Structure and properties of silver-containing a-C(H) films deposited by plasma immersion ion implantation

In this study, we have grown silver-containing hydrogenated (a-C:H) and non-hydrogenated (a-C) amorphous carbon coatings by two plasma immersion ion implantation methods: I) chemical vapor deposition of methane combined with pulsed filtered cathodic arc deposition of silver, and II) by alternating arc pulses from graphite and silver in a dual cathodic arc plasma source. This unique “bias selective” feature of the deposition system allowed the deposition of silver with the substrates at ground and avoided the sputtering of the grown a-C film. Chemical composition of the samples was analyzed by acquiring their compositional depth-profiles using radio-frequency Glow Discharge Optical Emission Spectroscopy (rf-GDOES), while the microstructural properties were analyzed by X-ray absorption near edge spectroscopy (XANES) and Raman spectroscopy. In this contribution, we compare mechanical and biomedical properties by means of nanoindentation and cell viability tests, respectively, of a-C(H) films obtained by two different plasma immersion ion implantation techniques.     

Duplex diamond-like carbon film fabricated on 2Cr13 martensite stainless steel using inner surface ion implantation and deposition

A duplex plasma immersion ion implantation and deposition (PIIID) process, involving carbon ion implantation and diamond-like carbon (DLC) film deposition, is proposed to treat the inner surface of a tube. Samples of 2Cr13 martensite stainless steel were placed inside the tube to investigate the performance of the films. Carbon ion implantation was finished by biasing the tube with a high voltage, and the DLC film deposition was obtained by biasing the tube with a medium voltage. Raman spectrum, ball-on-disc, indentation and scratch tests were used to investigate the structure, tribological property and adhesion strength of the as-deposited films. The Raman spectrum shows that the sp³ bonding is formed in the as-synthesized film. Tribological and scratch test results reveal that the duplex DLC coating with the implantation time of 1 h has the largest adhesion strength and the best wear resistance.     

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.     

Diamond-like carbon films synthesized on bearing steel surface by plasma immersion ion implantation and deposition

Diamond-like carbon (DLC) films were synthesized by plasma immersion ion implantation and deposition (PIIID) on 9Cr18 bearing steel surface. Influences of working gas pressure and pulse width of the bias voltage on properties of the thin film were investigated. The chemical compositions of the as-deposited films were characterized by Raman spectroscopy. The micro-hardness, friction and wear behavior, corrosion resistance of the samples were evaluated, respectively. Compared with uncoated substrates, micro-hardness results reveal that the maximum is increased by 88.7%. In addition, the friction coefficient decreases to about 0.1, and the corrosion resistance of treated coupons surface are improved significantly.     

Effect of metal ion implantation on thermal instability of diamond-like carbon films

In this work, molybdenum and tungsten ions were implanted onto the DLC films deposited by filtered cathodic vacuum arc. We investigated the effects of ion species and doses on carbon related bonding property such as the ratio of sp³ carbon to sp² phase, the chemical composition and tribological properties of the DLC films in the range of 200 to 600 °C. The oxidation starting temperature decreased with an increasing ion dose and ion mass owing to higher sp² carbon fraction. Oxidation of the implanted-metal element, however, keeps the DLC film from carbon sublimation by oxidation, offering stable tribological characteristics by covering it with a metal oxide layer at the high temperature.     

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.     

Plasma immersion ion implantation into cylindrical bore using internal inductively-coupled radio-frequency discharge

Plasma immersion ion implantation (PIII) is a potentially excellent interior surface treatment technique due to no line-of-sight restriction. However, some problems have been encountered due to the low ion energy and ion fluence non-uniformity especially for treatment of the interior wall of a thin tube. In this paper, a new method for inner surface PIII using internal inductively-coupled radio-frequency (RF) discharge is described. A cylindrical inductive coil inserted inside the tube serves as both the plasma source and grounded electrode to avoid overlapping of the plasma sheath fronts propagating from opposite sides. The effects of the gas species, gas pressure, RF power, and number of coil turns are investigated. Our results demonstrate the feasibility of this novel inner surface treatment method and the number of turns in the coil has a critical influence on the discharge behavior. If the number of turns is little, the plasma density is low and non-uniform inside the tube due to the relatively intense capacitively-coupled RF discharge at the two ends. In contrast, the plasma density and uniformity are evidently improved by using more turns in the coil.     

Fluorine and carbon ion implantation and deposition on metals by plasma source ion implantation

Deposition of fluorine containing diamond-like carbon films is an effective solution for the improvement of machine parts in an aggressive aqueous environment when the combination of a hydrophobic surface with good corrosion protection and low friction coefficients is required. Stainless steel and silicon were treated by plasma source ion implantation using the gases CF₄, C₆F₆ and C₆H₅F, in the latter case with previous methane implantation. Depending on the plasma gas there are differences in the fluorine content, depth distribution, film thickness, water contact angle and friction coefficient.     

V and N co-doped diamond-like carbon films deposited by pulsed bias arc ion plating

V and N co-doped diamond-like carbon (DLC–VN) composite films were deposited on cemented carbide substrates by pulsed bias arc ion plating. The effects of V and N contents on the structures and properties of the films were investigated by X-ray photoelectron spectroscopy (XPS), Raman spectra, grazing incident X-ray diffraction (GIXRD), transmission electron microscopy (TEM) and nano-indentation, respectively. The as-deposited films consist of a DLC–VN nanocomposite, where VN nanograins are embedded in an amorphous carbon matrix. The V and N contents have significant influences on the relative proportion of VN with respect to DLC. A proper concentration of VN nanocrystals in DLC induces even the formation of nano-diamond. The DLC–VN films have higher hardnesses than pure DLC films, which could be attributed to the nanocomposite structure.     

Elevated temperature nitrogen plasma immersion ion implantation of AISI 302 austenitic stainless steel

AISI 302 steel was modified using elevated temperature nitrogen plasma immersion ion implantation. The thickness of the modified layers is improved significantly compared with that of the layer implanted at room temperature. The surface nanohardness of the treated sample is much higher. Both the friction coefficient and wear rate are dramatically reduced due to the formation of new phases such as (Cr, Fe)₂N_1−x, ε-(Fe, Cr, Ni)_2+xN, nitrogen expanded austenite (γ_N) or noncrystalline phase in the near surface.     

The structure and adhesion of hydrogenated amorphous carbon (a-C:H) films synthesized on CoCrMo alloy by plasma immersion ion implantation and deposition at different flow ratios of acetylene to argon

Hydrogenated amorphous carbon (a-C:H) film is deposited on CoCrMo alloy by plasma immersion ion implantation and deposition (PIII-D) at different flow ratios of acetylene to argon (C₂H₂/Ar). The results show that Ar fraction in the C₂H₂-Ar gas mixture has an important effect on the structure and the adhesion of the a-C:H films. When Ar fraction in the C₂H₂-Ar gas mixture is less than 50%, the fabricated a-C:H film composition transfer from graphite-like to diamond-like which contains higher sp³ binding thanks to Ar ion bombardment, and the adhesion strength decreased with the increment of Ar fraction. But when Ar fraction in the C₂H₂-Ar gas mixture is beyond 50%, the fabricated film contains more sp² bonding for thermally driven and exhibits higher adhesion strength with the increment of the Ar fraction.     

Nanoindentation response of PEEK modified by mesh-assisted plasma immersion ion implantation

Polyetheretherketone (PEEK) surfaces have been treated by mesh-assisted plasma immersion ion implantation, significantly altering the viscoelastic properties of the near-surface modified region. The plasticity index derived from nanoindentation load-displacement data indicates that the treated surfaces exhibit greater elastic recovery and reduced plastic deformation compared to unmodified PEEK. Scanning probe microscopy (SPM) images of the surface before and after indentation also show evidence of increased elastic recovery.     

TiN/ZrO2 multilayers synthesized on GCr15 bearing steel using plasma immersion ion implantation and deposition

TiN/ZrO₂ multilayers with different modulation periods were synthesized on GCr15 bearing steel using plasma immersion ion implantation and deposition (PIIID). The total thickness of the TiN/ZrO₂ multilayers was approximately 2 μm and the modulation period was varied from 8 to 400 nm. The as-deposited films were characterized by scanning electron microscopy (SEM), micro-hardness, friction, scratch and corrosion tests. The SEM result indicates that the structure of the TiN/ZrO₂ multilayers has a good periodicity. Micro-hardness testing results show that the hardness enhancement effect takes place at the specific period of 15 nm, 100 nm and 200 nm. In addition, the friction coefficient declined from 0.8 to 0.1-0.3 and the cut-through number was increased greatly. The critical load in the scratch test exceeds 100 N, which shows a high adhesion strength. Moreover, the corrosion resistance of the TiN/ZrO₂ multilayers was improved significantly at the modulation period of 100 nm and 200 nm.     

Synthesis of indium oxide nanorods on indium phosphide substrate using plasma immersion ion implantation

We report the preparation of indium oxide (In₂O₃) nanorods on indium phosphide (InP) substrate by plasma immersion ion implantation (PIII). The InP substrate was first treated with PIII of acetylene (C₂H₂) ions, then followed by coating the surface with a 40 nm thick gold film. After rapid thermal anneal (RTA) at 750 °C for 15 s, In₂O₃ nanorods were found on InP surface. The In₂O₃ nanorods with diameters of 50-200 nm were examined by Raman spectroscopy, scanning electron microscopy (SEM) and cathodoluminescence (CL). Nanoparticles of gold were found at the tip of the nanorods, suggesting that a vapour-liquid-solid (VLS) mechanism was involved. However, the fact that other species such as nitrogen, argon or oxygen would not lead to the formation of In₂O₃ nanorods also suggests that the carbon liberated from C₂H₂ plays an important role as a catalyst. Carbon has previously been reported to be a reduction agent for the formation of group III sub-oxides. Such sub-oxides provide the vapour source for the growth of nano-materials through further oxidation.     

Si含量对多元等离子体浸没离子注入与沉积技术制备TiAlSiN涂层微结构和机械性能的影响(英文)

采用多元等离子体浸没离子注入与沉积制备TiAlSiN纳米复合涂层,利用EDX,XRD,SEM,XPS,纳米探针和划痕试验对涂层成分组成、微结构和机械性能进行测试分析。XRD测试表明,TiAlSiN涂层具有较强的TiN(200)择优取向。XPS测试表明,TiAlSiN涂层中也含有AlN、Si3N4、Al2O3和Ti2O3。与制备的TiN涂层相比,当涂层中的Si含量为0.9%时,TiAlSiN涂层表现出较高的硬度,达32GPa,但涂层的断裂韧性和结合强度较低;当涂层中的Si含量增加至6.0%时,TiAlSiN涂层具有超高的硬度57GPa,并表现出较好的断裂韧性和结合强度。     

Microstructural, mechanical and tribological properties of tungsten-gradually doped diamond-like carbon films with functionally graded interlayers

A series of tungsten-gradually doped diamond-like carbon (DLC) films with functionally graded interlayer were prepared using a hybrid technique of vacuum cathodic arc/magnetron sputtering/ion beam deposition. With ‘compositionally graded coating’ concept, the deposition of wear-resistant carbon-based films with excellent adhesion to metallic substrate was realized. In the films, a functionally graded interlayer with layer sequence of Cr/CrN/CrNC/CrC/WC was first deposited onto the substrate, and then, a DLC layer doped with gradually decreasing content of W was coated on. The W concentration gradient along depth of the film was tailored by adjusting the W target current and deposition time. The characterized results indicate that the microstructural, mechanical and tribological properties of these films show a significant dependence on the W concentration gradient. A high fraction of W atom in carbon matrix can promote the formation of sp² sites and WC_1 − x nanoparticles. Applying this coating concept, strongly adherent carbon films with critical load exceeding 100 N in scratch test were obtained, and no fractures or delaminations were observed at the end of the scratched trace. The hardness was found to vary from 13.28 to 32.13 GPa with increasing W concentration. These films also presented excellent tribological properties, especially significantly low wear rate under dry sliding condition against Si₃N₄ ball. The optimum wear performance with friction coefficient of 0.19 and wear rate of 8.36 × 10⁻⁷ mm³/Nm was achieved for the tungsten-gradually doped DLC film with a graded W concentration ranging from 52.5% to 17.8%. This compositionally graded coating system might be a potentially promising candidate for wear-resistant carbon-based films in the demanding tribological applications.     

Effect of pulse rise time on charging effects in plasma immersion ion implantation with dielectric substrates with planar and cylindrical geometries

Using a one-dimensional self-consistent fluid model, the effect of pulse rise time on charging effects at dielectric surfaces is investigated during plasma immersion ion implantation (PIII) with planar and cylindrical geometries. The numerical results demonstrate that the pulse rise time plays an important role in PIII process with dielectric substrates. It is found that the charge dose accumulated on the dielectric surface is significant as decreasing pulse rise time, and the surface potential decreases at the later stage of the pulse, which results in the lower ion impact energy. On the other hand, the longer pulse rise time would lead to the lower charge dose accumulated on the dielectric surface and higher ion impact energy at the later stage of the pulse, which would elevate the effective implanted dose and introduce the ions to the depth deep enough for surface modification.     

Deposition and properties of Al-containing diamond-like carbon films by a hybrid ion beam sources

Metal incorporation is one of the most effective methods for relaxing internal stress in diamond-like carbon (DLC) films. It was reported that the chemical state of the incorporated metal atoms has a significant influence on the film internal stress. The doped atoms embedding in the DLC matrix without bonding with C atoms can reduce the structure disorder of the DLC films through bond angle distortion and thus relax the internal stress of the films. In present paper, Al atoms, which are inert to carbon, were incorporated into the DLC films deposited by a hybrid ion beams system comprising an anode-layer ion source and a magnetron sputtering unit. The film composition, microstructure and atomic bond structure were characterized using X-ray photoelectron spectroscopy, transmission electron microscopy and Raman spectroscopy. The internal stress, mechanical properties and tribogoical behavior were studied as a function of Al concentration using a stress-tester, nanoindentation and ball-on-disc tribo-tester, respectively. The results indicated that the incorporated Al atoms were dissolved in the DLC matrix without bonding with C atoms and the films exhibited the feature of amorphous carbon. The structure disorder of the films tended to decrease with Al atoms incorporation. This resulted in the distinct reduction of the internal stress in the films. All Al-DLC films exhibited a lower friction coefficient compared with pure DLC film. The formation of the transfer layer and the graphitization induced by friction were expected to contribute to the excellent friction performance.     

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.