Crystallisation and performance characteristics of high‐temperature annealed electroless Ni‐W‐P coatings

Electroless deposition of Ni–P based alloys is a well‐known commercial process that has numerous applications because of their excellent anticorrosive and wear properties. However, for some special occasions, like the components for gas making furnaces in chemical fertiliser industry, the coatings must be reinforced to withstand short‐term high temperatures between 600 °C and 700 °C as well as light erosive wear. Therefore, co‐deposition of high melting point metallic element, W, has been considered as a preferred choice. In the present study, two Ni–W–P alloy coatings were deposited on mild steel panels from different alkaline baths. The microstructures of the annealed coatings were characterised by quantitative XRD, XPS and SEM/EDS analysis techniques and their microhardness, friction and wear behaviour, corrosion mechanism as well as microstrain and residual stress are discussed in comparison with the as‐plated state. The results indicate that the hardness mainly depends on the volume fraction and crystallite size of Ni₃P phase; the uniform corrosion in sulfuric acid solution is closely related to the ratio of I_Ni/I_Ni3P as well as grain size. The wear mechanism of the high‐temperature annealed coating is dominated by abrasive wear, but the wear in the early stages started from mild adhesive wear caused by adhesion between the friction couples. Electroless deposited Ni‐W‐P alloys with high phosphorus present relatively good properties, including hardness, wear and corrosion resistance when 700 °C is applied for annealing process.     

Microstructure evolution and grain size distribution in nanocrystalline FeNbBCu from synchrotron XRD and TEM analysis

The microstructure evolution during nanocrystallization of an Fe₇₇Nb₇B₁₅Cu₁ amorphous alloy is investigated using in situ synchrotron X-ray diffraction (XRD) and transmission electron microscopy (TEM). The microstructure of the nanocrystallized alloy consists in dispersion of bcc-Fe nanocrystals of 4–6 nm of diameter embedded in a stabilized amorphous remaining matrix. The grain size distribution of the nanocrystalline Fe₇₇Nb₇B₁₅Cu₁ alloy was obtained using three different methodologies: statistical analysis of TEM images, the Warren–Averbach and Langford methods to analyse the XRD patterns and modelling of the diffraction pattern from the Debye equation. A lognormal distribution function has been assumed in all three methods in order to obtain comparable results. A good agreement is found in the calculated average radius and dispersion although some deviations are found with the Langford approach. The microstructure evolution during crystallization was obtained from the XRD patterns during heating (5.0 · 10^?3 K s^?1) at temperatures between 700 and 900 K. A decrease and prompt saturation of the growth rate is obtained, indicative of the diffusion barrier caused to the overlap between the concentration gradients at the interface of growing grains (soft impingement). A simple model assuming nucleation and initial fast growth of the crystalline grains followed by reduced growth capable of predicting microstructural evolution is presented. The modelling results agree with the experimental observations.     

Microstructure evolution and thermal properties in FeMoPCB alloy during mechanical alloying

Fe_79.3Mo_4.5P_8.1C_6.75B_1.35 amorphous alloy composite powder from respective element powders of Fe, Mo, C, B, and Fe–P intermediate compound, was synthesized by mechanical alloying. Microstructure evolution analysis indicates that the synthesized amorphous alloy composite powder after a milling time of 70 h encompasses predominately amorphous matrix embedded by nanocrystalline α-Fe with a grain size of about 5.5 nm. However, unlike other Fe-based amorphous alloys, the synthesized amorphous alloy composite powder exhibits no obvious supercooled liquid region with only crystallization temperature. The corresponding crystallization onset temperature and exothermic enthalpy measured from DSC curves are about 762 K and 15.86 J/g, respectively. The results obtained provide good candidate materials for fabricating bulk metallic glass composites and related bulk nanocrystalline materials.     

The structure of amorphous and nanocrystalline W---Fe alloys prepared by high-energy ball milling

Tungsten powder (99.9% purity, 12 μm particle size) was milled in a hardened steel vial with six 440C stainless steel balls for 1–50 h. Because of the hardness of W, contamination and later alloying with Fe from abrasion of the stainless steel balls occurred. X-ray chemical analysis and weight-gain measurements of the milled powder indicated Fe contents varying from 3 at.% after 1 h to approximately 40 at.% after 50h milling. The powder pattern peaks of the nanocrystalline W were subjected to a Fourier analysis to determine the effective particle size and the microstrains within these particles. After 20 h milling, a particle size of 35 Å and microstrains of 0.5% were observed. The diffraction patterns from the W powder milled for 20 and 50 h were also analyzed in terms of the structure factor (interference function) and the atomic distribution function. The 20 h sample was predominantly nanocrystalline with a broad diffuse peak under the (110) and (211) reflections, while the 50 h sample was predominantly amorphous. After subtracting the remnant crystalline peaks, the position of the first peak in the reduced atomic distribution function, G_I(r), was found to be 2.7 Å.     

XPS characterization of corrosion films formed on the crystalline, amorphous and nanocrystalline states of the alloy Ti60Ni40

X-ray photoelectron spectroscopy investigations were carried out on the crystalline, amorphous and nanocrystalline states of the alloy Ti₆₀Ni₄₀ after corrosion test in 1 M HNO₃ aqueous medium using potentiodynamic polarization method. Polarization plots revealed that the nanocrystalline state is more corrosion resistant than the amorphous and crystalline states of the alloy Ti₆₀Ni₄₀. The XPS characterization of the oxide film formed after corrosion tests revealed that a multiple phase oxide film is formed on the crystalline and amorphous specimens of the alloy Ti₆₀Ni₄₀ consisting of Ti²⁺, Ti³⁺ and Ti⁴⁺ species along with some unoxidized Ti in metallic form (Ti⁰) in the case of crystalline specimen whereas the oxide film formed on nanocrystalline specimen consists of only Ti²⁺ and Ti⁴⁺ species. The high corrosion resistance of nanocrystalline state is attributed to the presence of fewer oxide species in the oxide film than that of the amorphous and crystalline states of the alloy Ti₆₀Ni₄₀.     

Effects of microalloying with 3d transition metals on glass formation in AlYFe alloys

The effects of microalloying on glass formation and stability were systematically investigated by substituting 0.5 at.% of all 3d transition metals for Al in Al₈₈Y₇Fe₅ alloys. X-ray diffraction and isothermal differential scanning calorimetry studies indicate that samples containing microadditions of Ti, V, Cr, Mn, Fe and Co were amorphous, while those alloyed with Ni and Cu were not. The onset temperatures for crystallization (devitrification) of the amorphous alloys were increased with microalloying and some showed a supercooled liquid region (ΔT_x = T_x − T_g) of up to 40 °C. In addition, microalloying changes the glass structure and the devitrification sequence, as determined by differential scanning calorimetry (DSC), X-ray diffraction (XRD), transmission electron microscopy (TEM), differential thermal analysis (DTA) and high energy X-ray diffraction. The results presented here suggest that the order induced in the alloy by the transition metal microaddition decreases the atomic mobility in the glass and raises the barrier for the nucleation of α-Al, the primary devitrifying phase in most cases. New intermetallic phases also appear with microalloying and vary for different transition metal additions.     

Magnetic response of Cu (25 wt.%)-316 grade stainless steel processed by ball milling

Powder blend comprising Cu (25 wt.%) and 316-stainless steel (75 wt.%) has been subjected to ball milling upto 70 h followed by isothermal annealing at the temperature range of 350–750 °C for 1 h to investigate the evolution of microstructure and magnetic properties. The ball milling of the powder blends after 10 h has resulted in partitioning of the austenite stabilizing elements such as Ni from 316-stainless steel to elemental Cu leading to the transformation of the Bravais lattice of the Fe-rich phase from fcc (γ) to bcc (α). During further ball milling of the powder mixture upto 20 h, the α-Fe has dissolved completely in Cu, leading to the formation of partial amorphous phase after 70 h of milling. The amorphous phase of the alloy has been found to stable after annealing at 350 °C and super paramagnetic in nature. Annealing of the alloy at higher temperatures has resulted in precipitation of nanocrystalline bcc-Fe in the Cu evolving ferromagnetic properties. Annealing at 750 °C has resulted in collapse of the hysteresis loop due to the diminished exchange interaction as the result of grain coarsening of the α-Fe and Cu.     

A simple synthesis of large-scale SiC–SiO2 nanocables by using thermal decomposition of methanol: Structure, FTIR, Raman and PL characterization

Large-scale SiC nanocables were synthesized on a Ni(NO₃)₂-catalyzed Si substrate by using a simple and cheap method based on thermal decomposition of methanol. Based on X-ray diffraction and high-magnification transmission electron microscopy, the as-grown nanocables consisted of crystalline SiC cores and amorphous SiO₂ shells. The diameters of SiC cores were 5.7–10 nm and the thicknesses of SiO₂ shells were 9–20 nm. Dividing of nanocables was observed and its origin was investigated. An asymmetric feature of SiC TO band with a shoulder at the high-frequency side was attributed to the contribution of SiC TO mode. The nanocables displayed strong violet–blue emission. A possible growth mechanism was proposed.     

Influence of nickel content on the electrochemical behavior of Finemet type amorphous and nanocrystalline alloys

The aim of this work has been the systematic study of the influence of partial substitution of Fe by Ni in the Ni_xFe_73.5−xSi_13.5B₉Nb₃Cu₁ alloy within the range 0 ⩽ x ⩽ 10% atom (x = 0, 2, 4, 6, 8, 10) on electrochemical behavior, corrosion rate and the structural changes in amorphous and nanocrystalline alloys. The amorphous nature of the alloys was confirmed by X-ray diffraction and the chemical compositions were determined by ICP. The glass transition and kinetic crystallization of amorphous alloys were studied by DSC. The technique of XPS was used for evaluating the chemical states of elements present in native oxide films. The electrochemical behavior of amorphous and nanocrystalline alloys have been investigated in 0.5 M KOH using cyclic voltammetry. The experimental results show that the formation of different nanocrystalline phases is not excessively transformed by the addition of small amount of nickel and the electrochemical behavior is improved as nickel content increased.     

Effect of P incorporation on aggregation of nanocrystallites in amorphous and nanocrystalline mixed-phase silicon thin films

We report the effects of P incorporation on the nanometer-scale structural and electrical properties of amorphous and nanocrystalline mixed-phase Si:H films. In the intrinsic and weakly P-doped (3 × 10¹⁸ at/cm³) films, the nanocrystallites aggregate to cone-shaped structures. Conductive atomic force microscopy images showed high current flows through the nanocrystalline cones and a distinct two-phase structure in the micrometer range. Adding PH₃ into the processing gas moved the amorphous/nanocrystalline transition to a higher hydrogen dilution ratio required for achieving a similar Raman crystallinity. In a heavily P-doped (2 × 10²¹ at/cm³) film, the nanocrystalline aggregation disappeared, where isolated grains of nanometer sizes were distributed throughout the amorphous matrix. The heavily doped mixed-phase film with 5–10% crystal volume fraction showed a dramatic increase in conductivity. We offer an explanation for the nanocrystalline cone formation based on atomic hydrogen enhanced surface diffusion model, and propose that the coverage of P-related radicals on the existing nanocrystalline surface during film growth and the P segregation in grain boundaries are responsible for preventing new nucleation on the surface of the existing nanocrystallites, resulting in nanocrystallites dispersed throughout the amorphous matrix.     

Structure and thermomagnetic properties of powders produced from melt spun FeNbBCu ribbons

Amorphous ribbons of Fe₇₇Nb₇B₁₅Cu₁ prepared by melt-spinning and powders produced from them by ball-milling were characterized by means of calorimetry, X-ray diffraction, scanning electron microscopy and vibrating sample magnetometry. Upon thermal treatment the amorphous alloy experiences a primary crystallization that leads to bcc-Fe nanocrystals dispersed in an amorphous matrix. Magnetic measurements indicate that this alloy in the amorphous and nanocrystalline state is a good soft magnetic material. Values of saturation magnetization and coercivity are 120 Am²/kg and 5 A/m respectively, for the alloy in the nanocrystalline state. Pre-annealing, post-relaxation and nanocrystallization as well as various milling parameters were explored and the structural and magnetic changes induced have been studied. The analysis of the particle size distribution and morphology of the powders show that the brittleness resulting from pre-annealing of the ribbons is very effective in reducing the particle’s size. Recovery of the high coercitive field induced by milling is achieved by post-annealing to an extent that depends mostly on the milling conditions.     

An EXAFS study of structural changes induced by mechanical milling of the Ni3Al ordered intermetallic compound

Extended X-ray absorption fine-structure (EXAFS) data from the Ni₃Al ordered intermetallic compound during structural evolution induced by mechanical milling (MM) are presented and discussed. X-ray diffraction and transmission electron microscopic observations confirm that the L1₂---Ni₃Al ordered intermetallic compound changes to a disordered fcc form of Ni₃Al at an early stage of milling and then changes to a two phase nanocrystalline and amorphous microstructure. Least-squares-fitting of the EXAFS data shows that both the Ni---Ni and the Ni---Al atomic distances increase slightly with milling time. During the first 5 h of milling, the Ni---Ni coordination decreased while the Ni---Al coordination increased. This observation is also indicative of an order-disorder transition. Subsequent milling produced a remarkable increase in the Ni---Ni coordination number as a nanocrystalline structure developed. Simultaneously, the Ni---Al coordination number decreased markedly, the total Ni coordination always remaining roughly constant. These EXAFS results suggest that segregation of Al from the Ni₃Al occurred during the MM process, and eventually a partly amorphous structure evolved. After the longest milling time, a Ni-rich nanocrystalline phase was surrounded by an Al-rich amorphous phase. The Al segregation may be at the nanocrystalline grain boundaries and/or within the more extensive amorphous regions observed by transmission electron microscopy.     

Corrosion behavior of solid solution (Ti,Al) N as a function of Al concentration

In this work, a series of (Ti, Al) N coatings with different Al contents were deposited on 304 stainless steel substrates by Hollow Cathode Discharge (HCD) method. The coatings were grown on 304 stainless steel substrates at 400 °C. The coatings were characterized using energy dispersive X‐ray spectroscopy (EDX), X‐ray diffraction (XRD), atomic force microscopy (AFM), and microhardness test. The XRD confirmed the transition from TiN phase to (Ti, Al) N phase and then to AlN phase with increasing Al concentration in the solid solution. It was found that with increasing Al concentration the hardness of the coatings initially increased up to a maximum value of about 30 GPa at around 32 at.% of Al and then the coating hardness decreased rapidly with further increase of Al content (Al > 32 at.%). The potentiodynamic polarization analysis was carried out in 3.5 wt.% NaCl solutions to study the corrosion resistance of the coatings. From the corrosion test it can be inferred that the amount of Al atoms in the coatings plays an important role for reducing the corrosion.     

Effect of heat treatment on corrosion properties of mixed sol gel silica-titania (7-3) coating

In this paper, the sol-gel method has been used for preparing silica-titania coats with a molar ratio of 7:3 on TiNi that were heat treated at 300 °C and 500 °C. For studying and investigating the property of corrosion and microstructure of coats; SEM (scanning electron microscopy), EIS (electrochemical impedance spectroscopy), polarization dynamic and roughness measurement have been used and XRD (X-ray diffraction) has been also used for characterizing the coats. Heat treatment at 500 °C caused the increase of porosity and coating cracking that finally caused the decrease of corrosion resistance. The best corrosion resistance was achieved for the sample that was heat treated at 300 °C. The structure of the heat treated sample at 300 °C was amorphous and the increase of temperature of heat treatment from 300 °C to 500 °C caused crystallization and decrease of the corrosion resistance. Crystallization affected both corrosion resistance and surface roughness.     

Glass formation in the MoO3–Nd2O3–La2O3–B2O3 system

In MoO₃–Nd₂O₃–B₂O₃ and MoO₃–Nd₂O₃–La₂O₃–B₂O₃ systems, glasses were obtained in the region between 20 and 30 mol% Ln₂O₃. A liquid-phase separation region was observed near the MoO₃–B₂O₃ side up to 20 mol% Ln₂O₃ (La, Nd). The amorphous phases were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), UV–VIS and infrared spectroscopy (IR). According to DTA data B₂O₃-rich glasses are stable up to 630 °C while glasses rich in MoO₃ are stable up to 430 °C. The glasses are transparent in the visible region. Structural models for the glasses network were suggested on the basis of IR spectral investigations. It was established that BO₃ (1380 cm⁻¹), BO₄ (1100–950 cm⁻¹) and MoO₄ (860 cm⁻¹) groups build up the glass network. MoO₆ units (band at 880 cm⁻¹) together with BO₃ units participate in the formation of the glass network with a high MoO₃ content (80–90 mol%).     

Light-induced changes in hydrogenated amorphous silicon solar cells deposited at the edge of crystallinity

A series of hydrogenated amorphous silicon (a-Si:H) films were deposited in the transition region from amorphous to nanocrystalline phases by changing hydrogen dilution ratio R, deposition gas pressure, and RF power. Single junction a-Si:H solar cells were made using these materials as the intrinsic layers in the structure of n–i–p type on ZnO/Ag/stainless steel substrates. Light-induced degradations in the photovoltaic parameters were characterized on these cells after 1 Sun solar illumination for 150 h. The stabilized efficiencies were compared in conjunction with the structures in the intrinsic layers, which were revealed by high resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectrometry (FTIR). It was found that the solar cells incorporated protocrystalline intrinsic layer as the i-layer give a better initial efficiency, while solar cells made from nanostructured i-layers have a better stability of ～7% degradation against light soaking, as a result, both have nearly the same final stabilized efficiency. The best device stabilized efficiency reaches ～10.2% (0.25 cm², AM1.5G) for the intrinsic layer deposited at a high pressure of 2 Torr.     

Effect of Nb in the nanocrystallization and magnetic properties of FeNbBCu amorphous alloys

The crystallization of melt-spun Fe_79?xNb_5+xB₁₅Cu₁ (x = 0, 2, 4) ribbons has been studied by differential scanning calorimetry and X-ray diffraction. A primary crystallization of bcc-Fe nanoparticles embedded in an amorphous matrix, followed by the precipitation of metastable borides from the residual matrix at higher temperatures is observed. The characteristic temperatures of crystallization events change with Nb concentration. The results obtained from thermal and structural characterization are related to the magnetic properties of the sample. A dependence of the magnetic behavior with the Fe/Nb content in the alloy is also unveiled. The decrease of Nb content in the alloy leads to an enhancement of both the saturation polarization and the Curie temperature due to variations in the exchange coupling between Fe atoms. However, the maximum values of magnetic entropy change do not vary appreciably among the three amorphous alloys. In nanocrystalline samples the amount of the nanocrystalline transformed fraction seems to be the main reason for the change in the saturation polarization of the sample.     

Effect of Co substitution for Ni on the microstructure and magnetic properties of (Fe, Ni)-based amorphous alloys produced by melt spinning

Transmission electron microscopy with selected area electron diffraction, and X-ray diffraction were applied to study the effect of Co substitution for Ni in (Fe, Ni)-based amorphous alloys. The investigation was performed to obtain information on correlations between microstructure and magnetic properties of the (Fe, Ni, Co)-based amorphous alloys. The examination of the microstructure reveals that there are small crystallized free surface regions because the actual quenching rate is distributed inhomogeneously over the cross-section of the ribbon. Since in the free surface region, the solidification rate is lower, a spontaneous annealing process occurs at the top surface of the ribbon. The crystallization degree of the free surface region is higher for alloy ribbons that contain Co up to a 15 at.% concentration. Magnetic domains pattern are sensitive to the surface crystallization and Co content of the (Fe, Ni)-based alloy ribbons. Fine-scaled stripe domains were evidenced on the free ribbon surface while on contact surface stress domain pattern appeared. With the increase of the Co content, the domain width became small and long stripes appeared. The striped domains are responsible for an increased coercivity of the ribbons. However, there is a critical Co content (x_Co = 10) for which spontaneous narrow stripe domains are no longer more energetically favourable for ribbons with specific magnetic applications.     

Effect of melt treatment on the microstructure and magnetic properties of Nd2Fe14B/α-Fe nanocomposites

Melt-spun Nd_9.5Fe₈₁Zr₃B_6.5 ribbons were prepared under different quenching temperature. The effect of melt treatment on the microstructure and magnetic properties of Nd₂Fe₁₄B/α-Fe nanocomposites was studied by X-ray diffraction, scanning electron microscopy (SEM), differential scanning calorimeter, transmission electron microscopy observations, and magnetization measurements. It was found that melt spinning at different quenching temperature caused the as-quenched ribbons to have distinctive structure. Depending on the quenching temperature, nanocrystalline structure, partially amorphous structure containing nanophases or entirely amorphous structure could be obtained. Moreover, with increasing initial quenching temperature, the microstructure of optimally heat treated ribbons becomes coarser and more irregular, and the magnetic properties of them deteriorated. It is believed that the alteration of melt characteristics which are highly sensitive to the melt temperature may be the cause for the change of glass forming ability, the microstructure and magnetic properties of the ribbons.     

Preferential Co partitioning to α-Fe in nanocrystalline CoFeNbB alloys by Mn addition

Influence of Mn addition on the microstructure and hyperfine parameters of amorphous and nanocrystalline Co₆₀(FeMn)₁₈Nb₆B₁₆ alloys has been studied. Although Mn addition does not yield significant differences in crystallization kinetics and in the phases formed after each transformation, it seriously affects the partitioning of Co during nanocrystallization. Whereas for Mn free alloy Co is homogeneously distributed throughout the amorphous matrix and the nanocrystals, in Mn containing alloy Co is enriched in the α-FeCo nanocrystals. This fact prevents the exhaustion in Fe of the amorphous matrix and the crystalline volume fraction achieved at the end of nanocrystallization in the case of Mn containing alloy is ∼20% higher than in the Mn free alloy.