Modification of the Kolmogorov–Johnson–Mehl–Avrami rate equation for non-isothermal experiments and its analytical solution

Avrami’s model describes the kinetics of phase transformation under the assumption of spatially random nucleation. In this paper we provide a quasi-exact analytical solution of Avrami’s model when the transformation takes place under continuous heating. This solution has been obtained with different activation energies for both nucleation and growth rates. The relation obtained is also a solution of the so-called Kolmogorov–Johnson–Mehl–Avrami transformation rate equation. The corresponding non-isothermal Kolmogorov–Johnson–Mehl–Avrami transformation rate equation differs from the one obtained under isothermal conditions only by a constant parameter, which depends only on the ratio between nucleation and growth rate activation energies. Consequently, a minor correction allows us to extend the Kolmogorov–Johnson–Mehl–Avrami transformation rate equation to continuous heating conditions.     

Synthesis of ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders by low-energy milling and subsequent carbothermal reduction–nitridation reaction

Ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders with globular-like particles of 50–300 nm were synthesized at static nitrogen pressure from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation (CRN) techniques. Reaction path of the (Ti, W, Mo, V)(C, N)–Ni system was discussed by X-ray diffraction (XRD) and thermogravimetry–differential scanning calorimetry (TG–DSC), and microstructure of the milled powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that CRN reaction has been enhanced by nano-TiO₂ and nano-carbon powders. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N)–20Ni is at only 1300 °C for 1 h. During synthesizing reaction, Ni solid solution phase forms at about 700 °C and reduction–carbonization of WO₂ and MoO₂ occurs below 900 °C. The reactions of TiO₂ → Ti₃O₅, Ti₃O₅ → Ti(C, O) and Ti(C, O) → Ti(C, N) take place at about 930 °C, 1203 °C and 1244 °C, respectively.     

Reinforcement of Al–Fe–Ni alloys with the in situ formation of composite materials

One of the most effective methods for the improvement of the mechanical properties of metals is their reinforcement with non-metallic materials. In the present work powder of K₂TiF₆ and KBF₄ was added in an Al–Fe–Ni alloy while the alloy was in liquid form at 1060 °C with a 5 wt.% mixture of powders and with simultaneous stirring for 30 min. The liquid was squeeze-casted at 150 bar. The as-cast specimens were examined with electron microscopy and X-ray diffraction. SEM analysis revealed that the as-formed material is composed by needle-like crystallites along with a dentritic form and an interdendritic phase. The composition of the needle-like crystallites may presumably be expressed by the formula (Fe-Ni)Al₃. The rest of the matrix consists of almost pure Al grown dentritically, while the interdendritic phase contains Fe and Ni dissolved in Al. EDS analysis also proved the existence of spots with high Ti concentration, which probably refer to the Ti–B compounds. Finally TEM verified the presence of nanocrystals in the matrix.     

The response of carbon black filled high-density polyethylene to microwave processing

Microwave processing has numerous advantages over traditional methods of heating. Most thermoplastics, such as high-density polyethylene (HDPE), are nearly transparent to electromagnetic radiation. Carbon black (CB) filled HDPE was prepared in order to improve the microwave heatability of HDPE. The heating response of HDPE/CB composites to microwave exposure and the effects of this exposure on the mechanical and physical properties of material were investigated. The addition of CB particles improved the microwave heatability of HDPE, and microwave heatability of composites varied with CB content, in which an average temperatures of up to 139 °C above ambient were measured for 20 wt% CB composites after a exposure duration of 150 s. Microwave exposure had no obvious effect on rheological property of HDPE/CB composites. Mechanical properties of HDPE/CB composites are relatively improved after microwave exposure. Scanning electronic micrograph (SEM) analysis presented that the interface defects between CB particles and HDPE matrix are significantly reduced and a better combination was found after microwave exposure. Differential scanning calorimetry (DSC) analysis showed that the melt point of HDPE with CB shifted toward high temperature and degree of crystallinity increased after microwave exposure.     

Characterization of crystallization kinetics of a Ni- (Cr, Fe, Si, B, C, P) based amorphous brazing alloy by non-isothermal differential scanning calorimetry

The thermal stability and crystallization kinetics of a Ni- (Cr, Si, Fe, B, C, P) based amorphous brazing foil have been investigated by non-isothermal differential scanning calorimetry. The glass transition temperature T_g, is found to be 720 ± 2 K. The amorphous alloy showed three distinct, yet considerably overlapping crystallization transformations with peak crystallization temperatures centered around 739, 778 and 853 ± 2 K, respectively. The solidus and liquidus temperatures are estimated to be 1250 and 1300 ± 2 K, respectively. The apparent activation energies for the three crystallization reactions have been determined using model free isoconversional methods. The typical values for the three crystallization reactions are: 334, 433 and 468 kJ mol⁻¹, respectively. The X-ray diffraction of the crystallized foil revealed the presence of following compounds Ni₃B (Ni₄B₃), CrB, B₂Fe₁₅Si₃, CrSi₂, and Ni_4.5Si₂B.     

The isothermal section of the Ti–Co–Zr ternary system at 773 K

The phase equilibria of the Ti–Co–Zr ternary system at 773 K have been investigated mainly by powder X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive analysis (EDX). The isothermal section consists of 16 single-phase regions, 31 two-phase regions and 16 three-phase regions. There are 11 binary compounds, i.e. CoZr₃, CoZr₂, CoZr, Co₂Zr, Co₂₃Zr₆, Co₁₁Zr₂, TiCo₃, h-TiCo₂, c-TiCo₂, TiCo, Ti₂Co in the system. The existence of two ternary compounds Co₁₀Ti₇Zr₃ and Co₆₆Ti₁₇Zr₁₇ has been confirmed at 773 K. Co₂Zr, CoZr₃ and TiCo have a range of homogeneity. The solubilities of Ti in CoZr was determined to be up to 8.1 at.% Ti.     

Characterization of an amorphous–crystalline Mg-based composite

An amorphous–crystalline Mg-based composite with the nominal composition of Mg₆₅Cu₂₀Zn₅Y₁₀ has been formed by casting. X-ray diffractometry, differential scanning calorimetry, backscatter electron imaging, and energy dispersive X-ray analysis were used to characterize the structure of the composite, which is linked to the hardness, modulus, and fracture toughness obtained by Vickers and nanoindentation. Comparisons of the structure–property relationships are also made to composite materials of a similar composition. The effects of the crystalline microstructure on localized deformation through shear banding are discussed and related to the hardness and toughness results.     

Differential calorimetric analysis of the binary system Sb–Zn

The experimental study of the system Sb–Zn by differential calorimetry made it possible to plot the whole phase diagram. We found the stability domains of existence of the stoichiometric compound SbZn and the solid solutions which extend on both sides from the compositions corresponding to Sb₃Zn₄ (forms γ and β) and Sb₂Zn₃ (forms η and ζ). Sb₃Zn₄ and Sb₂Zn₃ are both congruent melting compounds at 566 and 568 °C respectively with an eutectic transformation at 563 °C:

liquid(43% Zn) ↔ Sb₃Zn₄(γ) + Sb₂Zn₃(η).

Sb₂Zn₃(ζ) is formed at 407 °C starting from Sb₃Zn₄(β) and zinc. The decomposition, by cooling, occurs around 360 °C.     

Nanocrystalline electroless nickel poly-alloy deposition: incorporation of W and Mo

Autocatalytic quaternary Ni–W–Mo–P films were prepared using alkaline citrate based baths and compared with binary Ni–P and ternary Ni–W–P, Ni–Mo–P coatings. Energy dispersive X-ray analysis showed that the binary Ni–P deposit contained 12·2 wt-%P. Codeposition of tungsten in Ni–P matrix resulted in ternary Ni–W–P with 4·1 wt-%P and 5·2 wt-%W. Incorporation of molybdenum led to a ternary Ni–Mo–P deposit containing 4·1 wt-%Mo and 11·2 wt-%P. Presence of both sodium tungstate and sodium molybdate in the basic bath resulted in a quaternary coating with 3·6 wt-%W, 6·7 wt-%Mo and 2·5 wt-%P. X-ray diffraction patterns of all the deposits revealed a single peak for Ni (1 1 1). The quaternary alloy exhibited a sharper peak showing the more crystalline nature of the deposit. Field emission scanning electron microscopy studies of the deposits showed the presence of smooth nodules for ternary deposits, but coarse and well defined nodules for quaternary deposits. Phase transformation behaviour of the ternary Ni–W–P deposit revealed a single exothermic peak at 440°C. However, ternary Ni–Mo–P deposit exhibited a split type high temperature peak at 397 and 461°C and the quaternary Ni–W–Mo–P deposit showed a single high temperature peak at 485°C. Microhardness measurements showed that the quaternary Ni–W–Mo–P deposit exhibited increased hardness of 920 HV(50 gf) when heat treated for 1 h at 400°C.     

A study on electrochemical growth behavior of the Co–Ni alloy nanowires in anodic aluminum oxide template

This study shows the growth behavior of Co–Ni alloy nanowires in AAO template. Growth of nanowires consists of four different stages namely electronucleation, steady state growth, filling of pores, and coverage of filled nanowires and forming of a film on the template surface. TEM study of nanowires showed that the nanowires possess hemispherical head due to the preferable and more rapid growth phenomenon in central section of nanowires instead of edge sides. Studies on the relations between nanowires composition and ion concentration in solution showed that growth of nanowires is a diffusion-controlled process. The compositional, structural and magnetic properties of nanowires were investigated by means of EDX, TEM and VSM.     

Electrical behaviour of hydridofluorides of potassium–calcium KCaH3−xFx with x = 1, 1.5, 2, 2.5

This paper reports the results of the electrical conductivity measurements for KCaH_3−xF_x series with (x = 1, 1.5, 2, 2.5) in the temperature range 298–503 K.The activation energy of the electrical conductivity for the studied compounds depends on hydrogen amount and Reau's criteria. Differential thermal analysis curves were measured in the same temperature range 298–503 K.Possible correspondence between preferential order given by X-ray diffraction, thermal behaviour and electrical properties are discussed.     

Surface finishing of Ni–Cr–B–Si composite coatings by precision grinding

A Ni–Cr–B–Si/10vol%WC coating material has been precision ground to an optical quality surface finish (<10 nm R_a) using a combination of a very stiff precision machine tool, Tetraform “C”, 76 μm CBN grinding wheels and electrolytic in-process dressing (ELID) assisted grinding. When grinding without ELID, surface finish has been shown to be limited by damage to primary and secondary carbides. This damage may be in the form of carbide pull-out or localised fracture and removal of the larger primary WC particulate. ELID assisted grinding helps maintain CBN grit protrusion and sharpness and thus promotes efficient cutting during grinding, minimising pull-out and localised damage to the harder phases within the coating microstructure. ELID therefore improves both the overall surface finish and surface integrity of the workpiece.     

Thermal stability of nanocrystalline Ni- and Co-based pulsed current electrodeposits: correlation of calorimetric measurements and microstructure development upon annealing

The exceptional properties associated with nanocrystalline materials are, to a large extent, a result of their high inter-crystalline volume fraction. However, the intrinsic instability of the nanostructured state may compromise the gain in properties by the occurrence of grain growth during exposure at elevated temperatures. Thermal stability is, therefore, a fundamental materials issue for nanocrystalline materials. This article describes what can be deduced from calorimetric measurements in the context of what is known about the microstructural evolution upon annealing of nanocrystalline Ni- and Co-based pulsed current electrodeposits. Special emphasis is put on interpreting the shape of the curves obtained by a differential scanning calorimetry (DSC). The temperature ranges for relaxation, segregation, precipitation, as well as abnormal and normal grain growth can be predicted. Also, by evaluating the shift in peak temperature with heating rate (Kissinger plot), the activation energies for grain growth can be obtained for the different materials.     

The microstructure of liquid immiscible Fe–Cu-based in situ formed amorphous/crystalline composite

In the microstructures of slowly and rapidly cooled liquid of the immiscible alloy Fe₃₀Cu₃₂Ni₁₀Si₁₃Sn₄B₉Y₂ two distinct regions were observed following arc melting and slow cooling, confirming that liquid/liquid phase separation had occurred. Rapid cooling from a temperature within the liquid immiscibility gap, melt spinning, resulted in an amorphous/crystalline composite, formed from the previously melted Fe- and Cu-rich regions, respectively. Transmission electron microscopic studies of this melt-spun ribbon revealed the glassy nature of the Fe-rich matrix, as well as of the Fe-rich spheres formed within the previously existing Cu-rich liquid.     

Structural effects of shot-peening in bulk metallic glasses

Shot-peening induces surface compressive stresses in bulk metallic glass components, improving their plasticity. Structural changes in the peened surface of fully glassy and partially crystalline Zr₅₅Al₁₀Cu₃₀Ni₅ are studied by X-ray diffraction, transmission electron microscopy and differential scanning calorimetry. An earlier study is extended by examining the effect of sample temperature. While fully glassy samples show no phase change under peening, partially crystalline samples show either amorphization or crystallization depending on temperature. Peening can induce very large stored energy in metallic glasses rendering them susceptible to crystallization below room temperature, a result which may be relevant for improving the plasticity of these materials.     

Observations on the growth of Al–Ni–Co decagonal thin films by atomic force microscopy and transmission electron microscopy

Thin films of Al–Ni–Co alloy were produced by vacuum deposition technique using a substrate material of amorphous carbon thin-foil. Attempts were made to obtain a homogeneous decagonal quasicrystalline film, where the preparation technique was based on the direct evaporation of pre-alloyed ingot of Al₇₂Ni₁₅Co₁₃ onto the heated substrates. In order to explore early stages of the decagonal film growth, the Al–Ni–Co films with different thicknesses ranging from 2 nm to 30 nm were deposited on either substrates heated at 500 °C or non-heated substrates. The film samples so obtained were examined mainly by atomic force microscopy in combination with transmission electron diffraction and imaging techniques. On the basis of these observations, deposition conditions necessary for the growth of decagonal phase in the resulting films as well as the growth mechanism of the decagonal film will be discussed.     

Evaluation of WC–17Co and WC–10Co–4Cr thermal spray coatings by HVOF on the fatigue and corrosion strength of AISI 4340 steel

It is known that chromium electroplating is related to the reduction in the fatigue strength of base metal. However, chromium results in protection against wear and corrosion combined with chemical resistance and good lubricity. Environmental requirements are an important point to be considered in the search for possible alternatives to hard chrome plating. Aircraft landing gear manufactures are considering WC thermal spray coating applied by the high-velocity oxygen-fuel (HVOF) process an alternative candidate, which shows performance at least comparable to results, obtained for hard chrome plating. The aim of this study is to compare the influence of WC–17Co and WC–10Co–4Cr coatings applied by HVOF process and hard chromium electroplating on the fatigue strength of AISI 4340 steel, with and without shot peening. S–N curves were obtained in axial fatigue test for base material, chromium plated and tungsten carbide coated specimens. Tungsten carbide thermal spray coating results in higher fatigue strength when compared to hard chromium electroplated. Shot peening prior to thermal spraying showed to be an excellent alternative to increase fatigue strength of AISI 4340 steel. Experimental data showed higher axial fatigue and corrosion resistance in salt fog exposure for samples WC–10Co–4Cr HVOF coated when compared with WC–17Co. Fracture surface analysis by scanning electron microscopy (SEM) indicated the existence of a uniform coverage of nearly all substrates.