Reactive plasma immersion ion implantation for surface passivation

Plasma immersion ion implantation (PIII) using halogen or oxygen plasmas has been employed for the surface passivation of advanced alloys with a view to their applications for high-temperature oxidation protection and in medicine. Special devices have been designed to ensure efficient plasma generation and reduce sample contamination arising from the interaction of the aggressive plasmas with the chamber components under bias. The paper addresses two main applications of PIII, namely oxidation protection of gamma-titanium aluminides (γ-TiAl), and modification of the surface properties of shape-memory superelastic nickel-titanium (NiTi) alloys. TiAl intermetallics are of great interest for advanced automobile, aerospace and power generation applications due to their low specific weight and high strength. However, excessive oxidation occurring in these materials at temperatures above 700 °C has hindered their widespread use. Samples of technical γ-TiAl alloys have been treated by both beamline implantation of Cl or F, and PIII of Cl using an Ar/Cl gaseous blend or alternative precursor gases. High-temperature oxidation behavior has been examined under conditions of either isothermal or thermocyclic oxidation at 900 °C. Optimized implantation processing produces marked improvement in the oxidation behavior of the γ-TiAl samples. On the basis of these results, a commercially viable process for enhancing the high-temperature oxidation resistance of γ-TiAl alloys using PIII of halogens is being developed. NiTi alloys are promising materials for use in biomedicine, provided that the release of Ni ions into the body environment can be sufficiently reduced. Oxygen PIII at substrate temperatures below 250 °C results in the formation of a transparent rutile TiO₂ surface layer with a Ni content down to below 1 at.%. This layer in turn serves as a barrier to the corrosion and out-diffusion of Ni ions. Biocompatibility tests show superior in vitro blood compatibility in comparison with untreated NiTi samples.     

Electrochemical studies of stainless steel implanted with nitrogen and oxygen by plasma immersion ion implantation

Plasma Immersion Ion Implantation (PIII) of stainless steel with nitrogen at temperatures lower than 400 °C has been reported to increase the hardness of the material by several times. However, expectations that the corrosion resistance will remain unaffected after implantation were not found to be so. In the present study the influence of post-oxygen implantation on the corrosion resistance of nitrogen implanted stainless steel is presented. Stainless steel samples were subjected to oxygen, nitrogen and post-oxygen ion implantation at different temperatures. GIXRD and microRaman studies of the implanted samples showed that oxygen implantation leads to the formation of an oxide layer consisting of corundum and spinel structures. The corrosion properties of the implanted samples were studied by potentiodynamic polarization and electrochemical impedance techniques in 3.5% NaCl solution. After nitrogen implantation the corrosion current increased and the corrosion potential shifted to the less noble side to − 0.486 V as compared to − 0.284 V for the substrate. Oxygen implantation at 400 °C shifted the corrosion potential to the nobler side to − 0.2 V with decrease of corrosion current. For post-oxygen ion implantation at temperatures lower than 400 °C, the corrosion current was higher than the substrate and the corrosion potential was also on the less noble side. However, post-oxygen ion implantation at 400 °C after nitrogen ion implantation resulted in improved corrosion resistance as the corrosion potential shifted to nobler side and the corrosion current was lower than that of substrate.     

Influence of grain size on nitrogen diffusivity in austenitic stainless steel

Ion nitriding of austenitic stainless steel with the aim to improve the tribological properties while retaining the excellent corrosion resistance is a well-established method. At the same time, strongly varying microstructures can be obtained depending on the pretreatment. In this work, the influence of prior heat treatment in the temperature range between 950 and 1200 °C on the microstructure, especially the grain size, and the corresponding observed nitrogen diffusivity in austenitic stainless steel DIN 1.4301 (AISI 304, X6CrNi18.10) after nitrogen plasma immersion ion implantation (PIII) is studied. Cross-section and plan view samples were prepared and investigated. With increased annealing temperature, both larger grains and slower diffusion was observed, despite diffusion ranges much smaller than the average grain size. Another, still hidden effect of dislocation densities or other defects on both secondary parameters is suggested.     

Surface morphology and tribological behavior of AlSi10 alloys treated by plasma immersion ion implantation for automotive applications

Plasma immersion ion implantation (PIII) was used to implant nitrogen into Al at a temperature in the range of 320–520 °C. AlN phase was observed for temperatures above 450 °C, whereas no AIN detected by XRD diagnosis at temperatures below 380 °C. It was also observed that there was no effective increase in hardness of the material, but some wear resistance due to formation of AlN.     

Nitriding of austenitic stainless steel using pulsed low energy Ion implantation

Using a pulse low energy ion implantation with an electronic beam switch operating in the kHz regime, a more efficient nitriding process is possible than with either pulsed plasma immersion ion implantation (PIII) or continuous low energy ion implantation (LEII). Besides the pulsed mode, a fast and precise external heating system for controlling the substrate temperature is necessary. Using such an experimental setup, it is shown that the duty cycle itself does not influence the diffusion and phase formation, as long as the exact same substrate temperature is maintained, thus nitrogen uptake and diffusion are decoupled. Optimal nitriding efficiency was observed for a duty cycle between 20 and 35%. At lower duty cycles (below 15% duty cycle), not enough nitrogen was available to allow the formation of expanded austenite, while higher duty cycles led to a reduced layer thickness caused by higher sputtering induced by the increased ion bombardment itself.     

Effect of alloyed molybdenum on corrosion behavior of plasma immersion nitrogen ion implanted austenitic stainless steel

Plasma immersion ion implantation (PIII) of nitrogen has been performed on two austenitic stainless steels (with and without Mo addition) at three different temperatures namely, 250, 380 and 500 °C for 3 h. Grazing angle X-ray diffraction (GXRD) was carried out on the surface of the steels (both PIII treated and untreated). GXRD results suggest that PIII is more effective in Mo containing stainless steel (SS). The electrochemical corrosion studies examined through both by DC polarization and EIS technique in 3.5 wt.% NaCl reveals that, 3 h N-implantation at 250 and 380 °C improves the corrosion and pitting resistance of both the austenitic stainless steels under investigation. The effect N implantation on pitting resistance is seen more in the presence of Mo, than when it is not present in the SS. It is further emphasized that the pitting resistance of the alloys significantly deteriorates, when they are implanted at 500 °C.     

Improved properties of Ti6Al4V by means of nitrogen high temperature plasma based ion implantation

A stable heating source, providing steady temperatures in the range of 200 to more than 1000 °C, was used to perform high temperature plasma based ion implantation (PBII) on Ti6Al4V. The precise control of the heating of the samples in vacuum while performing PBII is accomplished by means of an efficient electron source, working independent of the conditions of the discharge.The electrons produced by a low work function (2.1 eV) barium, strontium and calcium oxide cathode help with the start-up of the discharge, with the increase of nitrogen ionization and heating of the samples. The large growth of the treated layer thickness was a result of the thermal diffusion of nitrogen, reaching up to 20 μm, in the total process time lasting only 100 min. Experiments were run by setting a constant substrate temperature during PBII to 800 °C but varying the pulse intensity and the duration of the process. Our results showed improvements of the mechanical and tribological properties, and also higher resistance to corrosion of the samples treated by high temperature PBII.     

Effects of implantation temperature and volume flow rate ratio of nitrogen and hydrogen on nitrogen concentration distribution, mechanical properties, fatigue life, fracture toughness, and tribological behavior of plasma-nitrided P20, 718 and 420 steels

In the present study, three steel materials, AISI P20 DEM NO.3, ASSAB 718 and AISI 420, were selected as the mold substrate materials in plastic injection forming. The plasma immersion ion implantation (PIII) system with an electron cyclotron resonance microwave source was applied to prepare the specimens by varying the implantation temperature (400 °C, 460 °C and 520 °C) and the volume flow rate ratio (4:1, 1:1 and 1:3) of nitrogen to hydrogen in the gas mixture (N₂:H₂). For the specimens with the same substrate material, the mean hardness was either invariant to or lowered by increase in the total penetration depth of nitrogen. The hardness was lowered by increasing the distance of the peak position of nitrogen concentration from the implantation surface. Both the fracture toughness and the fatigue life of a specimen at the nitrided layer were elevated by increasing the implantation temperature. The most significant increase in each of these two mechanical properties due to the temperature increase gives rise in the P20 specimens. Varying the N₂:H₂ ratio shows a fatigue life sequence of (FL)_4:1 > (FL)_1:3 ≥ (FL)_1:1 for all three substrate materials. X-ray diffraction (XRD) was applied to determine the phase structures at the nitrided layer which was formed by changing either the implantation temperature or the N₂:H₂ ratio. The (α-Fe + CrN) phase in the nitrided later can elevate the fatigue life and fracture toughness of the specimen. However, the increase in the hardness is due to the combined effect of all main phases formed in the nitrided later. The scratch wear resistance of a specimen with ion implantations is significantly enhanced compared with that exhibited in the “pure” specimen (without nitrided layer). However, most of the specimens with ion implantations showed severer adhesive wear than corresponding “pure” specimens.     

The oxidation of iron-carbon alloys at low temperatures

The formation of thin oxide films (<1000 Å) on polished iron-carbon alloys in the temperature range of 200–350°C and in 100 Torr of dry oxygen was investigated. A combination of vacuum microbalance and transmission electron microscopy techniques were employed to characterize the oxidation process kinetically and morphologically, respectively. The initial oxide formation on the iron-carbon alloys obeyed a two-stage logarithmic kinetic mechanism with activation energies of 0.26 eV and 0.32 eV for the first and second stage, respectively. These kinetics and activation energies are in agreement with the two-stage logarithmic kinetic theory developed by Uhlig, assuming electron transfer as the rate-controlling mechanism. Logarithmic kinetics were followed by parabolic kinetics with an activation energy of 1.08 eV, indicating cationic grain boundary diffusion as the rate controlling mechanism. The oxide formed over the iron-carbon alloys at 300°C was primarily due to the oxidation of the ferrite phase, but a thin protective oxide film (~ 150 Å) was formed on the carbide phase. At later stages, a lateral growth of the oxide crystallites formed over the ferrite phase resulted in a gradual coverage of the carbide phase. This lateral growth was the major effect of the second phase on the oxidation of two-phase iron-carbon alloys. A systematic study of the effect of the phase boundary length on the oxidation of iron-carbon alloys was quantitatively evaluated.This research was supported by grant number DA-18-035-98(A) from the Chemical Research Laboratory, Edgewood Arsenal, Department of the Army. This paper is based on work performed as part of a thesis submitted by H. J. Kim to Lehigh University in partial fulfillment of the requirements for the Ph.D. degree in Metallurgy and Materials Science.     

Ni tracer diffusion in the B2-compound NiAl: influence of temperature and composition

The effect of composition and temperature on Ni bulk self-diffusion is investigated for nine different single crystalline NiAl alloys with well-defined compositions between 46.8 and 56.6 at.% Ni in the temperature range from 1050 to 1630K. The diffusion penetration profiles of Ni in NiAl were determined by applying two different techniques of profile detection. Radiotracer experiments have been carried out using the ⁶³Ni tracer, a serial sectioning technique, and sensitive liquid scintillation counting for the high temperature measurements, while at lower temperatures the diffusion profiles were analyzed by secondary ion mass spectrometry (SIMS) using the highly enriched stable isotope ⁶⁴Ni. In contrast to the literature data on Ni self-diffusion in NiAl alloys by Hancock and McDonnell [Phys. stat. sol. A4, (1971) 143], the present measurements show an unexpected concentration dependence of the Ni diffusion coefficients D with nearly constant diffusivities for stoichiometric and Al-rich alloys and increasing D values with increasing Ni content on the Ni-rich side of the NiAl composition range. The effective diffusion activation enthalpy Q is equal to about 3.0±0.07 eV for the Al-rich, stoichiometric, and slightly Ni-rich NiAl alloys, while for the compositions with larger Ni content a decrease of Q was observed with increasing Ni content, for example, Q=2.39 eV for the Ni_56.6Al_43.4 alloy. The present experimental results imply that mainly the same diffusion mechanism operates on both sides of stoichiometry in NiAl. This mechanism is identified with the triple defect mechanism. Its contribution is compositionally independent. The activation energy of Q=3.18 eV was calculated for the triple defect mechanism using empirical EAM potentials in agreement with the experimental data. The decrease of Q at large Ni concentrations on the Ni-rich side is explained by an additional contribution of the anti-structure bridge mechanism with the activation energy of Q=1.73 eV.     

In vitro corrosion behavior of TiN layer produced on orthopedic nickel-titanium shape memory alloy by nitrogen plasma immersion ion implantation using different frequencies

In the present work, the NiTi surface was modified by nitrogen plasma immersion ion implantation (PIII) in an effort to improve the corrosion resistance and mitigate nickel release from the materials. The implanted nitrogen depths and thicknesses of the surface TiN barrier layers were varied by changing the pulsing frequencies during PIII. In order to determine the optimal parameters including the pulsing frequencies, electrochemical tests including open circuit potential (OCP) measurements and potentiodynamic polarization tests were conducted on the untreated and N-implanted NiTi in simulated body fluids (SBF). Our results reveal that the nitride layer produced using a frequency of 50 Hz has the best stability under the OCP conditions and the TiN layer produced using 200 Hz has the highest potentiodynamic stability after immersion in SBF for a long time. The observation can be correlated to the temperature during PIII and the thickness of TiN layer. The TiN layer on the NiTi surface favors deposition of Ca-P composites thereby compensating for the instability of the TiN layer produced at a higher frequency.     

Optical properties of antimony-implanted ZnO epilayers

Antimony ions were implanted into ZnO films grown on c-plane sapphire by pulsed-laser deposition. Raman scattering modes of the Sb-implanted samples were found to be influenced by the implantation dose. A characteristic peak at 576 cm^− 1 was observed with an asymmetric shape due to ion damage to the lattice of the implanted ZnO films. When the implant dose was low, the height of the peak was reduced by rapid thermal annealing at 400-600 °C and the symmetry of the spectra was recovered. However, when the Sb dose exceeded 1 × 10¹⁵ cm^− 2, the peak maintained unchanged after rapid thermal annealing at temperatures up to 600 °C. A broad and low Raman peak was observed at 437 cm^− 1, which is related to the surface damage caused by the energetic ion bombarding. Photoluminescence measurement showed a decrease of the bandedge emission at 3.36 eV, a clear effect of defects induced by the implantation, and confirmed partial recovery of the crystal by rapid annealing.     

Rapid nitriding of pure iron by thermal plasma jet irradiation

Pure iron samples were exposed to thermal plasma jet and nitrided for 15 min at a temperature ranging from 545 °C to 742 °C. For comparison purposes, conventional ion nitriding was also performed using glow discharge plasma at 580 °C for 8 h. For conventional plasma nitriding, a top compound layer and a bottom diffusion zone are observed. In contrast, an additional “transition zone” is observed between the compound layer and the diffusion zone for the thermal plasma jet treatment when the process temperature is 667 °C or above. This “transition zone” is quite thick (a few tens of micrometers), determined by the treatment temperature, and has unique features in the phase formation and nitrogen distribution. At 706 °C, the content of γ′phase, as well as the content of nitrogen and the hardness, reaches the maximum. Compared with the traditional plasma nitriding process, the reaction speed of thermal plasma irradiation is much higher. A nitrided case depth over a few tens of micrometers is obtained in plasma jet nitriding for only 15 min versus a depth of only a few micrometers in conventional plasma nitriding for 8 h. The formation of the “transition zone” and the mechanism for the high nitriding speed are discussed in the paper. It is believed that this technology can be applied at atmospheric pressure in field without the requirement for a vacuum system. Hence, this technology may be advantageous for practical applications.     

Effect of the pressure in the gas-discharge chamber on the depth of nitrogen diffusion in titanium alloys

Among all the kinds of surface hardening of titanium alloys ion nitriding in a hydrogen-free medium is the most efficient and environmentally safe. The time of nitrogen saturation of titanium alloys by this method is 10–15 times shorter than in conventional nitriding. The acceleration of the diffusion of nitrogen under conditions of a glow discharge makes it possible to conduct the nitriding of (α+β)-titanium alloys at low temperatures that correspond to those of their aging, which had been impossible earlier. Diffusion saturation in ion surface impregnation is a multifactor process, which makes it controllable. One of the main controlling factors of ion nitriding is the pressure of the working gas. A study of the effect of the pressure in the gas-discharge chamber on the depth of nitrogen diffusion in titanium alloys (under conditions of stable existence of the glow discharge) made it possible to determine the dependence of the thickness of the layer and the specific power of the discharge on the nitrogen pressure and to determine the interrelation between the specific power and the saturating capacity of the gas medium. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 9, pp. 32–35, September, 1998.     

Internal friction in Fe–Al–Si alloys at elevated temperatures

Anelastic effects in ternary Fe–Al–Si alloys at elevated temperatures (from 400 to ∼700 °C) have been studied by mechanical spectroscopy. The contributions of several damping mechanisms (high temperature background, Zener and grain boundary relaxations), which are sensitive to the structural state in the temperature range studied, are analysed. The structure of the alloys was examined by different methods. The results of computer analyses of the experimental data justify the superposition of several relaxation processes. Parameters of the Zener relaxation in two ternary Fe–Al–Si alloys are determined: the peak temperature is about 545 °C (f ≈ 2 Hz); the mean value of the activation energy of the Zener relaxation is about 2.54 eV.     

Internal-Nitriding Behavior of Ni-V and Ni-3Nb Alloys

Ni-2V, Ni-5V, Ni-12V, and Ni-3Nb alloys (w/o)were nitrided in 10 v/o NH₃(bal.H₂) over the range of 700-1000°C. Thegrowth rates of the reaction zones followed parabolicbehavior for all of the alloys from 700 to 900°C. At 1000°C, Ni-2V andNi-3Nb formed nitride scales, whereas Ni-5V and Ni12Vformed internal-nitride zones. Nitridation ratesdecreased with increasing vanadium content for the Ni-Valloys. VN precipitated in the Ni-V alloys and NbNprecipitated in Ni-3Nb for all exposure conditions inwhich internal nitridation occurred. The precipitatemorphology changed with temperature and distance from the gas-metal surface. The VN and NbNprecipitates were generally small and spheroidal nearthe surface, increasing in size with distance andtemperature. The NbN precipitates became Widmanstattenat higher temperatures and/or increasing distance withinthe nitrided zone. The solubility of nitrogen in pure Niwas determined and found to decrease with increasingtemperature from 700 to 1000°C. Expressions for the diffusion coefficient of nitrogen in nickelwere determined from the measured permeabilities of eachalloy and the nitrogen solubilities in nickel.     

A Study of nitrogen ion-implanted ti-6ai-4v eli by plasma source ion implantation at high temperature

Plasma source ion implantation target temperatures are estimated by measuring the diffusion coefficient of nitrogen in the target and subsequently deducing the temperature. The diffusion coefficient is measured by comparing measured nitrogen concentration profiles to Monte Carlo simulations. Auger results indicated the affected zone of implantation is about 0.5 μm thick. Surface Knoop hardness improved from 400 to 900 (for 1- g applied load). Wear behavior was studied using a pin-on-disk wear tester. The wear data show a factor of 30 increase in wear lifetime (1 μm wear depth was chosen as the failure criterion). Comparison shows that the wear behavior of Ti-6AI- 4V ELI (extra low interstitial) is as good as that of cobalt-chromium alloy, another candidate for surgical applications.     

Creep of Fe3Al-based alloys with vanadium and carbon additions

Creep experiments were conducted on Fe₃Al-based alloys with vanadium and carbon additions in the temperature range from 923 to 1023 K, corresponding to the occurrence of B2 lattice. The alloys contained (in atomic %) (i) 27.0 Al, 1.17 V, and 0.02 C and (ii) 27.0 Al, 1.13 V, and 0.73 C (Fe balance). The alloys were tested in the as-cast state and annealed at 1273 K for 50 h. Creep tests were performed in uniaxial compression at a constant load with stepwise loading. Stress exponents and activation energies for the creep rate were determined. The values of the stress exponent in low-carbon alloy correspond to a five-power-law creep. The activation energy is greater than the activation enthalpy of diffusion of both Fe and Al in Fe₃Al and is substantially greater than the activation enthalpy of diffusion of V in Fe₃Al. The creep rate is impeded in the high-carbon alloy by the presence of tiny carbide particles. Consequently, the creep resistance of the high-carbon alloy in the as-cast state is greater, especially for higher temperatures and lower stresses. The carbide particles coarsen during annealing at 1273 K and are unable to obstruct dislocation motion because the mean distance between them is too large. The high-carbon alloy is then creep-weaker due to the reduced amount of vanadium present in the matrix.     

PIII treatment of Ti alloys and NiTi for medical applications

PIII is a powerful method to obtain hard and wear resistant surface on Ti alloys and NiTi by oxygen or nitrogen implantation. By adjusting the temperature, treatment time and heating regime, different phase compositions and layer thickness can be obtained. Depending on the specific system, a strong influence of the resulting microstructure on the wear and fatigue properties was observed. By considering these restrictions, successful animal tests can be designed and executed, as shown in this review article.     

High frequency and low voltage plasma immersion ion implantation of nitrogen on industrial pure iron at different Rf power

Traditional plasma ion immersion implantation (PIII) can effectively improve material mechanical property and corrosion resistance. But the modified layer by PIII is too thin for many industrial applications. High frequency and low voltage plasma immersion ion implantation (HLPIII) has advantages of PIII and nitriding. Comparing with traditional ion nitriding, HLPIII can obtain higher implantation energy and create a thick modified surface layer. In the present paper nitriding layers were synthesized on industrial pure iron using high frequency and low voltage plasma immersion ion implantation with different RF power (400 W, 600 W, and 800 W). The microstructure of the nitriding layers was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The mechanical properties such as microhardness and wear resistance were analyzed using HXD1000 microhardness and CSEM pin-on-disk wear testing machine. The anodic polarization characteristics were measured in a 0.9% NaCl solution at room temperature to examine the corrosion resistance of the nitriding layer. The results reveal that Fe₂N, Fe₃N and Fe₄N coexist in the nitriding layer. The nitriding layer is a corrosion protective coating on industrial pure iron in 0.9% NaCl solution. The hardness, wear resistance and corrosion resistance of the nitrided layers on industrial pure iron increase with RF power.