Reactions of nitrogen and oxygen surface groups in nanoporous carbons under inert and reducing atmospheres

The reactions of surface functional groups have an important role in controlling conversion of char nitrogen to NOx during coal combustion. This study involved an investigation of the thermal stability and reactions of nitrogen surface functional groups in nanoporous carbons. Four suites of carbons, which were used as models for coal chars, were prepared with a wide range of nitrogen and oxygen contents and types of functional groups. The porous structures of the carbons were characterized by gas adsorption methods while chemical analysis, X-ray photoelectron spectroscopy, and X-ray near edge structure spectroscopy were used to characterize the surface functional groups. Temperature programmed desorption and temperature programmed reduction methods were used to study the reactivity of the surface functional groups during heat treatment under inert and reducing conditions. Heat treatment studies show that the order of stability of the functional groups is quaternary nitrogen > pyridinic > pyrrolic > pyridine N-oxide. Pyridine N-oxide surface groups desorb NO and form N-2 via surface reactions at low temperature. Pyrrolic and pyridinic functional groups decompose and react with surface species to give NH3, HCN, and N-2 as desorption products, but most pyrrolic groups are preferentially converted to pyridinic and quaternary nitrogen. The main desorption product is N-2. Approximately 15-40 wt % of the original nitrogen was retained in the carbons mainly as quaternary nitrogen after heat treatment to 1673 K. The results are discussed in terms of decomposition ranges for surface functional groups and reaction mechanisms of surface species.

Laser welding of thin foil nickel–titanium shape memory alloy

In this study, two L27 Taguchi experiments were carried out to study the effect of fibre laser welding parameters and their interactions upon the weld bead aspect ratio of nickel–titanium thin foil. The optimum parameters to produce full penetrated weld with the largest aspect ratio and desirable microstructure were successfully obtained by the Taguchi experimental design. The corrosion property of the optimized NiTi weld in Hank’s solution at 37.5 °C was studied and compared with the as-received NiTi. To improve the corrosion properties of the weld, the effect of post-weld-heat-treatments ranging from 573 to 1173 K was investigated. The corrosion properties, surface morphology, microstructure and Ti/Ni ratio of the heat-treated NiTi weld were analysed. It was found that a post-weld heat treatment at 573 K for 1 h provided the best pitting corrosion resistance at the weld zone.

Evaluation of Cyclic Deformation Behavior of Laser-welded Shape Memory NiTi Alloys at Different Working Temperatures

Post-weld heat-treatment (PWHT) has been established as one of the cost-effective ways to improve the functional properties, namely shape memory and super-elastic effects (SME and SE), of laser-welded NiTi alloys. However, the functional performance of the laser-welded joint at different working temperatures has not been explored yet. The purpose of this study is to investigate the effect of different working temperatures on the functional properties of the laser-welded NiTi alloys before and after PWHT by applying cyclic deformation tests. Two laser-welded samples: as-welded and heat-treated sample (after PWHT at 350 oC or 623 K) were tested in this work at room temperature, 50 oC (or 323 K) and 75 oC (or 348 K) respectively. The samples were cyclically loaded and unloaded for 10 cycles up to 4 % strain. The critical stress to induce the martensitic transformation and the residual strain after the cyclic tests were recorded. The results indicate that the heat-treated sample exhibited better functional properties than the as-welded sample at room temperature and 50 oC (or 323 K). However, both the as-welded and heat-treated samples failed in the cyclic tests at 75 oC (or 348 K). These findings are important to determine the feasible working temperature range for the laser-welded NiTi components to exhibit desirable functional properties in engineering applications involving cyclic loading.

Photocatalytic organic synthesis in an NMR tube:CC coupling of phenoxyacetic acid and acrylamide

NMR was used to study the semiconductor photocatalytic (SPC) CC coupling of phenoxyacetic acid (PAA) with acrylamide (ACM) in an NMR tube photoreactor. Using an NMR tube with a sol-gel titania inner coating as a photoreactor, this reaction is relatively clean, forming only 1 product, 4-phenoxybutanamide (4-PB), in yields up to 78%. This SPC reaction is used to assess the activity of the sol-gel titania coating as a function of their annealing temperature, which alters the surface area and phase of the titania, and the general reusability of the TiO coated NMR tubes. The optimum temperature range for annealing the sol-gel titania films is between 450 °C and 800 °C, with the maximum yield and rate attained at 450 °C. Despite a decrease in the initial rates of formation of 4-PB above an annealing temperature of 450 °C, the final product yields remained similar, giving maximum yields within 60 min of irradiation. The reusability study reveals that the activity of the sol-gel titania can quickly deteriorate with repeated use due to the adsorption of yellow/brown coloured, insoluble, most likely organic polymeric, material and its screening effect on the underlying photocatalyst. The titania can, however, be restored to its original activity by a simple heat treatment at 450 °C for 30 min.

The influence of high-temperature sintering on microstructure and mechanical properties of free-standing APS CeO-YO -ZrO coatings

In this study, ceria-yttria co-stabilized zirconia (CYSZ) free-standing coatings, deposited by air plasma spraying (APS), were isothermally annealed at 1315 °C in order to explore the effect of sintering on the microstructure and the mechanical properties (i.e., hardness and Young's modulus). To this aim, coating microstructure, before and after heat treatment, was analyzed using scanning electron microscopy, and image analysis was carried out in order to estimate porosity fraction. Moreover, Vickers microindentation and depth-sensing nanoindentation tests were performed in order to study the evolution of hardness and Young's modulus as a function of annealing time. The results showed that thermal aging of CYSZ coatings leads to noticeable microstructural modifications. Indeed, the healing of finer pores, interlamellar, and intralamellar microcracks was observed. In particular, the porosity fraction decreased from ~10 to ~5% after 50 h at 1315 °C. However, the X-ray diffraction analyses revealed that high phase stability was achieved, as no phase decomposition occurred after thermal aging. In turn, both the hardness and Young's modulus increased, in particular, the increase in stiffness (with respect to "as produced" samples) was equal to ~25%, whereas the hardness increased to up to ~60%. © 2010 Springer Science+Business Media, LLC.

Micro-scale wear characteristics of electroless Ni-P/SiC composite coating under two different sliding conditions

The electroless nickel composite (ENC) with various silicon carbide contents was deposited onto aluminium alloy (LM24) substrate. The wear behaviour and the microhardness of the composite coating samples were investigated and compared with particles free and aluminium substrate samples using micro-scale abrasion tester and microhardness tester respectively. The wear scar marks and wear volume were analysed by optical microscope. The wear tracks were further studied using scanning electron microscopy (SEM). The embedded particles were found to get pressed into the matrix which helps resisting further wearing process for composite samples. However, random orientation of microcuts and microfallow were seen for ENC sample but more uniform wearing was observed for EN sample. The composite coating with low content of SiC was worn minimum. Early penetration into the substrate was seen for samples with higher SiC content. Microhardness was improved after heat treatment for all the samples containing various SiC content. Under dry sliding condition, inclusion of particles in the matrix did not improve the wearing resistance performance in as-deposited state. The wearing worsened as the content of the particles increased generally. However, on heat treatment, the composite coatings exhibited improved wear resistance and the best result was obtained from the one with low particle contents.

A simple and low-cost method for the preparation of self-supported TiO2-WO3 ceramic heterojunction wafers

Robust, bilayer heterojunction photodiodes of TiO₂-WO₃ were prepared successfully by a simple, low-cost powder pressing technique followed by heat-treatment. Exclusive photoirradiation of the TiO₂ side of the photodiode resulted in a rapid colour change (dark blue) on the WO₃ surface as a result of reduction of W⁶⁺ to W⁵⁺ (confirmed by X-ray photoelectron spectroscopy). This colour was long lived and shown to be stable in a dry environment in air for several hours. A similar photoirradiation experiment in the presence of a mask showed that charge transfer across the heterojunction occurred approximately normal to the TiO₂ surface, with little smearing out of the mask image. As a result of the highly efficient vectorial charge separation, the photodiodes showed a tremendous increase in photocatalytic activity for the degradation of stearic acid, compared to wafers of the respective individual materials when tested separately.

Insight of the interface of electroless Ni-P/SiC composite coating on aluminium alloy, LM24

Electroless nickel composite coatings with silicon carbide, SiC, as reinforcing particles deposited with Ni–P onto aluminium alloy, LM24, having zincating as under layer were subjected to heat treatment using air furnace. The changes at the interface were investigated using scanning electron microscope (SEM) and energy dispersive X-ray (EDX) to probe the chemistry changes upon heat treatment. Microhardness tester with various loads using both Knoop and Vickers indenters was used to study the load effect clubbed with the influence of second phase particles on the coating at the vicinity of the interface. It was observed that zinc was absent at the interface after elevated temperature heat treatment at 400–500 °C. Precipitation of copper and nickel with a distinct demarcation (copper rich belt) along the coating interface was seen with irregular thickness of the order of 1 μm. Migration of copper from the bulk aluminium alloy could have been the factor. Brittleness of the coating was confirmed on heat treatment when indented with Vickers. However, in composite coating the propagation of the microcrack was stopped by the embedded particles but the microcracks continue in the matrix when not interrupted by second phase particles (SiC).

Phase composition, microstructure and microhardness of electroless nickel composite coating co-deposited with SiC on cast aluminium LM24 alloy substrate

Electroless Ni–P (EN) and composite Ni–P–SiC (ENC) coatings were developed on cast aluminium alloy substrate, LM24. The coating phase composition, microstructure and microhardness were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and microhardness tester, respectively, on as-plated and heat-treated specimens. The original microstructure of the Ni–P matrix is not affected by the inclusion of the hard particles SiC. No formation of Ni–Si phase was observed up to 500 °C of heat treatment. The microhardness is increased on incorporation of SiC in Ni–P matrix. The hardening mechanism is the formation of intermetallic phase Ni3P on annealing at elevated temperature.

Electroless nickel composite (Ni-P/SiC) coating - A study on interface and corrosion characteristic

Surface behaviour is of paramount importance as failure and degradation tend to initiate from the surface. Electroless composite coating (NiP/SiC) was developed using SiC as reinforcing particles. As heat treatment plays a vital role in electroless nickel coating owing to the changes in microstructure, phase structure and mechanical properties, an insight at the interface changes in chemistry and micromechanical behaviour was investigated using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) and microindentation techniques. Corrosion performance was analysed using electrochemical impedance spectroscopy (EIS). Absence of zinc and migration of copper at the interface was detected. Brittleness and microcracks was seen long the interface when indenting at load of 500 gf (Vickers). Corrosion performance is weaker than particles free coating. However, a thin blanket of NiP could enhance the resistance to corrosive medium.

Characterisation of phase composition, microstructure and microhardness of electroless nickel composite coating co-deposited with SiC on casting aluminium LM24 alloy substrate

Electroless Ni-P (EN) and composite Ni-P-SiC (ENC) coatings were developed on cast aluminium alloy, LM24. The coating phase composition, microstructure and microhardness were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and microhardness tester, respectively, on as-plated and heat-treated specimens. The original microstructure of the Ni-P matrix is not affected by the inclusion of the hard particles SiC. No formation of Ni-Si phase was observed upto 500°C of heat treatment. The microhardness is increased on incorporation of SiC in Ni-P matrix. The hardening mechanism is the formation of intermetallic phase Ni3P on annealing at elevated temperature. Overall, the composite coating (ENC) was found to be superior as compared to particles free (EN) coating in both as-deposited and heat-treated conditions.

Micro-scale abrasion behaviour of electroless Ni-P-SiC coating on aluminium alloy

Electroless nickel (EN) and electroless nickel composite (ENC) coatings were deposited on aluminium alloy substrate, LM24. The micro abrasion test was conducted to study the wear behaviour of the coatings with the effect of SiC concentration. Microhardness of the coatings was tested also. The wear scars were analysed using optical microscope and scanning electron microscope (SEM). The wear resistance was found to be improved in composite coating that has higher microhardness as compared to particles free and the bare aluminium substrate. In as-deposited condition for the composite coating, the wear volume increases on increase in SiC percentage in the coating but is found to be minimum for lower SiC percentage. The increase in hardness on heat treatment at 400°C is due to the hardening or grain coarsening with the formation Ni3P.

Mechanical behaviour of AISiC nano composites produced by Ball Milling and Spark Plasma Sintering

Neste trabalho foram produzidos nanocompósitos de AlSiC misturando alumínio puro com nano partículas de SiC com diâmetro de 45 – 55 nm, usando, de forma sequencial, a técnica da metalurgia do pó e a compactação por “ Spark Plasma Sintering”. O compósito obtido apresentava grãos com 100 nm de diâmetro, encontrandose as partículas de SiC localizadas, principalmente, nas fronteiras de grão. O nanocompósito sob a forma de provetes cilíndricos foi submetido a testes de compressão uniaxial e a testes de nanoindentação para analisar a influência das nanopartículas de SiC, da fração volúmica de ácido esteárico e do tempo de moagem, nas propriedades mecânicas do material. Para efeitos de comparação, utilizouse o comportamento mecânico do Al puro processado em condições similares e da liga de alumínio AA1050O. A tensão limite de elasticidade do nanocompósito com 1% Vol./Vol. de SiC é dez vezes superior à do AA1050. O refinamento de grão à escala nano constitui o principal mecanismo de aumento de resistência mecânica. Na realidade, o Al nanocristalino sem reforço de partículas de SiC, apresenta uma tensão limite de elasticidade sete vezes superior à da liga AA1050O. A adição de 0,5 % Vol./Vol. e de 1 % Vol./Vol. de SiC conduzem, respetivamente, ao aumento da tensão limite de elasticidade em 47 % e 50%. O aumento do tempo de moagem e a adição de ácido esteárico ao pó durante a moagem conduzem apenas a um pequeno aumento da tensão de escoamento. A dureza do material medida através de testes de nanoindentação confirmaram os dados anteriores. A estabilidade das microestruturas do alumínio puro e do nanocompósito AlSiC, foi testada através de recozimento de restauração realizado às temperaturas de 150 °C e 250 °C durante 2 horas. Aparentemente, o tratamento térmico não influenciou as propriedades mecânicas dos materiais, excepto do nanocompósito com 1 % Vol./Vol. de SiC restaurado à temperatura de 250 °C, para o qual se observou uma redução da tensão limite de elasticidade na ordem dos 13 %. No alumínio nanocristalino, a tensão de escoamento é controlada pelo efeito de HallPetch. As partículas de SiC, são segregadas pelas fronteiras do grão e não contribuem para o aumento de resistência mecânica segundo o mecanismo de Orowan. Alternativamente, as nanopartículas de SiC constituem um reforço das fronteiras do grão, impedindo o seu escorregamento e estabilizando a nanoestrutura. Deste modo, as propriedades mecânicas do alumínio nanocristalino e do nanocompósito de AlSiC poderão estar relacionadas com a facilidade ou dificuldade do escorregamento das fronteiras de grão, embora não seja apresentada prova explícita deste mecanismo à temperatura ambiente.

Alkali-free bioactive glasses for bone regeneration

Bioactive glasses and glass-ceramics are a class of third generation biomaterials which elicit a special response on their surface when in contact with biological fluids, leading to strong bonding to living tissues. The purpose of the present study was to develop diopside based alkali-free bioactive glasses in order to achieve good sintering behaviour, high bioactivity, and a dissolution/ degradation rates compatible with the target applications in bone regeneration and tissue engineering. Another aim was to understand the structure-property relationships in the investigated bioactive glasses. In this quest, various glass compositions within the Diopside (CaMgSi2O6) – Fluorapatite (Ca5(PO4)3F) – Tricalcium phosphate (3CaO•P2O5) system have been investigated. All the glasses were prepared by melt-quenching technique and characterized by a wide array of complementary characterization techniques. The glass-ceramics were produced by sintering of glass powders compacts followed by a suitable heat treatment to promote the nucleation and crystallization phenomena. Furthermore, selected parent glass compositions were doped with several functional ions and an attempt to understand their effects on the glass structure, sintering ability and on the in vitro bio-degradation and biomineralization behaviours of the glasses was made. The effects of the same variables on the devitrification (nucleation and crystallization) behaviour of glasses to form bioactive glass-ceramics were also investigated. Some of the glasses exhibited high bio-mineralization rates, expressed by the formation of a surface hydroxyapatite layer within 1–12 h of immersion in a simulated body fluid (SBF) solution. All the glasses showed relatively lower degradation rates in comparison to that of 45S5 Bioglass®. Some of the glasses showed very good in vitro behaviour and the glasses co-doped with zinc and strontium showed an in vitro dose dependent behaviour. The as-designed bioactive glasses and glass–ceramic materials are excellent candidates for applications in bone regeneration and for the fabrication of scaffolds for tissue engineering.

Optimisation du traitement thermomécanique de pièces d’acier fabriquées par métallurgie des poudres

Le forgeage de préformes fabriquées par métallurgie des poudres nous permet d’atteindre une densification voisine de la densité théorique ce qui a comme incidence directe une amélioration substantielle des propriétés mécaniques finales des pièces, notamment la résistance en fatigue. La démarche préconisée pour améliorer cette performance critique de pièces forgées par métallurgie des poudres consiste à optimiser leurs caractéristiques métallurgiques et leur densité concomitante. À ce propos, une nouvelle formulation d’acier MP a été développée et caractérisée. La stratégie de développement portait sur l’utilisation d’éléments de microalliage préalliés, comme le vanadium et le niobium. Pour ce faire, on a optimisé le paramètre de mise en œuvre primordial, qui est la température de forgeage, afin d’obtenir une fine taille de grains à la fin du cycle du traitement réalisé accompagnée d’une densité élevée des pièces forgées. Une série de traitements d’austénisation sur une gamme étendue de température variant entre 900 °C à 1250 °C a été effectuée ce qui nous a permis par la suite de connaître, pour chaque mélange, l’évolution de la taille des grains en fonction de la température d’austénisation. La nouvelle formulation de composition chimique a démontré un impact marqué quant au contrôle de la taille de grains en fonction de la température d’austénitisation. Une étude comparative nous a permis d’identifier la température de forgeage la plus appropriée pour ce type de pièces et de dégager la méthodologie à suivre en fonction des propriétés mécaniques et microstructurales.