The annealing and re-oxidation of oxidized CuNi alloys

A study has been made of the effects of an intermediate, isothermal annealing treatment in argon on the oxidation kinetics in dry oxygen of Cu10%Ni and Cu24%Ni at 800°C and Cu80%Ni at 1000°C using a semi-automatic microbalance. Changes in scale morphology and composition have been investigated using various techniques.Oxidation of Cu10%Ni and Cu24%Ni produces external scales consisting of a thick, inner Cu₂O layer and a thin, outer CuO layer, together with nickel-rich internal oxide in the adjacent alloy. Oxidation of Cu80%Ni yields an external scale consisting of a thick, inner NiO layer and a thin, outer CuO layer, together with a few nickel-rich internal oxide particles in the adjacent alloy. During annealing, the outer CuO layers on the three alloys dissociate to give Cu₂O and oxygen. With Cu80%Ni only, further dissociation to give copper metal takes place after long annealing times. In all cases, the annealing treatment leads to a reduction in the cation vacancy gradient across the scale and a reduction in the total vacancy level in the scale due to the reduction in oxygen activity at the oxide-gas interface.In Cu10%Ni and Cu24%Ni, internal oxide formation during annealing stimulates dissociation of the Cu₂O scale near the oxide-alloy interface to give copper metal and oxygen. Similarly, internal oxide formation stimulates dissociation of the NiO layer on Cu80%Ni, although to a lesser extent than for the copper-rich alloys.During re-oxidation, the kinetics are partly determined by the extent of scale thinning during the prior annealing treatment, giving more rapid weight gains than expected from those recorded during the initial oxidation period. Nevertheless, particularly for Cu80%Ni, where the scale thinning is relatively small, the reduction in the cation vacancy gradient across the scale and the reduction in the total vacancy level in the scale do result in a reduced oxidation rate compared with the rate recorded during the initial oxidation period.     

Corrosion behaviour of the extruded and unidirectionally solidified AlAl4Ca eutectic alloy in a neutral sodium chloride solution

The corrosion behaviour of extruded and unidirectionally solidified AlAl₄Ca eutectic alloy in a neutral sodium chloride solution has been compared with the behaviour of commercially pure Al and AlCu alloy. From both anodic and cathodic cyclic linear potentiodynamic measurements and from S.E.M. observations it was possible to point out that the corrosion behaviour of unidirectionally solidified alloy is substantially equal to that of the extruded alloy, slightly different from that of commercially pure Al and better than AlCu alloy. Therefore, the use of this new lamellae-reinforced AlAl₄Ca composite is promising, even though from the corrosion point of view further studies involving different techniques and conditions (solutions, temperature, surface state, stress, etc.) should be undertaken.     

The effect of electronic delocalization in organic groups R in substituted thiocarbamoyl RCSNH2 and related compounds on inhibition efficiency

Polarization of mild steel in 1.OM hydrochloric acid containing a substituted thiocarbamoyl RCSNH₂ and related compounds has been studied at various inhibitor concentrations. The inhibition efficiency of the compound is related qualitatively to the electronic resonance in the R group.     

Effect of boron on the thermodynamic stability of amorphous polymer-derived Si(B)CN ceramics

The reason for the higher thermal persistence of amorphous polymer-derived SiBCN ceramics (T ～ 1700–2000 °C) compared to SiCN ones (T ～ 1500 °C) has been a matter of debate for more than a decade. Despite recent experimental results which indicate a major kinetic effect of boron on the thermal persistence of the ceramics, no experimental investigation of the thermodynamic stability of the materials has been reported. In this work, we present measured energetics of a series of the amorphous ceramics with various boron contents (0–8.3 at.%) using high-temperature oxidative drop-solution calorimetry. Through measurement of the drop-solution enthalpies in molten sodium molybdate at 811 °C, the formation enthalpies of the amorphous ceramics from crystalline components (SiC, BN, Si₃N₄, C) at 25 °C were obtained and found to be between ?1.4 and ?26.6 kJ g-atom^?1. The determined enthalpy data plus the estimated positive entropy of formation values point to the thermodynamic stability of the amorphous ceramics relative to the crystalline phases, but such stabilization diminishes with increasing boron content. In contrast, the higher boron content increases the temperature of Si₃N₄ crystallization despite less favorable energetics for the amorphous phase, implying more favorable energetics for crystallization. Thus the so-called “stability” of SiBCN ceramics in terms of persistence against Si₃N₄ crystallization appears to be controlled by kinetics rather than by thermodynamic stability.     

DLC薄膜摩擦行为对微拉深工艺的影响

为了降低微成形中的摩擦尺寸效应,采用基于离子注入、沉积法和磁控溅射技术在模具表面分别镀上3种涂层（DLC、TiN和MoS2）。考虑试样在接触面的塑性变形,分析了表面涂层的摩擦行为。分析表明：当使用DLC涂层时,摩擦因数较低,并且在大应力应变条件下具有较高的抗磨损性能。当进行100次摩擦实验后,DLC薄膜出现石墨化。从摩擦功影响而导致能量降低的角度分析了石墨化机理。通过减小壁厚等研究了DLC薄膜的性能对微拉深件质量的影响。结果表明,DLC薄膜有助于改善微型构件的质量。     

The role of mercury in the dissolution of aluminium sacrificial anodes: A study using ion implantation

Implantation of Hg⁺ ions into Al was used to produce, on Al, surface alloy layers consisting of a metastable AlHg solid solution. The anodic behaviour of these surface alloys was examined using potentiodynamic polarization, current-time transients at constant potential and galvanic coupling with steel. The electrochemical studies were supplemented by scanning electron microscopy and glancing-angle Rutherford backscattering measurements. The results obtained indicated that the presence of Hg in Al, even when homogeneously distributed in metastable solid solution, produced an alloy which was extremely reactive, electrochemically, and which had little immediate tendency to passivate. The reactivity was not associated with the grain boundary regions; the whole alloy dissolved more or less uniformly. The effects of implanted Hg on the dissolution of Al were relatively persistent, although they were eventually lost. The implications of these results are considered in the context of the role of mercury in the dissolution of commercial AlZnHg sacrificial anodes. In the latter materials the mercury is thought to be located primarily as a second phase in the grain boundaries but, although they exhibit some preferential grain boundary corrosion, their grain interiors also dissolve readily.     

Atom site preference and γ′/γ mismatch strain in NiAlCoTi superalloys

The structure and chemistry of NiCoAlTi quaternary superalloys are investigated at the microstructural and atomic scale. Atom probe tomograghy (APT) is used to quantify phase compositions and elemental partitioning behavior. Using aberration corrected electron microscopy, the site occupancy of the atoms within the A₃ B structure (L1₂–type) γ′ phase is determined via atomic resolution energy dispersive X-ray spectroscopy (EDX). Ni is observed to preferentially occupy the A sub-lattice positions for all alloys, while Al and Ti occupy the B sub-lattice. In contrast, Co's site preference changes from a random distribution to the A sub-lattice as the alloy composition changes, in agreement with theoretical predictions from literature. Finally, the lattice strain across the γ′/γ interfaces is measured as a function of alloy composition.     

Superhard and tougher SiC/diamond-like-carbon composite films produced by electron beam physical vapour deposition

SiC/diamond-like carbon (DLC) composite films have been produced on metal substrates via electron beam physical vapour deposition process with various substrate temperatures. The films deposited at 700 °C contain a DLC matrix and nanocrystalline 3CSiC. However, the films deposited at 900 °C contain a 3CSiC matrix and DLC plus nanocrystalline diamond. Both nanoindentation and Hysitron testing have shown that the Young’s moduli and hardnesses of the films increased with the substrate temperature. The hardness could reach ～60 GPa in some parts of the films produced at 900 °C. Meanwhile, the fracture toughness, measured using a micro-beam bending technique, reached 9.2 ± 2 MPa^1/2 for such a composite film. Both high hardness and toughness could be explained by the unique microstructure of the composite film.     

Preparation of hybrid films of aluminosilicate nanofiber and conjugated polymer

We have demonstrated the preparation of hybrid films of aluminosilicate nanofiber (imogolite) and water-soluble poly(p-phenylene) (WS-PPP), which has sulfonate groups. The imogolite/WS-PPP hybrid gel could be prepared by mixing a solution of these two materials and subsequent centrifugation. The aluminol (AlOH) groups on the surface of imogolite would be protonated under acidic conditions to afford AlOH₂⁺ groups that can interact with sulfonate groups (SO₃^?) of WS-PPP. Based on this ionic interaction, a layer-by-layer (LBL) assembly was applied to fabricate the hybrid films of imogolite nanofibers and WS-PPP. The deposited amounts of WS-PPP and imogolite were measured by quartz crystal microbalance (QCM) measurements and scanning electron microscopy (SEM) observation. Atomic force microscopy (AFM) observation revealed that imogolite nanofibers were well networked in the LBL hybrid film.     

Thermophysical properties of TiB2SiC ceramics from 300 °C to 1700 °C

In the present work, high-frequency induction heating is used to fabricate TiB₂SiC ceramics and the relative density was more than 97%, and then the thermophysical properties of TiB₂SiC ceramics were investigated in detail. The specific heat showed the weak dependence on the test temperature due to the presence of the interface gap because the relative density was not 100%. As the sintering temperature increased, the thermal diffusivity of TiB₂SiC ceramics increased, which was due to the increase of relative density and grain growth. The thermal conductivity of TiB₂SiC ceramics showed a marked increase with increasing grain size and relative density. This could be attributed to a reduction in the number of grain boundaries that interrupt the heat flow path, resulting in an increase in the mean free path of the phonons. Larger grains led to an increase of mean free path of the phonons and thus contributed to a further increase in thermal conductivity.     

The annealing and re-oxidation of oxidized CuNi alloys

A study has been made of the effects of an intermediate, isothermal annealing treatment in argon on the oxidation kinetics in dry oxygen of Cu10%Ni and Cu24%Ni at 800°C and Cu80%Ni at 1000°C using a semi-automatic microbalance. Changes in scale morphology and composition have been investigated using various techniques.Oxidation of Cu10%Ni and Cu24%Ni produces external scales consisting of a thick, inner Cu₂O layer and a thin, outer CuO layer, together with nickel-rich internal oxide in the adjacent alloy. Oxidation of Cu80%Ni yields an external scale consisting of a thick, inner NiO layer and a thin, outer CuO layer, together with a few nickel-rich internal oxide particles in the adjacent alloy. During annealing, the outer CuO layers on the three alloys dissociate to give Cu₂O and oxygen. With Cu80%Ni only, further dissociation to give copper metal takes place after long annealing times. In all cases, the annealing treatment leads to a reduction in the cation vacancy gradient across the scale and a reduction in the total vacancy level in the scale due to the reduction in oxygen activity at the oxide-gas interface.In Cu10%Ni and Cu24%Ni, internal oxide formation during annealing stimulates dissociation of the Cu₂O scale near the oxide-alloy interface to give copper metal and oxygen. Similarly, internal oxide formation stimulates dissociation of the NiO layer on Cu-80%Ni, although to a lesser extent than for the copper-rich alloys.During re-oxidation, the kinetics are partly determined by the extent of scale thinning during the prior annealing treatment, giving more rapid weight gains than expected from those recorded during the initial oxidation period. Nevertheless, particularly for Cu-80%Ni, where the scale thinning is relatively small, the reduction in the cation vacancy gradient across the scale and the reduction in the total vacancy level in the scale do result in a reduced oxidation rate compared with the rate recorded during the initial oxidation period.     

Designed fabrication of hard CrCr2O3Cr7C3 nanocomposite coatings for anti-wear application

Nanocrystalline CrCr₂O₃Cr₇C₃ composite coatings were fabricated by electrodeposition followed by thermal treatment. The structures of coatings were investigated using high-resolution transmission electron microscopy and X-ray diffraction analysis. The composition, elemental chemical state, mechanical properties and wear resistance of coatings were determined using energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, nanoindentation and oscillating friction-wear testing, respectively. Wear tracks were observed by scanning electron microscopy. The results show that the as-deposited coating exhibits amorphous structure. The subsequent thermal treatment at 600 °C induces the crystallization and the generation of nanoscale Cr₂O₃ and Cr₇C₃ particles in the Cr-matrix, which results in the hardness of the coating increasing to 21 GPa with slight increase in elastic modulus. Owing to the compromise between high hardness and low elastic modulus, the obtained CrCr₂O₃Cr₇C₃ composite coating exhibits excellent wear resistance.     

Manufacture of a new kind diamond grinding wheel with Al-based bonding agent

A new kind diamond grinding wheel with Al-based bonding agent was prepared in this paper. The influence of sintering temperature to the relative density (R.D.), hardness and service life of diamond grinding wheels with AlSnTi, AlSnTiNiCo, AlSnTiNi and AlSnNiCo bonding agent was studied. The microstructure of different bonding agent sintered at different temperature was observed. The service life of the Al-based grinding wheels was compared with Cu-based or resin-based ones. The results showed that the AlSnTiNiCo is the best composition system in this research. The best sintering temperature is 300 °C. The sample has a high relative density after sintered at 300 °C. The retention of Al-based bonding agent to diamond grit is strong. The service life of this Al-based diamond grinding wheel is about three times as long as that of resin-bonded grinding wheel.     

Crystal structure and magnetic properties of an ionic multi-component complex of fullerene (OMTTF·I3)·C60: Comparison with OMTTF·I3 salts

A new ionic multi-component complex (OMTTF·I₃)·C₆₀ comprising neutral C₆₀ molecules and OMTTF⁺ and I₃⁻ ions has been obtained by the diffusion method. The complex has a layered structure with the alternation of closely packed hexagonal C₆₀ layers and the layers composed of OMTTF⁺ and I₃⁻ ions arranged in a chequer-like manner. The polycrystalline complex shows a strongly asymmetric EPR signal consisting of four components in the 4–293 K range attributable to OMTTF⁺. Temperature dependent magnetic susceptibility indicates an antiferromagnetic interaction of spins localized on OMTTF⁺ with an antiferromagnetic hump near 4.5 K. According to the one-dimensional Heisenberg antiferromagnet model the exchange interaction was estimated to be J/k_B = −3.3 K. Two possible pathways contribute to this interaction: through the diamagnetic I₃⁻ anions and the direct interaction between adjacent OMTTF⁺. The crystal structures of three phases of the OMTTF·I₃ salt are also presented.     

New 1,3,4-oxadiazole containing materials with the effective leading substituents: The electrochemical properties,optical absorptions,and the electronic structures

The electrochemical and optical absorption properties as well as the thermal stabilities of a series of 1,3,4-oxadiazole dimers 1,3-bis[2-(4-methylphenyl)-1,3,4-oxadiazol-5-yl]benzene (OXD-X) and its derivatives with the different alkoxy substituents on the central benzene ring such as O(CH₂)_n−1CH₃ (OXD-An, n = 3, 7, 10, 16), O(CH₂)_nOC₆H₅CH₃ (OXD-Bn, n = 6), and O(CH₂)_nOC₆H₄NNC₆H₄OCH₃ (OXD-Cn, n = 3, 6, 10) are studied. The DSC measurements exhibit dramatically elevated glass transition temperatures for OXD-X and OXD-An (120–245 °C) in contrast to the well-known PBD (∼60 °C), indicating the better thermal stabilities. From OXD-X to OXD-An, OXD-Bn or OXD-Cn, the cyclic voltammograms and UV–vis absorption spectroscopy display significant variation, in which the later three species show additional lower energy absorptions at λ > 330 nm compared with OXD-X and particularly, both of OXD-Bn and OXD-Cn display an oxidation peak at ∼+1.0 V and two successive redox reactions occur for OXD-Cn. Theoretically, the B3LYP/6-31g calculations explore that these extraordinary properties are due to the influence of the substituents on the benzene ring to the frontier molecular orbital distribution, especially the O(CH₂)_nOC₆H₄NNC₆H₄OCH₃ groups in OXD-Cn deduce the new pictures of the frontier molecular orbitals, causing the electron-transporting behavior originally happening on the molecular skeleton transferred to the side chain.     

Study on the formation of core–rim structure in Ti(CN)-based cermets

Ti(CN)-based cermets were synthesized from Ti(CN)WCMo₂CTaCNiCo composite powders by vacuum-low pressure sintering. The phase evolution and the formation of core–rim structure in Ti(CN)-based cermets were systemically investigated during difference reaction stages at 950–1450 °C. The results show that the secondary carbides such as Mo₂C and TaC are begun to dissolve at 950 °C, finished at 1150 °C, and the solution temperature of WC phase is range from 1150 to 1300 °C, which are result in increase of the cermets lattice constant. At the same time, the inner rim is also formed, and Ti(CN)-based cermets are composed of (Ti, W, Mo, Ta)(CN) and Ni/Co solid solution phase. While at 1350 °C, it was found that the outer rim began to precipitate from the liquid phase with the metal binder. With increase of sintering temperature, mechanical properties of cermets improved obviously were related intimately to the increase of outer rim thickness.     

Effects of deep cryogenic treatment on the microstructure and properties of WCFeNi cemented carbides

The effects of deep cryogenic treatment on microstructure and properties of WCFeNi cemented carbides were investigated in this paper. The WCFeNi cemented carbides were deep cryogenically treated at about − 196 °C for 2, 12 and 24 h. In order to study the phase composition and quantitative analysis of the deep cryogenically treated specimens, a selective electrolytic corrosion was used. The internal friction, mechanical properties, wear properties and corrosion behavior of the deep cryogenically treated WCFeNi cemented carbides were measured. The results show that with an increase in deep cryogenic treatment time, martensitic phase transformation of binder phase from γ → α has taken place, the α-(Fe,Ni) phase content in the binder phase gradually increases from 12.7% to 86.8% (wt.%) and W particles precipitate from the binder phase. Compared with the as-sintered specimens, the maximum hardness and transverse rupture strength of the specimens treated by cryogenic environment increase by almost 20% and 7.7%, respectively. The fracture toughness decreases from 25.7 MPam^½ for as-sintered specimens to 19.6 MPam^½ for the alloy after deep cryogenic treatment. The wear rate and friction coefficient decrease by almost 56% and 17.2%, while the corrosion resistance slightly decreases compared with the alloys without deep cryogenic treatment. The change of the properties can be primarily attributed to the fact that the martensite phase transformation from γ-(Fe,Ni) to α-(Fe,Ni) and precipitation of W particles in the binder phase improve the hardness and strengthen the binder phase during the deep cryogenic treatment.     

First-principles investigation of magnetic properties and metamagnetic transition of NiCoMnZ(Z = In,Sn, Sb) Heusler alloys

We employed the density functional theory to investigate the structural, magnetic properties and metamagnetic transition on Mn and Co doped-Ni₂MnZ (Z = In, Sn, Sb) Heusler alloys. The calculated formation energy indicates that excess Mn and Co prefer to occupy Z and Ni sites, respectively. The energy difference between austenite and martensite phases exhibits a monotonic increase with Mn doping, and a decrease with Co doping, which are consistent with the trend of experimental martensitic transformation temperature. The evaluated magnetic exchange parameters show a strong dependence on Z element, which can be explained by the super-exchange interaction mediated by Z sp states near the Fermi level. Bond analysis of martensite phase reveals that the strength of MnSb bond is stronger than that of MnIn and MnSn bond and it explains the larger driving magnetic field in NiMnSb than NiMnZ(Z = In, Sn) is need for metamagnetic phase transformation. In addition, we predict NiCoMnZ (Z = Sn, Sb) alloys require a smaller compressive epitaxial strain for metamagnetic transition than NiCoMnIn alloys.     

Supramolecular associations of poly(ketanil)s with sulfonic acid derivatives of benzenetricarboxamide via Brönsted acid–base interactions: Preparation,spectroscopic morphological and thermal investigations

Supramolecular aggregations have been obtained via ionic self-assembly of conjugated poly(ketanil)s and sulfonic acid derivatives of benzenetricarboxamides. To achieve this goal a new protonating molecule has been synthesized which is a derivative of 1,3,5-benzenetricarboxamide with sulfonic acid group at each of its ends. 1,3,5-benzenetricarboxamides of C₃ symmetry tend to form ordered supramolecular aggregations via π-stacking and this property is retained in their sulfonic acid derivative. Because of their Brönsted acid nature the new molecules can additionally associate conjugated polymers with basic centers such as poly(ketanil)s. Depending on the processing solvent used (MC or DMA) 1,3,5- the sulfonic acid derivative of benzenetricarboxamide and its associations with poly(ketanil)s form aggregations of spherullite-like or feather-like morphologies as evidenced by polarized optical microscopy and atomic force microscopy. The similarity of this supramolecular organization is also corroborated by DSC studies which in both cases show endothermic type transitions of the same origin. The supramolecular acid–base associations are semi-crystalline in nature and exhibit good mechanical properties at room temperature because of a rather low T_g, in the vicinity of 300 K. This unusual lowering of T_g by ca. 90 K as compared to the case of poly(ketanil)s in their basic form is caused by the plasticizing effect of the protonating agent. Finally polyketanil–1,3,5-benzenetricarboxamide sulfonic acid derivatives show tunable photoluminescence which depends on the solvent and SO₃H/CN molar ratio.     

Nitridation of Ti6Al4V alloy under ultrasonic impact treatment in liquid nitrogen

X-ray photoelectron spectroscopy and scanning electron microscopy with energy dispersive X-ray microanalysis were employed to study the effect of mechanical treatment on the surface chemical state, composition and morphology of commercial Ti6Al4V alloy. It has been demonstrated that ultrasonic impact treatment of Ti6Al4V in a liquid nitrogen (LN2) environment results in substantial grain refinement and formation of nitrides and oxynitrides of all the alloy components. The mechanochemical synthesis of the nitrides and oxynitrides from LN2 was found to efficiently occur not only within the impacted area but outside it as well. The layer with a high content of incorporated nitrogen and average atomic ratio N/Ti = 0.94 was estimated to be at least ～2 μm thick. As a result of the combined effect of cryogenic deformation, nanoscale grain refinement and nitriding, a 3-fold increase in the microhardness of Ti6Al4V alloy is obtained. The impact treatment in LN2 was observed to be accompanied by material transfer from the hardened steel pin to the alloy followed by incorporation of the pin components into Ti6Al4V and formation of the FeN, FeC and TiC bonds.