Electrochemical Evaluation of Corrosion on Borided and Non-borided Steels Immersed in 1 M HCl Solution

In this study the corrosion resistances of AISI 1018 and AISI 304 borided and non-borided steels were estimated using polarization resistance and electrochemical impedance spectroscopy (EIS) techniques. Boriding of the steel samples was conducted using the powder-pack method at 1223 K with 6 h of exposure. Structural examinations of the surfaces of the borided steels showed the presence of a Fe₂B layer with isolated FeB teeth on the AISI 1018 steel, whereas a compact layer of FeB/Fe₂B was formed on the AISI 304 steel. Polarization resistance and EIS of the borided and non-borided steels surfaces were performed in a corrosive solution of 1 M HCl. The EIS data were analyzed during 43 days of exposure to the acid solution. Impedance curves obtained during this period for the borided and non-borided steels were modeled using equivalent electrical circuits. The results of both electrochemical techniques indicated that boride layers formed at the steel surfaces effectively protect the samples from the corrosive effects of HCl. The main corrosion processes observed on the boride layers were pitting and crevice corrosion.     

Characterization of borided pure molybdenum under controlled atmosphere

In this study, the structural characterization and boriding kinetics of the molybdenum borides formed on the surface of borided pure molybdenum (Mo) have been investigated. Boronizing was carried out in solid medium with boron component forming Ekabor ® 2 (90% SiC, 5% KBF₄, 5%B₄C) powders at 1273 K, 1373 K for 2, 4, 6, 8 hours under a controlled atmosphere containing argon gas flow. The boride layer was characterized by the scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Energy dispersive spectroscopy (EDS) and Vickers microhardness tester. X-ray diffraction analysis showed that the boride layers on molybdenum consisted of MoB and Mo₂B phases. However, the MoB phase was observed at certain boriding temperature and boriding times. The thickness of boronized layers almost ranged from 12 to 42.5 μm with boriding time. A parabolic relationship was observed between boride layer thickness and boriding time. The growth rate constant and activation energy for the boride layer were calculated. The hardness of borides compounds formed on the surface of molybdenum ranged from 925 to 1150 HV_0.05, whereas the hardness of the untreated molybdenum sample was 258 HV_0.05.     

Kinetics and Boron Diffusion in the FeB/Fe2B Layers Formed at the Surface of Borided High-Alloy Steel

In the present study, boron diffusion in the surface layers of AISI M2 borided steels and the growth kinetics of the FeB/Fe₂B layers were estimated. The boriding of AISI M2 steel was performed according to the powder-pack method and was conducted at 1173-1323?K and at various exposure times. As a result of the boriding process, the diffusion-controlled growth of the FeB/Fe₂B layers was obtained at the surface of the high-alloy steel, and the kinetics of the growth process changed parabolically over time. The boron diffusion coefficients were estimated by solving two simultaneous equations based on the limits of the boron concentration in each layer, the boride incubation time, and the parabolic growth constant. With the proposed diffusion model, an expression, which describes the evolution of the FeB/Fe₂B layers, was obtained. Moreover, the proposed model and diverse empirical models presented in the literature provided a good fit to the experimental data obtained for 10?h of exposure and different boriding temperatures.     

Fracture Toughness of Thick Boride Layers Estimated by the Cross-Sectioned Scratch Test

New results about the fracture toughness (K_c) of thick boride layers estimated by the cross-sectioned scratch test are presented in this study. The FeB-Fe₂B layers developed at the surface of borided AISI 1018 and AISI 1045 steels and the Fe₂B layer formed on the borided AISI 1045 steel exposed to a diffusion annealing process (DAP) were used for this purpose. The cross-sectioned scratch tests were performed with a Vickers diamond stylus drawn across the thick boride layer under a constant load to produce a half-cone-shaped fracture near to the top surface of the borided steels. The height of the half-cone-shaped fracture as a function of the cross-sectioned scratch loads was used to determine the fracture toughness of the FeB and Fe₂B layers. The results showed a fracture resistance of \(\sim2.8\,{\text{MPa}}\sqrt m\) for the FeB layer formed at the surface of borided AISI 1045 steel. Likewise, the effect of the DAP on the surface of the borided AISI 1045 steel promoted the formation of an exclusively Fe₂B layer, with an increase in the fracture toughness of the whole boride layer around \(5\,{\text{MPa}}\sqrt m\). Finally, the principle of the technique can be used to minimize the influence of the anisotropic properties on the fracture toughness along the depth of boride layers.     

Tribological behaviour of borided bearing steels at elevated temperatures

Borided steels are known to exhibit excellent wear resistance at room temperature. However, the sliding wear behaviour of borided steels at high temperatures is not known. In the present study, AISI 440C and 52100 bearing steels which are extensively used in industry, were borided by pack method at 950 °C for 2 h. X-ray diffraction analysis of boride layers on the surface of steels revealed various peaks of FeB, Fe₂B and CrB. The thickness and hardness of boride layers on the 52100 and 440C steels were 56 ± 6 and 47 ± 4 μm and 1970 and 2160 HK, respectively. Dry sliding wear tests of these borided steels were performed against Si₃N₄ bearing ball at a constant sliding speed and load at elevated temperatures. The temperature changed between room temperature and 600 °C. These tests indicated that the wear rates of unborided and borided steels increase with temperature and borided 52100 and 440C steels exhibit considerably lower wear rate at all temperatures, compared with unborided steels. At temperature of 600 °C, borided 52100 and 440C steels have a wear resistance of about 3 and 2.5 times higher than that of unborided steels, respectively. Examination of the worn surface of borided steels showed that, worn surfaces were covered with a discontinuous compact layer especially above temperature of 300 °C.     

A Kinetic Model for the Boriding Kinetics of AISI D2 Steel During the Diffusion Annealing Process

In this work, a diffusion model was proposed to estimate the boron activation energies for FeB and Fe₂B layers during the pack-boriding of AISI D2 steel at temperatures of 1223, 1253 and 1273 K for a treatment time varying between 2 and 10 h. This model considers the effect of boride incubation times during the formation of the FeB and Fe₂B phases. To study the influence of diffusion annealing process on the boriding kinetics of AISI D2 steel, the mass balance equations were modified in order to follow the evolution of boride layers as a function of annealing time for the specified boriding parameters. Finally, the kinetic model was validated by a comparison of the experimental thicknesses of boride layers with the predicted ones at a temperature of 1243 K for 2, 4 and 6 h. A simple equation was then obtained for estimating the total time necessary to get a single boride layer (Fe₂B) that depends on the boriding parameters and on the thickness of each boride layer prior to the diffusion annealing process.     

Indentation size effect on the Fe2B/substrate interface

This study evaluated the indentation size effect on the Fe₂B/substrate interface using the Berkovich nanoindentation technique. First, the Fe₂B layers were obtained at the surface of AISI 1018 borided steels by the powder-pack boriding method. The treatment was conducted at temperatures of 1193, 1243 and 1273 K for 4, 6 and 8 h at each temperature. The boriding of AISI 1018 steel resulted in the formation of saw-toothed Fe₂B surface layers. The formation of a jagged boride coating interface can be attributed to the enhanced growth at the tips of the coating fingers, due to locally high stress fields and lattice distortions. Thus, the mechanical properties achieved at the tips of the boride layer are of great importance in the behavior of borided steel.Applied loads in the range of 10 to 500 mN were employed to characterize the hardness in the tips of the Fe₂B/substrate interface for the different conditions of the boriding process. The results showed that the measured hardness depended critically on the applied load, which indicated the influence of the indentation size effect (ISE). The load-dependence of the hardness was analyzed with the classical power-law approach and the elastic recovery model. The true hardness in the tips of the Fe₂B/substrate interface was obtained and compared with the boriding parameters. Finally, the nanoindentation technique was used to estimate the state of residual stresses in this critical zone of the Fe₂B/substrate interface.     

Role of RE Element Nd on Boronizing Kinetics of Steels

Boronizing of AISI 1045 and ASTM W1-111/2 steels was carried out by pack boriding using Nd₂O₃-containing agent in the temperature range of 1053 to 1213?K. The effect of RE element Nd on boronizing kinetics was analyzed in terms of possible chemical reactions in boriding agent, surface elemental distribution and morphology evolution of the steels boronized at different temperatures. The results showed that the RE element Nd has two opposite effects on boronizing process, i.e., promoting effect at high temperatures and hindering effect at low temperatures. Boronizing using Nd₂O₃-containing agent can remarkably reduce the diffusion activation energy at higher temperatures. Empirical equations relating the boride layer thickness with processing time and temperature are established. Based on these equations, the contour diagrams of boride layer thickness for the studied steels boronized with addition of 5% Nd₂O₃ are presented.     

65Mn钢渗硼层的微观组织、硬度及生长动力学

采用固体渗硼工艺对65Mn钢进行渗硼处理,并借助光学显微镜、X射线衍射仪、电子探针及维氏硬度计等手段系统研究了渗硼温度(800~1000 ℃)和渗硼保温时间(2~8 h)对65Mn钢渗硼层厚度、微观组织和硬度的影响规律以及渗硼层的生长动力学。结果表明,随着渗硼温度的升高或渗硼时间的延长,渗硼层的厚度不断增大,但当渗硼温度超过900 ℃时,渗硼层中黑色孔洞的数量、大小以及距离渗硼层表面的深度都逐渐增大。65Mn钢渗硼层都由Fe₂B柱状晶,以及位于Fe₂B柱状晶生长前沿及晶粒间的Fe₃(B,C)相、二元铁硅化合物和三元铁碳硅化合物组成,其维氏硬度(800~1590 HV0.05)远大于65Mn钢基体的硬度(238 HV0.05)。由于硬度较低的Fe₃(B,C)相和富硅相分布于高硬度的Fe₂B柱状晶晶粒之间,导致渗硼层的硬度并不随离渗硼层表面距离的增加而单调减小。渗硼层厚度的平方与渗硼时间呈线性关系,B原子在65Mn钢渗硼层中的扩散激活能为220.96 kJ/mol。     

Experiment and modeling of TiB2/TiB boride layer of Ti−6Al−2Zr−1Mo−1V alloy

The influence of the boriding conditions on the boride layers was examined by boriding Ti−6Al−2Zr− 1Mo−1V alloy in the temperature range of 920−1120°C. The experimental results show that the boride layers were composed of a continuous thin outer layer of TiB₂ and a thick inner layer of TiB with whiskers or needle-like morphologies that extended into the substrate. Thick and compact boride layers were obtained when the boriding temperatures were 1000−1080 °C, and the treatment time exceeded 8 h. The boride layer depth increased with the boriding temperature and time, and the growth kinetics of the boride layers was characterized by a parabolic curve. The growth kinetics of the boride layers, including both TiB₂ and TiB layers, were predicted by establishing a diffusion model, which presented satisfactory consistency with the experimental data. As a result, the activation energies of boron in the TiB₂ and TiB layers were estimated to be 223.1 and 246.9 kJ/mol, respectively.     

Evaluation of the corrosion resistance of iron boride coatings obtained by paste boriding process

An evaluation of corrosion resistance of boride coatings in AISI 304 steel was carried out. Formation of iron boride layers (FeB and Fe₂B) at the material surface was obtained by paste boriding process. Boron paste thicknesses of 4 and 5 mm were applied to the steel surface. A thermochemical treatment, for each boron potential, was carried out at temperatures of 1173, 1223 and 1273 K; with exposure times of 4 and 6 h. Corrosion resistance of the borided samples was evaluated by the electrochemical techniques of open circuit and polarization resistance with a 0.1 M solution of NaCl. Dependence between the polarization resistance and the experimental parameters is observed. The results show that the corrosion resistance is maximized with a treatment time of 4 h and a boron paste thickness of 4 mm.     

Investigation of kinetics of borided ductile and lamellar graphite cast iron

In this study, kinetics of borided ductile iron and lameller graphite grey cast iron were investigated by processing boronizing treatment (was carried out in Ekobor-II powders). The process temperatures and durations respectively 1123, 1173, 1223 K for 2, 4 and 6 hours, with pack boronizing method and under atmospheric pressure in electrical resistance furnace. Changing of borided layer properties was investigated by using optical and scanning electron microscopy, X-ray diffraction and micro-Vickers hardness testers. The growth kinetics of the boride layers forming and thickness of boride layer were computed for both cast iron. The main phases for two processes Fe₂B and FeB were defined on the surface.     

Investigation of corrosion behaviors at different solutions of boronized AISI 316L stainless steel

In this study, corrosion behaviors of boronized and non-boronized AISI 316L stainless steel (AISI 316L SS) were investigated with Tafel extrapolation and linear polarization methods in different solutions (1 mol dm^?3 HCl, 1 mol dm^?3 NaOH and 0.9% NaCl) and in different immersion times. AISI 316L SS were boronized by using pack boronizing method for 2 and 6 hours at 800 and 900°C within commercial Ekabor®-2 powder. Surface morphologies and phase analyses of boride layers on the surface of AISI 316L SS were characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) analysis. SEM-EDS analyses show that boride layer on AISI 316L SS surface had a flat and smooth morphology. It was detected by XRD analyses that boride layer contained FeB, Fe₂B, CrB, Cr₂B, NiB and Ni₂B phases. Boride layer thickness increases with increased boronizing temperature and time. The corrosion experiments show that boride layer significantly increased the corrosion resistance of the AISI 316L SS in 1 mol dm^?3 HCl solution. While no positive effect of the boride layer was observed in the other solutions the corrosion resistance of the borid layer on AISI 316L SS was increased in all solution with the increase of the waiting periods.     

The effect of boron-pack refreshment on the boriding of mild steel by the spark plasma sintering (SPS) process

Mild steel samples were borided with and without boron pack refreshment using the spark plasma sintering (SPS) process. Results show that the borided samples with boron pack refreshment developed a thicker boride layer compared to that without boron pack refreshment for the same boriding duration. When boriding duration is t < 120 min, the boriding growth in the samples borided with boron pack refreshment followed a parabolic growth pattern. In contrast, the boride growth in samples processed without boron-pack refreshment deviates from parabolic at t = 60 min. Computer simulation shows that the boron concentration change in the boriding media during the boriding process is an important factor affecting the composition and final thickness of the boride layer.     

La2O3包埋渗硼TB2钛合金的腐蚀与磨损性能

为了改善TB2合金的表面性能,采用4％La2O3(质量分数)包埋渗硼法对TB2合金进行1100℃,20 h渗硼处理,研究TB2钛合金的渗硼层组成与厚度以及腐蚀与磨损性能.结果表明,La2O3在渗硼过程中促进硼化物层的生长,提高其连续性和致密性,TiB晶须长度从16.80增至21.84μm.这是因为La2O3能与B反应生...     

Investigation of Boronizing Kinetics of AISI 51100 Steel

In this study, some mechanical properties of borided AISI 51100 steel with high C concentration were investigated. Boronizing heat treatment was carried out in solid medium consisting of Ekabor-II at 850, 900, and 950 °C for 2, 4, 6, and 8 h. Morphology and mechanical properties of boride layer, and the effect of chemical composition on properties and kinetics of borides were investigated. The results of this study indicated that the morphology of the boride layer has a saw-tooth nature, and its hardness is over 1500 HV. Depending on process time and temperature, the depth of boride layer ranged from 30 to 106 μm. Optical and SEM studies and XRD analysis revealed that borides formed on the surface of steel substrates have dominantly single Fe₂B boride phase in addition to small amount of Cr₂B.     

Formation and kinetics of FeB/Fe2B layers and diffusion zone at the surface of AISI 316 borided steels

The kinetics of the FeB/Fe₂B layers and diffusion zone at the surface of AISI 316 steels exposed to the powder-pack boriding process were studied in this work. FeB/Fe₂B layers and diffusion zone measurements were taken at different temperatures and exposure times to validate diffusion-controlled growth during the boriding process. In order to obtain the boron diffusion coefficients at the FeB/Fe₂B layers and diffusion zone, a mathematical model based on the mass balance at the growing interfaces was proposed. The activation energy values estimated for the FeB and Fe₂B layers were 204 and 198 kJ mol^− 1 respectively. In addition, the activation energy value obtained for the diffusion zone was 116 kJ mol^− 1. The diffusion model was extended to estimate the FeB/Fe₂B layer thicknesses, and the depth of the diffusion zone at the temperature of 1243 K with 3 and 5 h of exposure, based on the experimental parameters ascribed to the boriding process. Finally, the effects of the FeB/Fe₂B growth and diffusion zone, on the weight gain of borided steels and on the instantaneous velocity of the interfaces were incorporated in the model.     

Influence of process duration on structure and chemistry of borided low carbon steel

In this study, we employed an ultra-fast boriding technique to grow hard boride layers on low carbon steel substrates using an induction furnace at 900 °C. The technique utilizes an electrochemical cell in which it is possible to achieve very thick (i.e., about 90 μm thick) boride layers in about 30 min. The effects of process duration on boride layer thickness, composition, and structural morphology were investigated using microscopic and X-ray diffraction (XRD) methods. We also developed an empirical equation for the growth rate of boride layers. XRD results revealed two principal boride phases: FeB and Fe₂B thickness of which was very dependent on the process duration. For example, Fe₂B phase was more dominant during shorter boriding times (i.e., up to 15 min.) but FeB became much more pronounced at much longer durations. The growth rate of total boride layer was nearly linear up to 30 min of treatment. However during much longer process duration, the growth rate assumed a somewhat parabolic character that could be expressed as d = 1.4904 (t)^0.5 + 11.712), where d (in μm) is the growth rate, t (in s) is duration. The mechanical characterization of the borided surfaces in plane and in cross-sections has confirmed hardness values as high 19 GPa at or near the borided surface (where FeB phase is present). However, the hardness gradually decreased to 14 to 16 GPa levels in the region where Fe₂B phase was found.     

Mechanical behavior of borides formed on borided cold work tool steel

In this study, some mechanical properties of borided cold work low-alloy tool steels were investigated. Boronizing was performed in a solid medium consisting of Ekabor-I powders at 1000°C for 2, 4 and 6 h. The substrate used in this study was high-carbon, low-alloy tool steel essentially containing 1.18 wt.% C, 0.70 wt.% Cr, 0.30 wt.% Mn, 0.10 wt.% V and 0.25 wt.% Si. The presence of borides (FeB+Fe₂B) formed on the surface of steel substrate was confirmed by optical microscope and X-ray diffraction (XRD) analysis. The hardness of the boride layer formed on the surface of the steel substrate and unborided steel substrate were 1854 and 290 kg/mm², respectively. Experimental results revealed that longer boronizing time resulted in thicker boride layers. Optical microscope cross-sectional observation of the borided layers revealed denticular morphology. The fracture toughness of the boride layers measured by means of a Vickers indenter with a load of 3 N was in the range of 2.52–3.07 MPa m^1/2.     

Electrochemical and XPS studies of the passive film formed on stainless steels in borate buffer and chloride solutions

The passivity of AISI 304L and AISI 316L stainless steels in a borate buffer solution, with and without the addition of chloride ions, was studied using cyclic voltammetry and potentiodynamic measurements. The passive layers formed by electrochemical oxidation at different passivation potentials on both the stainless steels were studied by X-ray photoelectron spectroscopy, their compositions were analysed as a function of depth, and the cationic fraction of the passive film was determined. The passive films established on the two stainless steels in the borate buffer solution at pH = 9.3 contained the oxides of two main elements, i.e., Fe and Cr. The oxides of the alloying elements Ni and, optionally, Mo, also contribute to the passive layer. In the presence of chloride ions a strong chromium enrichment was observed in the passive layers.