Effects of Surface Morphology on the Wear and Corrosion Resistance of Post-Treated Nitrided and Nitrocarburized 42CrMo4 Steel

The surface of alloyed carbon steel was subjected to thermochemical modification by nitrocarburizing and nitriding with or without postoxidation in order to improve its mechanical properties, corrosion, and wear resistance. Treated samples were characterized by testing their basic properties (compound layer thickness, nitriding, nitrocarburizing depth, and surface hardness) according to standards. Detailed estimation of the modified metal surface was performed by additional testing: X-ray diffraction, microstructure, surface roughness and topography, and wear and corrosion resistance. The surface layer obtained after nitrocarburizing treatment consists mainly of ε-Fe_2-3(N,C) and γ’-Fe₄(N,C); similarly, the nitrided surface is formed by ε-Fe_2-3N and γ’-Fe₄N iron nitrides. The surface layer after postoxidation contains additionally Fe₃O₄. The results obtained show that nitrocarburization, nitridation, and postoxidation result in better mechanical, wear, and corrosion resistance of 42CrMo4 steel, and postoxidized sample properties are influenced by surface morphology.     

H13热作模具钢的表面热处理

H13(4Cr5MoSiV1)钢成分 (% )为 0 32～ 0 4 5C ,0 80～ 1 2Si,0 2 0～ 0 5 0Mn ,4 75～ 5 5 0Cr,1 10～1 75Mo ,0 80～ 1 2 0V是目前广泛用于热挤压模和压铸模的热作模具钢 ,工作温度达 6 0 0℃。介绍了离子渗氮、N C共渗、N C V共渗、O S N共渗、S N C共渗、多元共渗等提高H13钢抗热疲劳、耐热磨损和耐蚀性能的表面低温化学热处理工艺 ,以及激光表面处理、高能束表面合金化、离子注入表面改性处理等高能束流表面处理及其最新进展。     

Theoretical treatment of nitriding and nitrocarburizing of iron

Mathematical models are developed for both nitriding and nitrocarburizing of iron taking into account the diffusion of N or C and N through various phases and the thermodynamic properties of the ternary Fe-C-N system. Analytical solutions are obtained for the ε/γ′ bilayer growth of the compound layer assuming constant diffusion coefficients, and the results are compared with those obtained from numerical simulations taking into account the concentration-dependent diffusivities. No significant difference was found between these two methods for nitriding of iron. For nitrocarburizing of iron, it was found that the off-diagonal diffusivities of the ε and γ′ phases must be taken into account in the analytical solution in order to obtain reasonable results. In addition, it is shown that the phase constitution of the compound layer produced during nitrocarburizing of iron can be predicted by the numerical simulation. Formerly Graduate Student, Department of Materials Science and Engineering, Royal Institute of Technology, Sweden     

Influence of titanium content and grain size on hydrogen cracking behaviour of hot-rolled steels

Hydrogen induced cracking was investigated for hot-rolled titanium steels. Aim of the present work was to observe the influence of titanium content and grain size on the cracking behaviour. Three titanium steels (0.12-0.30 % Ti; O.0057-0.0480 % C) and one non-titanium steel (0.0056 % C) were used for the investigation. Various grain sizes were generated by heat treatment at 950, 1050 and 1150 °C; furnace cooling was applied. The specimens were electrolytically charged with hydrogen at various current densities. It was found that cracks are generated at low charging current densities for the investigated steels. The titanium steels showed better performance than the non-titanium steel. It was shown that the charging current density does not correspond to the hydrogen concentration in a steel; the hydrogen concentration in steel B was 3.8 ppm at 1 mA/cm², in steel D it was found to be 15.5 ppm at 0.5 mA/cm². The total hydrogen concentration was found to be influenced by content of precipitates and grain size. It was shown that the percentage of cracked grain boundary area increases with increasing grain size. This increase is linear for the non-titanium steel whilst for the titanium steels a plateau was observed at a grain size diameter of 50 μm.     

Corrosion study of Al–Fe (20 wt-%) alloy in artificial sea water with NaOH additions

The corrosion behaviour of the Al–Fe (20?wt-%) alloy was investigated by electrochemical methods in an artificial sea water solution at various alkaline pH values adjusted by a NaOH solution. The electrochemical results showed lower current density values at a temperature of 23°C, varying from 0.008 to 0.873?mA/cm². The potentiodynamic polarisation results suggest the formation of a sensitive layer, which decreases with increasing pH. EIS results showed a corrosion mechanism control governing by diffusion of the solution ions across the permeable scale. SEM characterisation showed a scale formation composed of hydroxides as the main corrosion products; this was associated with increases in both the pH and the immersion time.     

Modification of the T15K6 hard alloy with high-power pulsed ion beams and compression plasma fluxes

The change in the morphology, phase composition, hardness of surface layers, microstructure, and elemental composition of the inner layers of an alloy under the effect of high-power pulsed ion beams (HIBs) and compression plasma streams (CPSs) is investigated. It is found that the thickness of the molten surface layer increases to 3–4 μm after the HIB effect: 300 pulses 9 × 10^?2 μm long with a summary energy density of 430 J/cm². The features of the CPF treatment are a larger time of pulse effect (100 μs) and the preferential convection agitation of the molten layer. As a result, a thicker layer of the (W, Ti)C solid solution with uniform elemental distribution over the depth and high hardness (30 GPa) is formed.     

Structural Changes in the Vanadium Sample Surface Induced by Pulsed High-Temperature Deuterium Plasma and Deuterium Ion Fluxes

The structural changes in the vanadium sample surface are studied as functions of the conditions of irradiation by pulsed high-temperature deuterium plasma and deuterium ion fluxes in the Plasma Focus installation. It is found that processes of partial evaporation, melting, and crystallization of the surface layer of vanadium samples take place in the plasma flux power density range q = 10⁸–10¹⁰ W/cm² and the ion flux density range q = 10¹⁰–10¹² W/cm². The surface relief is wavelike. There are microcracks, gas-filled bubbles (blisters), and traces of fracture on the surface. The blisters are failed in the solid state. The character of blister fracture is similar to that observed during usual ion irradiation in accelerators. The samples irradiated at relatively low power density (q = 10⁷–10⁸ W/cm²) demonstrate the ejection of microparticles (surface fragments) on the side facing plasma. This process is assumed to be due to the fact that the unloading wave formed in the sample–target volume reaches its irradiated surface. Under certain irradiation conditions (sample–anode distance, the number of plasma pulses), a block microstructure with block sizes of several tens of microns forms on the sample surfaces. This structure is likely to form via directional crack propagation upon cooling of a thin melted surface layer.     

The development of nitrogen concentration profiles on nitriding iron

On nitriding iron specimens nitrogen concentration profiles within the specimens are built up. A numerical method for the calculation of such concentration profiles was developed. The results calculated were compared with experimental data. It was found that during nitriding the nitrogen surface concentration approached relatively slowly the equilibrium value. This effect strongly influenced the development of the nitrogen concentration profile. The model predicted correctly the incubation time for compound(i. e., iron nitride) layer formation at the surface. If the fatigue resistance is strongly dependent on the (compressive) residual surface stress, the present treatment allows calculation of anoptimum nitriding time by determining when the maximum (compressive) residual surface stress occurs.     

Microstructure and mechanical properties of surface layers of 30CrMnSiA steel plasma nitrocarburized with rare earth addition

The pulse plasma nitrocarburizing for 30CrMnSiA steel was conducted at 560 °C for 8 h in mixed gases of N2:3H2 and different flow rates of rare earths (RE) addition. Effects of rare earths (RE) addition in the carrier gas on the surface morphology, phase structure and mechanical properties of the nitrocarburized layer were characterized by optical microscopy (OM), X-ray diffraction (XRD), scanning electron microscopy (SEM), microhardness testing and wear testing, respectively. The results showed that the surface phase structures changed from dual phases ε-Fe2-3N(C) and γ’-Fe4N(C) to phase Fe3C and incipient nitrides, and the nitrocarburized surface hardness value decreased slightly from 756 to 681 HV0.1 with the RE addition increasing in the carrier gas, and the corresponding morphology of the nitrocarburized surface was granular nitride group (diameter 0.8-1.5 μm) and compact-fine Fe3C stick and patch (mean size 100-300 nm), respectively. The wear resistance of the experimental steel could be improved remarkably by plasma RE nitrocarburizing. The nitrocarburized layer with Fe3C phase formed in the mixed gases of N2:3H2 and flow rate of 0.5 L/min RE addition showed the lowest friction coefficient and the narrowest wear track.)     

Effect of Pulsed Nitrogen Plasma and Nitrogen Ion Fluxes on the Structure and Mechanical Properties of Vanadium

The effect of powerful pulsed fluxes of nitrogen plasma and nitrogen ions generated in the PF-4 Plasma Focus setup (LPI; energy flux density of plasma pulse was 10⁸–10¹⁰ W/cm²) on the modification of vanadium surface is studied. Melting and ultrafast solidification result in a fine cellular structure (cell size of 100–200 nm) in a thin surface layer in samples. There are irradiation regimes causing directional crack growth after solidification and cooling of the surface layer and the formation of a block microstructure with a block size of several tens of micrometers. The thickness of the melted layer in the samples is 2–4 μm. Cracks propagate to a depth of 5–20 μm. It is established that irradiation by pulsed nitrogen plasma and high-energy nitrogen ions changes the microhardness of the vanadium surface layers. The microhardness increases by a factor of three with the number of plasma pulses and the distance between a sample and the anode of the Plasma Focus (PF) setup. The increase in the microhardness is in agreement with the refinement of coherent scattering regions, the increase in lattice microstrain ε, and the formation of vanadium nitrides. Pulsed fluxes of nitrogen plasma and nitrogen ions decrease the lattice parameter much greater than cold working (rolling) does. The lattice parameter decreases when the total irradiation power is increased (the number of pulses increases or the distance between a sample and the anode of the PF setup decreases). Such changes seem to be caused by the action of the residual macrostresses induced by pulsed plasma irradiation. In addition, X-ray diffraction analysis showed a change in the texture of the surface layer after ion-plasma treatment of coldworked vanadium samples in the PF setup.     

Effects of tribologically-penetrated hydrogen on the abrasive wear of mild steel in H2SO4 solution

The present work examines how tribologically-penetrated hydrogen affects the abrasive wear of mild steel in H₂SO₄ solution. The pin-on-disc type wear tests were carried out as a function of applied load at 298 K in 0.5 M H₂SO₄ aqueous solution in the presence and absence of 10^?4 As₂O₃ mol I^?1 as a hydrogen recombination poison with and without concurrent hydrogen-charging into the mild-steel pin specimen. Hydrogen-charging was electrolytically made for 4 h as a function of current density of 0.5 to 100 mA cm^?2. Subsequently, hydrogen-extraction measurements were performed from the worn pin specimen by using electrochemical hydrogen permeation technique, in order to determine the amount of hydrogen tribologically-penetrated into the pin specimen. The increased amount of the penetrated hydrogen by abrading action indicated tribologically-enhanced hydrogen penetration. The amount of penetrated hydrogen increased with charging current density or by addition of hydrogen recombination poison. As the current density increased, the corrosive-wear rate decreased and then increased, regardless of applied load or addition of hydrogen recombination poison. This indicated that a critical amount of the penetrated hydrogen exists, which is necessary for transition to cracking and dominates the mechanism in abrasive wear. Two-staged variation of the corrosive-wear rate with respect to the amount of penetrated hydrogen is discussed in terms of ploughing/cutting to cutting/cracking transition in the mechanism of abrasive wear.     

Room-temperature diffusion in Cu/Ag thin-film couples caused by anodic dissolution

Thin, 100-nm films of first silver and then copper were deposited consecutively onto inert substrates by magnetron sputter deposition. Constant anodic current densities were applied at room temperature to dissolve the outer copper film to varying depths. The 50Cu/50Ag interface, derived from the auger electron spectroscopic concentration-depth profile, initially moved into the copper toward the outer dissolving surface, indicating enhanced diffusion of copper into silver. After longer times at all anodic current densities, the interface reversed and moved back toward the underlying silver-rich layer, indicating that eventually diffusion of silver into copper predominated. The reversal time was inversely proportional to the anodic current density. These effects are explained by anodic formation of subsurface vacancies which migrate as divacancies to the copper/silver interface where they affect interface movements by the well-known Kirkendall mechanism. Calculated diffusivities up to 10⁻¹² cm²/s at maximum anodic current densities of 900 μA/cm² are dramatically above any that are normally observed at room temperature.     

Effects of grain size and secondary phase on corrosion behavior and electrochemical performance of Mg-3Al-5Pb-1Ga-Y sacrificial anode

Grains with size of 4.5—20.5 μm were studied for their corrosion behavior and electrochemical performance in a Mg-3 Al-5 Pb-1 Ga-Y sacrificial anode using immersion testing,electrochemical measurements and microstructure analysis.The results show that fine-grained microstructure has higher chemical activity and more negative discharge potentials than coarse-grained samples.The sample with the smallest average grain size of 4.5 μm exhibits corrosion current density of 7.473×10~(-5) A/cm~2,and work potentials of-1.721 V at current density of 10 mA/cm~2.The density of grain boundaries and LAGBs increases with grain refinement,which leads to higher rates of dissolution and diffusion for the atoms.The secondary phases promote the occurrence of corrosion and improve the chemical activity of alloy due to their higher potential than the substrate.Higher corrosion rate and discharge activity are directly attributed to the higher density of grain boundaries and LAGBs,as well as the secondary phase.     

Electron beam surface modification of a porous bronze-graphite composite

Elemental powders were mixed to obtain a 90 wt pct copper, 8 wt pct tin, and 2 wt pct graphite composite. The porosity level of the sintered specimens was reduced from 25 to 10 pct, which resulted in an increase in the macrohardness value from 17 Hv (90 MPa) to 67 Hv (355 MPa); the density of the sintered specimen was 7.80 g · cm⁻³. The synthesized material was then subjected to electron beam (EB) surface melting. The resultant surface was homogeneous and the microstructural features were refined. The segregation level and variation in the microhardness were drastically reduced. The morphology of the otherwise irregular pores changed to spherical, thereby reducing their interfacial energy. An intriguing modification in the EB melted layer had a density gradient with depth that is sensitive to the heating time of the material using EB. At a heating time of 250 ms, the upper region of the melted layer was dense and hard; the density and the hardness were 8.5 g · cm⁻³ and 103 ± 7 Hv, respectively, while the lower region had density of 6.7 g · cm⁻³ (porosity 22 pct). If the heating time was reduced to 17 ms, the distribution of pores was reversed; the density of upper and lower layers changed to 3.9 and 8.2 g · cm⁻³, respectively. In spite of the higher density of pores, the EB processed composite exhibited increased hardness, compressive strength, and tensile strength. The formation of pores in the lower EB melted region was explained using a qualitative fluid flow model. The combination of a dense substrate and porous surface was desirable, since the former improved the strength and the thermal conductivity of the composite and the latter could be impregnated with oil to achieve the required lubrication levels.     

高温氢还原法制备纳米硅/石墨烯复合材料的结构与电化学性能

将Hummers法制备的氧化石墨烯(graphene oxide,GO)与纳米硅粉进行超声复合和高温氢还原,制备锂离子电池用纳米硅/石墨烯(Si/G)复合材料。利用扫描电镜、透射电镜、X射线衍射和Raman光谱分析,对Si/G复合材料的形貌与结构进行分析与表征,并测试其电化学性能。结果表明,通过高温氢还原,氧化石墨烯全部还原为石墨烯,无其它杂质相生成。石墨烯包覆在纳米硅颗粒表面,形成层状复合结构;与纯纳米硅粉相比,Si/G复合材料的电化学性能明显提高,在300 m A/g电流密度下,首次放电比容量为2 915.0(m A·h)/g,首次充电比容量为1 080.5(m A·h)/g,20次循环后比容量稳定在969.6(m A·h)/g,库伦效率为99.8%;而纯纳米硅粉的首次放电比容量和首次充电比容量分别为932.7和349.4(m A·h)/g,20次循环后比容量仅为6.4(m A·h)/g。     

Microstructure modification and surface hardening of 12% chromium steels by pulsed gas plasma flows

The changes in the microstructure and the surface hardening of chromium (12 wt % Cr) ferritic–martensitic steels in various initial states treated by high-temperature pulsed gas plasma flows (flux energy density Q = 17–78 J/cm², pulse duration τ_p = 15–20 μs) have been studied experimentally. Treatment of fuel-element pipes and monolithic specimens of 12% chromium steel under melting of near-surface layers is found to form a gradient structure–phase state with a submicrocrystalline (~130 nm) surface layer up to 10 μm thick. The parameters of the formed cellular submicrostructure and the modified layer thickness are found to weakly depend on the composition and the thermomechanical treatment of the steels. It is shown that treatment of fuel-element pipes made of 12% chromium steels by plasma flows leads to their surface hardening by 40–60% and by a factor of 1.7–1.9 upon surface liquid-phase alloying with aluminum and chromium irrespective of steel composition.     

Residual stress-affected diffusion during plasma nitriding of tool steels

Plasma nitriding of tool materials is common practice to improve the wear resistance and lifetime of tools. Machining-induced compressive residual stresses in shallow layers of some tenths of microns are observed accompanied by other characteristic properties of machined surfaces in these high-strength materials. After plasma nitriding of M2 high-speed steel, previously induced compressive residual stresses remain stable and the depth of diffusion layers decreases with increasing compressive residual stresses. This article reports investigations of plasma nitrided samples with different levels of residual stresses induced prior to the nitriding process. For comparison, experiments with bending load stresses during plasma nitriding have also been carried out. The plasma nitriding treatment was performed at constant temperature of 500 °C with a gas mixture of 5 vol pct N₂ in hydrogen. Nitriding time was varied from 30 to 120 minutes. All samples were characterized before and after plasma nitriding concerning microstructure, roughness, microhardness, chemical composition, and residual stress states. Experimental results are compared with analytical calculations on (residual) stress effects in diffusion and show a clear effect of residual and load stresses in the diffusion of nitrogen in a high-strength M2 tool steel.     

循环等离子渗氮工艺对38CrMoAl钢渗氮层组织和性能的影响

试验了38CrMoAl钢(%:0.35～0.42C、1.35～1.65Cr、0.15～0.25Mo、0.70～1.10Al)280 Pa 560℃,12 h常规渗氮和170 Pa 560℃3 h快冷至室温循环等离子渗氮对渗氮层组织、硬度、硬度梯度和耐磨性的影响。结果表明,循环等离子体渗氮工艺有利于表层ε相分解,更有利于氮渗入钢中γ′相;在获得相同的渗层表面硬度和硬度梯度下,循环等离子渗氮速度明显高于常规渗氮速度,并改善渗氮后钢的耐磨性。     

预氮化对Cr-Co-Mo-Ni轴承钢渗碳层组织和性能的影响

化学热处理工艺对轴承钢的服役性能具有重要影响。研究了预氮化工艺对新型Cr-Co-Mo-Ni轴承钢渗碳层组织和性能的影响规律。结果表明,经预氮化处理的渗碳层组织可划分为析出物和针状马氏体区,析出物、针状马氏体和板条马氏体混合区,以及析出物和板条马氏体区,且在原渗氮形成的白亮层位置有数量较多的微小孔洞出现。预氮化全工艺试样表层含铬碳化物析出较少,随渗层深度的增加,次表层析出较多的含铬碳化物且尺寸较大。相较于仅渗碳试样,在表层相同位置,经预氮化处理的试样在回火后,析出物的尺寸更细小。预氮化能够提高渗碳效率,增加渗层硬度,在全工艺试样渗层深度为0.12~0.82 mm,预氮化试样的硬度高于仅渗碳试样,且经渗后热处理的硬度增加程度也显著高于仅渗碳试样。     

Room-temperature diffusion in Cu/Ag thin-film couples caused by anodic dissolution

Thin, 100-nm films of first silver and then copper were deposited consecutively onto inert substrates by magnetron sputter deposition. Constant anodic current densities were applied at room temperature to dissolve the outer copper film to varying depths. The 50Cu/50Ag interface, derived from the auger electron spectroscopic concentration-depth profile, initially moved into the copper toward the outer dissolving surface, indicating enhanced diffusion of copper into silver. After longer times at all anodic current densities, the interface reversed and moved back toward the underlying silver-rich layer, indicating that eventually diffusion of silver into copper predominated. The reversal time was inversely proportional to the anodic current density. These effects are explained by anodic formation of subsurface vacancies which migrate as divacancies to the copper/silver interface where they affect interface movements by the well-known Kirkendall mechanism. Calculated diffusivities up to 10⁻¹² cm²/s at maximum anodic current densities of 900 μA/cm² are dramatically above any that are normally observed at room temperature.