spraying under different environmental pressures. The results show that as the environmental pressure decreased, the column-like structural coating turned into a vertical crack segmented structure, as well as a dramatic decrease in surface roughness. More nanoparticle agglomerates were formed in the coating under lower environmental pressures. The real porosity of the coating increased with a decrease in environmental pressure.     

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.     

Isothermal oxidation and TGO growth behaviors of YAG/YSZ double-ceramic-layer thermal barrier coatings

In this study, yttrium aluminum garnet/yttria-stabilized zirconia (YAG/YSZ) double-ceramic-layer thermal barrier coatings (DCL TBC) and yttria-stabilized zirconia (YSZ) single-ceramic-layer thermal barrier coatings (SCL TBC) were deposited by atmosphere plasma spray (APS) on the Inconel 738 alloy substrate, and isothermal oxidation tests were performed to investigate the formation and growth behavior of thermally grown oxide (TGO). Results showed that the Al₂O₃ TGO thickness of both TBC groups increased by increasing the isothermal oxidation time,and then slowly decreased with the appearance and growth of the adverse multilayer structure comprising CoCr₂O₄, (Ni,Co)Al₂O₄, NiCr₂O₄, and NiO mixed oxides. However, since the significant inhibition effect of the YAG coating to oxygen ionic diffusion, the mixed oxides appearance time and TGO growth behaviors were delayed in the DCL TBC. As a result, the TGO thickness of the DCL TBC was always smaller than that of the SCL TBC in the entire oxidation process. And the Al₂O₃ layer thickness proportion in the total TGO of the DCL TBC was greater than or equal to that of the SCL TBC after oxidation for the same period. The results of weight gain showed that compared with the SCL TBC, the parabolic oxidation rate of the DCL TBC was decreased approximately 35%. Consequently, the DCL TBC has better high-temperature oxidation resistance than the SCL TBC.     

Comparative study on thermal shock behavior of thick thermal barrier coatings fabricated with nano-based YSZ suspension and agglomerated particles

Two kinds of segmentation-crack structured YSZ thick thermal barrier coatings (TTBCs) were deposited by suspension plasma spraying (SPS) and atmospheric plasma spraying (APS) with nano-based suspension and agglomerated particles, respectively. The phase composition, microstructure evolution and failure behavior of both TBCs before and after thermal shock tests were systematically investigated. Microstructure of the APS coating exhibits typical segmentation-crack structure in the through-thickness direction, similar with the SPS coating. The densities of segmentation-crack in APS and SPS coatings were about 3 cracks mm⁻¹ and 4 cracks mm⁻¹_, respectively. The microstructure observation also showed that the columnar and equiaxed grains existed in the SPS coating. As for the thermal shock test, the spallation life of the APS TTBCs was 146 cycles, close to that of the SPS TTBCs (166 cycles). Failure of the APS coating is due to the spallation of fringe segments and splats.     

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.     

Thick thermal barrier coatings with different segmentation crack densities: Microstructure analysis and thermal oxidation behavior

Thick thermal barrier coatings (TTBCs) have been developed to increase the lifetime of hot section parts in gas turbines by increasing the thermal insulating function. The premeditated forming of segmentation cracks was found to be a valuable way for such an aim without adding a new layer. The TTBC introduced in the current study are coatings with nominal thickness ranging from 1 to 1.1 consisting of MCrAlY bond coat and 8YSZ top coat deposited by air plasma spray technique (APS). TTBCs with segmented crack densities of 0.65 mm^?1 (type-A) and 1 mm^?1 (type-B) were deposited on a superalloy substrate by adjusting the coating conditions. It was found that the substrate temperature has an influential role in creating the segmentation crack density. The crack density was found to increase with substrate temperature and liquid splat temperature. The two types of coatings (type-A and B) with different densities of segmentation crack were heat-treated at 1000 °C (up to 100 h) and 1100 °C (up to 500 h). The variation of hardness measured by indentation testing indicates a similar trend in both types of coatings after heat treatments at 1000 °C and 1100 °C. Weibull analysis of results demonstrates that higher preheating coating during the deposition results in a denser YSZ coating. The growth rate of TGO for TTBCs was evaluated for cyclic and isothermal oxidation routes at 1000 °C and 1100 °C. The TGO shows the parabolic trend for both two types of coatings. The Kps value for two oxidation types is between 5.84 × 10^?17 m²/s and 6.81 × 10^?17 m²/s. Besides, the type B coating endures a lifetime of more than 40 cycles at thermal cycling at 1000 °C.     

Changes in thermal conductivity and thermal shock resistance of YSZ-SiO2 suspension plasma spray coatings according to various raw material particle sizes

Recently, a technique for improving the thermal efficiency of automotive engines has received considerable attention, namely the application of thermal insulation coatings to automotive engine components to reduce heat loss. This study presents thermal shock resistance and related microstructural changes and thermal properties of 8 wt% yttria-stabilized zirconia (8YSZ)/SiO₂ multi-compositional thermal insulation coatings with suspensions of various particle sizes, when subjected to suspension plasma spray. After 10,000 cycles of thermal shock testing of the coatings, it was found that different degradation behavior related to the different microstructure of the coatings was influenced by the particle sizes of the suspension. The thermal conductivity of the coatings was significantly reduced by increasing the distribution of the unmelted particles within the coating.     

In situ inelastic neutron scattering studies of the rotational and translational dynamics of molecular hydrogen adsorbed in single-wall carbon nanotubes (SWNTs)

Inelastic neutron scattering (INS) spectra were measured in situ from progressively increased amounts of para-hydrogen physisorbed in bundles of single-walled carbon nanotubes at temperatures in the vicinity of 20 K. INS from the bound H₂ molecules consists of two distinct parts carrying complementary information. In the low energy and momentum transfer region, at about 14.5 meV we observe a sharp line corresponding to rotational transitions between the ground para-J = 0 state and the ground ortho-J = 1 state without change of the translational state of the molecular centre of mass (CoM). This we call the “bound” spectrum. At higher energy transfers, a series of broad peaks are observed, corresponding to rotational transitions between the para-J = 0 state and different ortho-states (J = 1, 3, 5, … ,) shifted out in energy transfer by an amount equal to the CoM recoil energy. This we call the “recoil” spectrum. Both parts of each spectrum are analysed using the Young and Koppel model. From the “bound” spectrum we estimate the mean height of the barrier to rotation and the mean square displacements of the molecules accommodated at different adsorption sites. The “recoil” spectrum allows us to derive the mean translational kinetic energy of the adsorbed hydrogen as a function of the surface concentration.     

Quantitative image analysis of bubble cavities in iron ore green pellets

Scanning electron microscopy and image analysis was used for quantitative analysis of bubble cavities in iron ore green pellets. Two types of pellets prepared with and without addition of flotation reagent prior to balling were studied. The bubble cavity porosity amounted to 2.8% in the pellets prepared without addition of flotation reagent prior to balling. When flotation reagent was added prior to balling, the bubble cavity porosity increased by a factor of 2.4 and the median bubble diameter was decreased slightly. It was also shown that mercury intrusion porosimetry is not suitable for determination of the distribution of bubble cavities. Finally, our data suggested that the difference in total porosity determined by mercury intrusion porosimetry and pycnometry between the two types of pellets was due to the bubble cavities.     

Agglomeration in suspension of salicylic acid fine particles: influence of some process parameters on kinetics and agglomerate final size

Agglomeration in suspension is a size-enlargement method that facilitates operations of solid processing (filtration, transport, galenic) and preserves the solubilization properties of fine particles. It consists in adding to a suspension of microparticles a small quantity of a second liquid acting as an interparticle binder; in a suitably agitated equipment with a critical quantity of binder, spherical and dense agglomerates of a few millimeters in diameter may be formed. This paper presents a new methodology to study the agglomeration process. The system [salicylic acid/aqueous solution/chloroform] is chosen as a model system. To follow in situ the agglomerate formation and growth, an original device based on image acquisition and analysis is developed; agglomerate porosity and compressive strength are also measured. These measurements allow us to identify the influence of the process parameters on the agglomeration kinetics, the size and the compressive strength of the final agglomerates. They also give interesting insights into the mechanisms.     

Characterisation of thermal barrier coatings and ultra high temperature composites deposited in a low pressure plasma reactor

A low pressure plasma process working at 600-800 Pa was used to deposit from aqueous solution ZrO₂-4 mol% Y₂O₃ (Yttria partially stabilized Zirconia-YpSZ) layers and stacks of Ta₂O₅/YpSZ layers for use as thermal barrier coatings (TBC). The observation of the cross section revealed a high porosity. The thermal diffusivity of the layers (1 × 10⁻⁷ m² s⁻¹) was measured by a laser flash technique and compared with values obtained on air plasma sprayed material (3 × 10⁻⁷ m² s⁻¹). The plasma reactor were also used to deposit ZrB₂-ZrO₂-SiC layers used as Ultra High Temperature Composite (UHTC) from aqueous solutions of zirconyl and Boron nitrates containing suspensions of SiC. Layers up to 100 μm thick were obtained on SiC substrates. XRD was used to study the crystallinity of the layer. The presence of ZrB₂ and SiC phases was confirmed after the deposition. XRD analysis showed that heat treatment at 1073 K under oxidizing conditions led to the loss of ZrB₂ and the appearance of ZrO₂ phases. To understand the behaviour of the layers to interaction with atomic oxygen (combustion for TBC and spacecraft re-entry phase for UHTC), we have measured the atomic oxygen recombination coefficient to determine the number of adsorption sites on the surface of the coatings. This was accomplished by using a low pressure plasma reactor coupled with optical spectroscopic measurements as a diagnostic technique.     

3D characterization of porosity in an air plasma‐sprayed thermal barrier coating and its effect on thermal conductivity

Air plasma spray (APS) thermal barrier coatings (TBCs) contain pores, cracks and splat interfaces that are preferentially aligned normal to the heat flux direction. These significantly reduce (by as much as 50%) the thermal conductivity over a fully dense coating. Here the microstructures of APS thermal barrier coatings (TBCs) have been characterized in 3D using X‐ray microcomputed tomography (μ‐CT). Pores larger than 2.8 μm³ are resolved and their contribution to thermal conductivity reduction is evaluated using image‐based microstructurally realistic numerical models. However, the models overestimate (by almost 50%) the measured thermal conductivity of the as‐deposited TBC sample. It is shown that this discrepancy is due to very fine (micrometer and submicrometer) cracks which readily sinter after short‐term exposure to temperatures representative of TBC operating conditions causing the measured thermal conductivity to rise to within 15% of that predicted. This suggests that under the realistic service conditions, the 3D image‐based models based on CT images provide a good indicator of the likely long‐term TBC performance. Virtual experiments showed that for the retained pores, the larger pores which are flatter and more oriented in the plane of the APS splats, contribute disproportionately to the beneficial reduction in thermal conductivity. Our results demonstrate that X‐ray imaging is a useful tool in establishing APS process conditions that give rise to a beneficial distribution of such pores.     

Specimen preparation and image processing and analysis techniques for automated quantification of concrete microcracks and voids

Specimen preparation and image processing/analysis techniques were developed for use in automated quantitative microstructural investigation of concrete, focusing on concrete microcracks and voids. Different specimen preparation techniques were developed for use in fluorescent and scanning electron microscopy (SEM) of concrete; then techniques produce a sharp contrast between microcracks/voids and the body of concrete. The image processing/analysis techniques developed specifically for use with concrete address the following usages: automatic threshold; development of intersecting microcracks/voids and connected voids; distinction of microcracks form voids based on geometric attributes; and noise filtration.     

Failure analysis of thermally cycled columnar thermal barrier coatings produced by high-velocity-air fuel and axial-suspension-plasma spraying: A design perspective

Axial-suspension-plasma spraying (ASPS) is a fairly recent thermal spray technology which enables production of ceramic top coats in TBCs, incorporating simultaneously the properties of both the conventional-plasma sprayed (highly insulating porous structures) and electron-beam-physical-vapor-deposited (strain-tolerant columnar structures) top coats. TBCs are required to insulate the hot components in a gas turbine engine against high temperature and harsh operating conditions. Periodic heating and cooling of turbine engines during operation can create severe thermal cyclic fatigue conditions which can degrade the performance of these coatings eventually leading to the failure. An in-depth experimental investigation was performed to understand the failure behavior of columnar TBCs subjected to thermal cyclic fatigue (TCF) test at 1100?C. The study revealed that the TCF performance was influenced to an extent, by the top coat microstructure, but was primarily affected by the severity of thermally grown oxide (TGO) growth at the bond coat-top coat interface. Mixed failure modes comprising crack propagation through the bond coat-TGO interface, through TGO and within the top coat were identified. Based on the analysis of the experimental results and thorough discussion a novel design of microstructure for the high TCF performance columnar TBC is proposed.     

热分析技术在芳纶结构性能研究中的应用

介绍了热重分析法、差热分析法、动态热分析法、热力学分析法等热分析技术在芳纶结构和性能分析中的应用。指出国内对芳纶热性能研究应将各种热分析技术和其他结构分析技术联合使用,揭示芳纶结晶结构和无定形区链分子的运动规律,分析芳纶结构与芳纶制品性能之间的关系,为我国芳纶材料设计、芳纶结构性能的研究及芳纶制品的开发应用提供思路。     

Hot corrosion resistance of air plasma sprayed ceramic Sm2SrAl2O7 (SSA) thermal barrier coatings in simulated gas turbine environments

Samarium strontium aluminate (Sm₂SrAl₂O₇-SSA) and Yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBCs) were developed on NiCrAlY bond coated Inconel 718 superalloy substrate using air plasma spray process. The hot corrosion study was conducted in simulated gas turbine environments (molten mixtures of 50?wt% Na₂SO₄ + 50?wt% V₂O₅ and 90?wt% Na₂SO₄ + 5?wt% V₂O₅ + 5?wt% NaCl) for two different temperatures of 700 and 900?°C. A developed SSA TBCs showed about 8% and 22% lower lifetime at 700 and 900?°C, respectively than YSZ TBCs in 50?wt% Na₂SO₄ +?50?wt% V₂O₅ (vanadate). The hot corrosion life of SSA TBCs being found about 13% and 39% lower than YSZ TBCs in 90?wt% Na₂SO₄ +?5?wt% V₂O₅ +?5?wt% NaCl (chloride) at 700 and 900?°C, respectively. X-ray diffraction results showed the formation of SmVO₄, SrV₂O₆, and SrSO₄ as a major hot corrosion product in 50?wt% Na₂SO₄ +?50?wt% V₂O₅ and 90?wt% Na₂SO₄ +?5?wt% V₂O₅ +?5?wt% NaCl environments respectively for SSA TBCs. Similarly, YSZ TBCs also showed YVO₄ as hot corrosion product in vanadate and chloride environments. Both the TBCs suffer a more severe hot corrosion attack in chloride environment at 900?°C. The leaching of Sr²⁺ and Y³⁺ ions from SSA and YSZ respectively play a vital role in the destabilization of coating in vanadate and chloride environments at 700 and 900?°C. In both SSA and YSZ TBCs, the leaching of ion has significantly low influence as compared to attack by chloride ions at the bond coat-top coat interface in the presence of chloride environment. The hot corrosion resistance of SSA TBCs was improved three times higher in the presence of MgO and NiO inhibitor in vanadate environment at 900?°C mainly due to the formation of a stable Ni₃V₂O₈ phase at the surface.     

Chemical and thermal analysis of the biopolymers in the lavandin

Who does not know the lavender's perfume so characteristic of the Provence? The lavandin presents a better yield in essential oil that is used mainly in perfumes and cosmetics, but also in washing powders and cleaning materials. The chemical and thermal study, made on the same stalk of the lavandin, during the period from January to August, responds to two goals. First for economic appearance, we observed a higher yield of essential oil in open or wilted flowers. The automation of the flowers gathered has induced a decreasing of the essential oil in distillation, on account of the recovery of the branches without oil. Moreover, the water, mineral ashes, cellulose, lignin, holocellulose, and hemicellulose contents are computed in all the aerial parts (new and old leaves, branches). Second, the wild lavender, like other plants of the land of Provence, could be at the start of the forest fire. The inflammability risk can be observed by thermal analysis at about 300°C: presence of an exothermic peak by DTA, weight loss by TG, and determination of the maximum decomposition rate by differential thermogravimetry (DTG). In high‐heating rates (about 50°C/min), the decomposition of the aerial parts of the plant increases mainly with the cellulose level. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1629–1641, 2000     

Evaluation of hot corrosion behavior of CSZ,CSZ/micro Al2O3 and CSZ/nano Al2O3 plasma sprayed thermal barrier coatings

Hot corrosion is one of the main destructive factors in thermal barrier coatings (TBCs) which come as a result of molten salt effect on the coating–gas interface. Hot corrosion behavior of three types of plasma sprayed TBCs was evaluated: usual CSZ, layer composite of CSZ/Micro Al₂O₃ and layer composite of CSZ/Nano Al₂O₃ in which Al₂O₃ was as a topcoat on CSZ layer. Hot corrosion studies of plasma sprayed thermal barrier coatings (TBCs) were conducted in 45 wt% Na₂SO₄+55 wt% V₂O₅ molten salt at 1050 °C for 40 h. The graded microstructure of the coatings was examined using scanning electron microscope (SEM) and X-ray diffractometer (XRD) before and after hot corrosion test. The results showed that no damage and hot corrosion products was found on the surface of CSZ/Nano Al₂O₃ coating and monoclinic ZrO₂ fraction was lower in CSZ/Micro Al₂O₃ coating in comparison with usual CSZ. reaction of molten salts with stabilizers of zirconia (Y₂O₃ and CeO₂) that accompanied by formation of monoclinic zirconia, irregular shape crystals of YVO₄, CeVO₄ and semi-cubic crystals of CeO₂ as hot corrosion products, caused the degradation of CSZ coating in usual CSZ and CSZ/Micro Al₂O₃ coating.