A model for studying the kinetics of the formation of Fe2B boride layers at the surface of a gray cast iron

The present work estimates, using a kinetic model, the growth kinetics of Fe₂B boride layers generated at the surface of a gray cast iron via the powder-pack boriding considering three different temperatures (1173, 1223 and 1273 K) and four treatment times (2, 4, 6 and 8 h). By the use of the mass balance equation at the (Fe₂B/substrate) interface under certain assumptions and considering the effect of the boride incubation time, it was possible to estimate the corresponding parabolic growth constant in terms of two parameters and β(T) depending on the boron content in the Fe₂B phase and on the process temperature, respectively. The mass gain at the material surface and the instantaneous velocity of the (Fe₂B/substrate) interface were also estimated. A fairly good agreement was observed between the experimental parabolic growth constants taken from a reference work (Campos-Silva et al., Characterization of boride layers formed at the surface of gray cast irons, Kovove Mater. 47 (2009) 1-7.) and the simulated values of the parabolic growth constants. Furthermore, the boride layer thicknesses were predicted and experimentally verified for three process temperatures and four treatment times.     

Simulation of the growth kinetics of the (FeB/Fe2B) bilayer obtained on a borided stainless steel

The present work is an attempt to simulate the growth kinetics of the (FeB/Fe₂B) bilayer grown on a substrate made of AISI 316 stainless steel by the application of the powder-pack boriding process, and using four different temperatures (1123, 1173, 1223 and 1273 K) and five exposure times (2, 4, 6, 8 and 10 h). The adopted diffusion model solves the mass balance equation at each growth front: (FeB/Fe₂B or FeB/substrate) under certain assumptions and without considering the diffusion zone. To consider the effect of the incubation times for the borides formation, the temperature-dependent function ?(T) was incorporated in the model. To validate this model, a computer code written in Matlab (version 6.5), was developed with the purpose of simulating the kinetics of the boride layers. This computer code uses the following parameters as input data: (the boriding temperature, the treatment time, the upper and lower limits of boron concentration in each iron boride, the diffusion coefficients of boron in the FeB and Fe₂B phases as well as the ?(T) parameter). The outputs of the computer code are the parabolic growth constant at each growth front and the thicknesses of the FeB and Fe₂B layers. A good agreement was obtained between the experimental parabolic growth constants taken from a reference work [I. Campos-Silva et al., Formation and kinetics of FeB/Fe₂B layers and diffusion zone at the surface of AISI 316 borided steels, Surf. Coat Technol., 205 (2010) 403-412] and the simulated values of the parabolic growth constants (k_FeB and k₁). The present model was also able to predict the thicknesses of the FeB and Fe₂B layers at a temperature of 1243 K during 3 and 5 h.In addition, the mass gain at the material surface was also estimated as a function of the time and the upper boron content in each iron boride phase. It was shown that the simulated values of the generated mass gain are very sensitive to the increase of both temperature and the upper boron contents in the FeB and Fe₂B phases.     

A diffusion model for describing the bilayer growth (FeB/Fe2B) during the iron powder-pack boriding

In this paper, a diffusion model is proposed for studying the bilayer growth kinetics (FeB/Fe₂B) on pure iron substrate during the powder-pack boriding in the temperature range of 1023-1273 K.This model based on Fick's laws was solved, under certain assumptions, considering a parabolic growth of iron borides.For this purpose, a computer simulation program was created for predicting the boride layer thickness as a function of process parameters (temperature, time and surface boron content). A fairly good agreement was observed between the simulation calculations and experimental data derived from the literature.     

Kinetics of the formation of Fe2B layers in gray cast iron: Effects of boron concentration and boride incubation time

The growth kinetics of Fe₂B layers formed at the surface of gray cast iron were evaluated in this study. The pack-boriding process was applied to produce the Fe₂B phase at the material surface, and the variables included three temperatures (1173, 1223 and 1273 K) and four exposure times (2, 4, 6 and 8 h). Taking into account the growth fronts obtained at the surface of the material and the mass balance equation at the Fe₂B/substrate interface, the boron diffusion coefficient on the borided phase was estimated for the range of treatment temperatures. Likewise the parabolic growth constant, the instantaneous velocity of the Fe₂B/substrate interface, and the weight gain in the borided samples were established as a function of the parameters τ(t) and α(C), which are related to the boride incubation time (t₀(T)) and boron concentration at the Fe₂B phase, respectively. Observation of the growth kinetics of the Fe₂B layers in gray cast irons suggest an optimum value of boron concentration that is in good agreement with the set of boriding experimental conditions used in this work.     

Computer simulation of monolayer growth kinetics of Fe2B phase during the paste-boriding process: Influence of the paste thickness

This paper deals with the effect of boron paste thickness on the study of the monolayer growth kinetics of Fe₂B phase forming on AISI 1045 steel by the paste-boriding process. A mathematical diffusion model based on the Fick's phenomenological equations was applied in order to estimate the growth rate constant at (Fe₂B/γ-Fe) interface, the layer thickness of iron boride as well as the associated mass gain depending on the boriding parameters such as time, temperature and surface boron concentration related to the boron paste thickness. The simulation results are found to be in a fairly good agreement with the experimental data derived from the literature.     

Growth kinetics of borided layers: Artificial neural network and least square approaches

The present study evaluates the growth kinetics of the boride layer Fe₂B in AISI 1045 steel, by means of neural networks and the least square techniques. The Fe₂B phase was formed at the material surface using the paste boriding process. The surface boron potential was modified considering different boron paste thicknesses, with exposure times of 2, 4 and 6 h, and treatment temperatures of 1193, 1223 and 1273 K. The neural network and the least square models were set by the layer thickness of Fe₂B phase, and assuming that the growth of the boride layer follows a parabolic law. The reliability of the techniques used is compared with a set of experiments at a temperature of 1223 K with 5 h of treatment time and boron potentials of 2, 3, 4 and 5 mm. The results of the Fe₂B layer thicknesses show a mean error of 5.31% for the neural network and 3.42% for the least square method.     

Effect of boron paste thickness on the growth kinetics of polyphase boride coatings during the boriding process

The growth kinetics of FeB and Fe₂B phases forming on AISI M2 steel by paste boriding was studied using different values of paste thickness, treating temperature and exposure time. The growth of iron boride layers is described by the mass balance equation between phases in thermodynamic equilibrium, assuming that the boron concentration at the interfaces remain constant during the treatment. The experimental results show that boron mobility and growth kinetics of iron borides are considerably increased when the paste thickness is increased at constant values of temperature and exposure time.     

Microstructure and properties of borocarburized and laser-modified 17CrNi6-6 steel

Two-step process: carburizing followed by boriding was applied to the formation of borocarburized layers. The boride layer formed on the substrate of changeable chemical and phase composition (e.g. borocarburized layer) was called “gradient boride layer”, in contrast to “typical boride layer”, formed on the substrate of constant chemical and phase composition. Until now, the typical heat treatment of borocarburized layer consisted of treatment through hardening: quenching in oil and low-temperature tempering. In this paper, instead of treatment through hardening, laser-heat treatment was employed. The properties of such layer were compared to the properties of typical carburized layer. Three zones characterized the microstructure of laser-modified borocarburized layer: iron borides (FeB+Fe₂B) of modified morphology, hardened carburized zone (heat affected zone) and carburized layer without heat treatment. X-ray microanalysis indicated the increased boron concentration close to the surface due to the occurrence of a mixture of FeB and Fe₂B borides. Near to the hardened carburized zone, Fe₂B phase occurred in the laser-modified boride zone. Laser-heat treated borocarburized layer was characterized by higher microhardness at the surface than that obtained in case of carburized layer. It was caused by the iron borides (FeB+Fe₂B) occurrence at the surface, as a consequence of boriding process. However, the carburized layer was characterized by considerably larger hardened zone. Higher abrasive wear resistance, but lower low-cycle fatigue strength in comparison with the carburized layer, characterized the gradient boride layer formed by borocarburizing and laser surface modification. The indentation craters obtained on the surface of laser-heat treated borocarburized layer revealed sufficient cohesion (HF3 standard). The use of laser-modified borocarburized layers may be advantageous under conditions of high abrasive wear of mating parts. In case of parts, which require high resistance to fatigue, the carburized layer is irreplaceable.     

Characterization of AISI 4140 borided steels

The present study characterizes the surface of AISI 4140 steels exposed to the paste-boriding process. The formation of Fe₂B hard coatings was obtained in the temperature range 1123-1273 K with different exposure times, using a 4 mm thick layer of boron carbide paste over the material surface. First, the growth kinetics of boride layers at the surface of AISI 4140 steels was evaluated. Second, the presence and distribution of alloying elements on the Fe₂B phase was measured using the Glow Discharge Optical Emission Spectrometry (GDOES) technique. Further, thermal residual stresses produced on the borided phase were evaluated by X-ray diffraction (XRD) analysis. The fracture toughness of the iron boride layer of the AISI 4140 borided steels was estimated using a Vickers microindentation induced-fracture testing at a constant distance of 25 μm from the surface. The force criterion of fracture toughness was determined from the extent of brittle cracks, both parallel and perpendicular to the surface, originating at the tips of an indenter impression. The fracture toughness values obtained by the Palmqvist crack model are expressed in the form K_C(π/2) > K_C > K_C(0) for the different applied loads and experimental parameters of the boriding process.     

Possibilities of the formation of carbides and borides by ion implantation

In the system of boron and carbon, the formation of boron carbide was investigated after ion implantation of 25 keV B ions into carbon or of 25 keV C ions into boron and subsequent annealing. TEM and electron diffraction studies showed that the crystallization of boron carbide begins only at temperatures above 1050°C. By implantation of 20 keV C ions into iron (ion dose 10¹⁷ C ions/cm²) only the metastable ε-Fe₂O will be generated, which at above 220°C transforms into the stable cementite Fe₃C. After implantation of 20 keV B ions into iron, no formation of iron boride could be found. These experimental facts can be understood qualitatively with the help of the thermal-spike model. The energy density or the temperature in the thermal spikes is not sufficient for the generation of cementite iron boride or boron carbide.     

Growth kinetics of iron boride layers: Dimensional analysis

Dimensional analysis is presented as a powerful tool in the study of the paste boriding process. In particular, a dimensional method is used to study the growth kinetics of the boride layers FeB and Fe₂B. Experiments were performed in AISI 1045 steel and AISI M2 steel, to test the suggested model. Samples of 1045 steel were prepared and treated using boron paste thickness of 3-5 mm, at temperatures of 1193, 1223 and 1273 K, with 2, 4 and 6 h of treatment time. The M2 specimens had boron paste thickness of 3 and 4 mm and temperatures of 1223, 1253 and 1273 K for 2 and 6 h. Results indicate that the growth of boron layers obeys power laws of the form y = αx^β, where α and β constants are a function of the material and the interface of interest. Validation of the model was carried out using experimental data with an average error percentage of 7.6% for Fe₂B in 1045 steel, 15.8% for FeB and 3.4% for Fe₂B in M2 steel.     

Kinetics of electrochemical boriding of low carbon steel

In this study, the growth kinetics of the boride layers forming on low carbon steel substrates was investigated during electrochemical boriding which was performed at a constant current density of 200 mA/cm² in a borax based electrolyte at temperatures ranging from 1123 K to 1273 K for periods of 5-120 min. After boriding, the presence of both FeB and Fe₂B phases were confirmed by the X-ray diffraction method. Cross-sectional microscopy revealed a very dense and thick morphology for both boride phases. Micro hardness testing of the borided steel samples showed a significant increase in the hardness of the borided surfaces (i.e., up to (1700 ± 200) HV), while the hardness of un-borided steel samples was approximately (200 ± 20) HV. Systematic studies over a wide range of boriding time and temperature confirmed that the rate of the boride layer formation is strongly dependent on boriding duration and has a parabolic character. The activation energy of boride layer growth for electrochemical boriding was determined as (172.75 ± 8.6) kJ/mol.     

X-ray photoelectron spectroscopy of boron implanted 4145 steel surface

The near-surface region of 4145 steel following boron implantation was investigated by x-ray photoelectron spectroscopy (XPS). The steel surface was implanted with¹¹B⁺ ions to a constant dose of 1.0×10¹⁷ ions cm^–2 at energies of 30 and 135 keV. The XPS spectrum of the implanted surface showed a shift in the B(1s) level towards the higher binding energy. The observed 188.0 eV binding energy of the B(1s) level was found to be in good agreement with the characteristic binding energy of the B(1s) level corresponding to iron boride (Fe₂B). Hence the increase in surface hardness reported previously is related to the formation of an iron boride layer in the near-surface region known for its hardening capabilities.     

Mössbauer and EXAFS studies of amorphous iron produced by thermal decomposition of carbonyl iron in liquid phase

Decomposition of iron carbonyl Fe(CO)₅ and Fe₂(CO)₉ in liquid phase gave amorphous and crystalline iron powders in the absence and presence of catalyst, respectively. The hyperfine fields were large in amorphous phases prepared from Fe(CO)₅ than from Fe₂(CO)₉. Crystalline iron, iron carbide and a trace amount of Fe₃O₄ were detected in the decomposition products of the amorphous phase prepared from Fe(CO)₅, and iron carbide was mainly included in the decomposition products of the amorphous phase prepared from Fe₂(CO)₉.     

Microstructural evolutions of Pr13Fe80B7 alloys during solid HDDR process

Microstructural evolutions of Pr₁₃Fe₈₀B₇ alloys during solid hydrogenation disproportionation desorption recombination (HDDR) process is systematically investigated. The results show that the early-disproportionated products of Pr₁₃Fe₈₀B₇ alloys are mainly characteristic of rod-like morphology, and the rods are PrH₂ while the matrix is Fe. Moreover, all the PrH₂ rods have the same crystallographic orientation, and grow with a definite orientation related to the Fe matrix. However, it is notable that no iron boride phase except for NdH₂ and Fe is found. With the prolonged disproportionation time, the rod-like disproportionated products coarsen, and the Fe₂B come to form. When the disproportionation time is 17 h, the rod-like disproportionation morphology transforms into sphere, and a large amount of Fe₂B is found. Subsequent investigations for the recombination show that the recombination reactions start at the boundaries between PrH₂ rods and Fe matrix, and the rim-like Pr₂Fe₁₄B is formed on the PrH₂ rods. Moreover, the recombined PrFeB powder of the rod-like microstructure has strong magnetic anisotropy.     

Structural study of borided layers obtained on synthetic Fe−Ni alloys

Carbon free Fe?Ni alloys (12 and 20 wt.% Ni) have been analysed by X-ray diffraction and surface Mössbauer spectroscopy (CXMS and CEMS) after boriding treatment at 1273 K for 20 hours. Some (Fe _x Ni _l-x )₂B and Fe _x Ni _l-x B samples, with different values ofx, obtained by heating at 1073 K mixtures of elements in powder form, were used as reference. Besides (Fe _x Ni _l-x )₂B and Fe _x Ni _l-x B, a third boride phase rich in boron has been detected in the outer borided layers of the alloy specimens. A third phase appears also in the corresponding X-ray patterns. A comparison between CXMS and CEMS data show that (Fe _x Ni _l-x )₂B is present only in the deeper part of the borided layers and that the outer surface layer is a mixture of a nickel and boron rich boride and of a superparamagnetic oxide.     

Brownian relaxation of magnetic nanoparticles in fluid: the effect of the solvent

A simple, environmentally friendly hydrothermal stripping route for synthesizing highly size-controlled spherical ferric oxide nanoparticles was developed that involved stripping ferric ion from iron-loaded organic phase. The particle size was found to be influenced by the initial concentration of iron in organic phase, stripping temperature and time, and a mathematical model about the size was established based on the experimental results and theoretical analysis. The model suggests that the process apparent activation energy of stripping iron from organic phase is 97.3? kJ·mol^?1, the energy of crystal growth is 51.6? kJ·mol^?1, and the synthesis of Fe₂O₃ is controlled by the crystal growth of embryo at low temperature (T < 590?K). The sizes calculated by the model comparatively accord with the experimental data and this provides a method for controlling the sizes.     

Preparation of nanosized iron oxide and its application in low temperature CO oxidation

A method to prepare iron oxide material which has a higher surface area and nanosized particle was developed. It was used as a catalyst for CO oxidation at low temperature. Iron oxide materials were prepared by precipitation under constant pH value. The effects of preparation parameters, such as iron salt (FeCl₃, Fe(NO₃)₃ and FeCl₂), pH value (between 8 and 12), drying temperature (between 120°C and 300°C), and feeding rate of the aqueous solution of the iron salt, on the characteristics of iron oxide have been investigated. The materials were characterized by N₂ sorption, powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The surface area of iron oxide was greater than 400 m²/g using FeCl₃ as the starting material with very low feeding rate of 10 ml/min, the pH value of 11, and drying at 120°C. The XRD patterns indicated that the iron oxide samples heated at a temperature below 180°C was either amorphous or of a particle size too small (<4 nm) for the samples prepared with FeCl₃. Depending on the preparation conditions, the iron oxide samples showed a phase transition from amorphous to various crystalline phases. Large amount of hydroxyl groups were preserved if the drying temperature was below 200°C. TEM images showed that the particle diameters were less than 4 nm for the samples prepared with FeCl₃ at pH value of 11 with a low feeding rate of 10 ml/min, and heated below 200°C. XPS Fe 2p_3/2 spectra showed the phase transition of iron oxide from Fe₃O₄ to FeO. The feeding rate of starting material and pH value during precipitation played the important roles to obtain iron oxide with high surface area. The nanosized iron oxide demonstrated high activity for CO oxidation even at ambient condition. The higher activity of Fe _x O _y nanoparticles in CO oxidation was attributed to a small particle size, high surface area, high concentration of hydroxyl groups, and more densely populated surface coordination unsaturated sites.This revised version was published online in August 2005 with a corrected issue number.     

Preparation of nanosized iron oxide and its application in low temperature CO oxidation

A method to prepare iron oxide material which has a higher surface area and nanosized particle was developed. It was used as a catalyst for CO oxidation at low temperature. Iron oxide materials were prepared by precipitation under constant pH value. The effects of preparation parameters, such as iron salt (FeCl₃, Fe(NO₃)₃ and FeCl₂), pH value (between 8 and 12), drying temperature (between 120°C and 300°C), and feeding rate of the aqueous solution of the iron salt, on the characteristics of iron oxide have been investigated. The materials were characterized by N₂ sorption, powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The surface area of iron oxide was greater than 400 m²/g using FeCl₃ as the starting material with very low feeding rate of 10 ml/min, the pH value of 11, and drying at 120°C. The XRD patterns indicated that the iron oxide samples heated at a temperature below 180°C was either amorphous or of a particle size too small (<4 nm)=" for=" the=" samples=" prepared=" with=">₃. Depending on the preparation conditions, the iron oxide samples showed a phase transition from amorphous to various crystalline phases. Large amount of hydroxyl groups were preserved if the drying temperature was below 200°C. TEM images showed that the particle diameters were less than 4 nm for the samples prepared with FeCl₃ at pH value of 11 with a low feeding rate of 10 ml/min, and heated below 200°C. XPS Fe 2p_3/2 spectra showed the phase transition of iron oxide from Fe₃O₄ to FeO. The feeding rate of starting material and pH value during precipitation played the important roles to obtain iron oxide with high surface area. The nanosized iron oxide demonstrated high activity for CO oxidation even at ambient condition. The higher activity of Fe _x O _y nanoparticles in CO oxidation was attributed to a small particle size, high surface area, high concentration of hydroxyl groups, and more densely populated surface coordination unsaturated sites.     

Thermal evolution of high dose iron implanted sintered alumina

Sintered plates of alumina have been implanted at room temperature with 110 keV⁵⁷Fe⁺ at a dose of 1.2×10¹⁷ ions.cm^?2. The analysis of the Conversion Electron Mössbauer Spectrum indicated that implantation introduces iron in alumina in three charge state: Fe²⁺ (two components), Fe⁴⁺ and Fe⁰ (metallic clusters). The evolution of the iron depth distribution during annealings in oxiding or in neutral atmosphere has been followed using the Rutherford backscattering spectroscopy. Up to 800°C the profile as well as the charge states of iron evolve very slowly. A drastic change occurs' for annealing temperature around 1000°C. The total amount of iron is distributed among α-Fe₂O₃ and α-(Fe_1?x Al _x )₂O₃ precipitates. Some scanning electron micrographs have allowed to locate these precipitates. For highest temperature anneals, up to 1600°C, only substitutional iron remain.