Effects of Al and N plasma immersion ion implantation on surface microhardness,oxidation resistance and antibacterial characteristics of Cu

A1 and N were introduced into copper substrate using plasma immersion ion implantation （PIII） in order to enhance its hardness and oxidation resistance. The dosage of N ion is 5 × 1016 cm-2, and range of dosage of A1 ion is 5× 1016-2× 1017 cm-2. The oxidation tests indicate that the copper samples after undergoing PIII possess higher oxidation resistance. The degree of oxidation resistance is found to vary with implantation dosage of AI ion. The antibacterial tests also reveal that the plasma implanted copper specimens have excellent antibacterial resistance against Staphylococcus aureus, which are similar to pure copper.

ION HEATING PROCESS DURING PLASMA IMMERSION ION IMPLANTATION

The research on plasma immersion ion implantation has been conducted for a little over ten years. Much is needed to investigate including processing technlogy, plasma sheath dynamics, interaction of plasma and surface, etc. Of the processing methods elavated temperature technique is usually used in PIII to produce a thick modified layer by means of the thermal diffusion. Meanwhile plasma ion heating is more recently developed by Ronghua Wei et al[1]. Therefore the temeperature is a critical parameter in plasma ion processing. In this paper we present the theoretical model and analysize the effect of imlantation voltage, plasma density, ion mass,etc on the temperature rise.

TWO-DIMENSIONAL NUMERICAL ANALYSIS OF PLASMA IMMERSION ION IMPLANTATION OF CYLINDRICAL BORES

Plasma immersion ion implantation (PIII), unrestricted by sight-light process, is considered a proper method for inner surface strengthening. Two-dimensional simulation oj inner surface PIII process of cylindrical bores were carried out in this paper using cold plasma fluid model, and influence of the bore's dimension on impact energy, retained dose and uniformity of inner surface were investigated.

Structure and Tribological Property of TiBN Nanocomposite Multilayer Synthesized by Ti-BN Composite Cathode Plasma Immersion Ion Implantation and Deposition

A Ti-BN complex cathode is made from Ti and h-BN powders by the powder metallurgy technology, and TiBN coating is obtained by plasma immersion ion implantation and deposition with this Ti-BN composite cathode. The TiBN coating shows a self-forming multilayered nanocomposite structure while with relative uniform elemental distributions. High resolution transmission electron microscopy images reveal that the multilayered structure is derived from different grain sizes in the nanocomposite. Due to the existence of h-BN phase, the friction coefficient of the coating is about 0.25.

Realization of conformal doping on multicrystalline silicon solar cells and black silicon solar cells by plasma immersion ion implantation

Emitted multi-crystalline silicon and black silicon solar cells are conformal doped by ion implantation using the plasma immersion ion implantation （PⅢ） technique. The non-uniformity of emitter doping is lower than 5 %. The secondary ion mass spectrometer profile indicates that the PⅢ technique obtained 100-rim shallow emitter and the emitter depth could be impelled by furnace annealing to 220 nm and 330 nm at 850 ℃ with one and two hours, respectively. Furnace annealing at 850 ℃ could effectively electrically activate the dopants in the silicon. The efficiency of the black silicon solar cell is 14.84% higher than that of the mc-silicon solar cell due to more incident light being absorbed.

Effect of Yttrium Pre-Implantation on Implantation Behavior of Ti-6Al-4V Alloy in Nitrogen Plasma Immersion Ion Implantation

In order to increase the peak depth of nitrogen atoms during the nitrogen plasma immersion ion implantation of Ti-6Al-4V alloy, the rare earth metal yttrium was applied. In the experiment, yttrium and nitrogen ions were implanted under the voltage of 20 and 30 kV, respectively. In the samples with yttrium pre-implantation for 30 min, the Anger electron spectroscopy (AES) analysis shows that the peak depth of the nitrogen atoms increases from 50 up to 100 nm. It can also be seen from the tribological tests that the wear resistance of these samples is increased remarkably.

Two-dimensional particle-in-cell plasma source ion implantation of a prolate spheroid target

A two-dimensional particle-in-cell simulation is used to study the time-dependent evolution of the sheath surrounding a prolate spheroid target during a high voltage pulse in plasma source ion implantation. Our study shows that the potential contour lines pack more closely in the plasma sheath near the vertex of the major axis, i.e. where a thinner sheath is formed, and a non-uniform total ion dose distribution is incident along the surface of the prolate spheroid target due to the focusing of ions by the potential structure. Ion focusing takes place not only at the vertex of the major axis, where dense potential contour lines exist, but also at the vertex of the minor axis, where sparse contour lines exist. This results in two peaks of the received ion dose, locating at the vertices of the major and minor axes of the prolate spheroid target, and an ion dose valley, staying always between the vertices, rather than at the vertex of the minor axis.

Work Function Enhancement of Indium Tin Oxide via Oxygen Plasma Immersion Ion Implantation

Indium tin oxide （ITO） transparent conducting film was treated with oxygen plasma immersion ion implantation （PIII）. X-ray photoelectron spectroscopy （XPS） was employed to characterize the effect. The results suggested that the oxygen content in the surface was increased and maintained for more than 50 h compared with traditional plasma-treated samples. Meanwhile, the work function of ITO estimated by comparing the peak shift in the XPS diagram suggested a corresponding increase by more than 1 eV.

Deposition of DLC Coating on Biomedical TiNi Alloys by Plasma Based Ion Implantation to Improve Surface Properties

Diamond-like carbon （DLC） films were successfully deposited on Ti- 50.8 at% Ni using plasma based ion implantation （PBII） technique. The influence of the pulsed negative bias voltage applied to the substrate from 12 kV to 40 kV on the microstracture, nano-indentation hardness and Young＇ s modulus, the surface characteristics and corrosion resistant property as well as hemocompatibility were investigated. The experimental resalts showed that C 1 s peak depended heavily on the bias voltage. With the increase of bias voltage, the ratio of sp2 / sp3 first decreased, reaching a minimum value at 20 kV, and then increased. The DLC coating deposited at 20 kV showed the highest hardness and elastic modulus values as a result of lower sp2/sp3 ratio. The RMS values first decreased from 7.202nm（12 kV） to 5.279 nm（20 kV）, and then increased to 11.449 nm（30 kV） and 7.060 nm（ 40 kV）. The uncoated TiNi alloy showed severe pitting corrosion, due to the presence of Cl-ions in the solution. On the contrary, the DLC coated sample showed very little pitting corrosion and behaved better corrosion resistant property especially for the specimens deposited at 20 kV bias voltages. The platelet adhesion test show that the hemocompatibility of DLC coated TiNi alloy is much better than that of bare TiNi alloy, and the hemocompatibility performance of DLC coated TiNi alloy deposited at 20 kV is superior to that of other coated specimens.

Fluid simulation of the pulsed bias effect on inductively coupled nitrogen discharges for low-voltage plasma immersion ion implantation

Planar radio frequency inductively coupled plasmas（ICP） are employed for low-voltage ion implantation processes,with capacitive pulse biasing of the substrate for modulation of the ion energy. In this work, a two-dimensional（2D） selfconsistent fluid model has been employed to investigate the influence of the pulsed bias power on the nitrogen plasmas for various bias voltages and pulse frequencies. The results indicate that the plasma density as well as the inductive power density increase significantly when the bias voltage varies from 0 V to-4000 V, due to the heating of the capacitive field caused by the bias power. The N＋fraction increases rapidly to a maximum at the beginning of the power-on time, and then it decreases and reaches the steady state at the end of the glow period. Moreover, it increases with the bias voltage during the power-on time, whereas the N2-＋ fraction exhibits a reverse behavior. When the pulse frequency increases to 25 kHz and40 kHz, the plasma steady state cannot be obtained, and a rapid decrease of the ion density at the substrate surface at the beginning of the glow period is observed.

Development and experimental study of large size composite plasma immersion ion implantation device

Plasma immersion ion implantation （PI） overcomes the direct exposure limit of traditional beam- line ion implantation, and is suitable for the treatment of complex work-piece with large size. Pm technology is often used for surface modification of metal, plastics and ceramics. Based on the requirement of surface modification of large size insulating material, a composite full-directional PHI device based on RF plasma source and metal plasma source is developed in this paper. This device can not only realize gas ion implantation, but also can realize metal ion implantation, and can also realize gas ion mixing with metal ions injection. This device has two metal plasma sources and each metal source contains three cathodes. Under the condition of keeping the vacuum unchanged, the cathode can be switched freely. The volume of the vacuum chamber is about 0.94 m3, and maximum vacuum degree is about 5 x10-4 Pa. The density of RF plasma in homogeneous region is about 109 cm-3, and plasma density in the ion implantation region is about 101x cm-3. This device can be used for large-size sample material PHI treatment, the maximum size of the sample diameter up to 400 mm. The experimental results show that the plasma discharge in the device is stable and can run for a long time. It is suitable for surface treatment of insulating materials.

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.

Modeling of Inner Surface Modification of a Cylindrical Tube by Plasma-Based Low-Energy Ion Implantation

The inner surface modification process by plasma-based low-energy ion implantation（PBLEII）with an electron cyclotron resonance（ECR）microwave plasma source located at the central axis of a cylindrical tube is modeled to optimize the low-energy ion implantation parameters for industrial applications.In this paper,a magnetized plasma diffusion fluid model has been established to describe the plasma nonuniformity caused by plasma diffusion under an axial magnetic field during the pulse-off time of low pulsed negative bias.Using this plasma density distribution as the initial condition,a sheath collisional fluid model is built up to describe the sheath evolution and ion implantation during the pulse-on time.The plasma nonuniformity at the end of the pulse-off time is more apparent along the radial direction compared with that in the axial direction due to the geometry of the linear plasma source in the center and the difference between perpendicular and parallel plasma diffusion coefficients with respect to the magnetic field.The normalized nitrogen plasma densities on the inner and outer surfaces of the tube are observed to be about 0.39 and 0.24,respectively,of which the value is 1 at the central plasma source.After a 5μs pulse-on time,in the area less than 2 cm from the end of the tube,the nitrogen ion implantation energy decreases from 1.5 keV to 1.3 keV and the ion implantation angle increases from several degrees to more than 40°;both variations reduce the nitrogen ion implantation depth.However,the nitrogen ion implantation dose peaks of about 2×10^（10）-7×10^（10）ions/cm^2 in this area are 2-4 times higher than that of 1.18×10^（10）ions/cm^2 and 1.63×10^（10）ions/cm^2 on the inner and outer surfaces of the tube.The sufficient ion implantation dose ensures an acceptable modification effect near the end of the tube under the low energy and large angle conditions for nitrogen ion implantation,because the modification effect is mainly determined by the ion implantation dose,just as the mass transfer process in PBLEII is dominated by low-energy ion implantation and thermal diffusion.Therefore,a comparatively uniform surface modification by the low-energy nitrogen ion implantation is achieved along the cylindrical tube on both the inner and outer surfaces.

A combination strategy of functionalized polymer coating with Ta ion implantation for multifunctional and biodegradable vascular stents

Biodegradable stents made of magnesium(Mg)and its alloys have been developed to minimize persistent inflammation or in-stent restenosis,which are the main problems for permanent stents.However,their rapid corrosion behavior under physiological conditions leads to poor vascular compatibility and premature structural failure,which remains an important unsolved clinical problem.Herein,we demonstrate a new strategy for solving this problem by combining poly(ether imide)(PEI)coating and subsequent tantalum(Ta)ion implantation.The PEI coating covers the whole surface of the Mg stent uniformly via a spray coating technique and provides Mg with superior corrosion resistance and stable sirolimus-carrying ability.Ta ion implantation is conducted by a sputtering-based plasma immersion ion implantation technique only onto the luminal surface of the PEI-coated Mg stent.Its extremely short processing time(<30 s)permits preservation of the PEI coating’s corrosion protection ability and sirolimus loading characteristics.In addition,a Ta-implanted skin layer that forms on the topmost surface of the PEI coating plays an effective role in not only preventing a rapid release of sirolimus from the surface but also improving the PEI coating’s surface hydrophilicity.Based on in vitro cellular response and blood compatibility tests,Ta ion implantation leads to the improvement of endothelial cell adhesion/proliferation and suppression of platelet adhesion/activation regardless of sirolimus loading.These results indicate that the combination of PEI coating and Ta ion implantation has significant innovative potential to provide excellent vascular compatibility and prevent in-stent restenosis and thrombosis.

Characteristics of Cu implantation into Si by PBII using UBMS cathode

The implantation of Cu into Si substrate was carried out by plasma based ion implantation (PBII) using unbalanced magnetron sputtering (UBMS) cathode as the metal plasma source. The different pulse bias ( U p) and the distance between the cathode and the samples ( d s-t ) were chosen to research the characteristics of this method. The results show that the implantation of metal ions can be realized by the metal plasma source of UBMS cathode. The physical process such as the metal ion pure implantation, the gas ion implantation, the recoil implantation of the metal atoms, the deposition of the metal particles and the re sputtering of the metal film depend on the energy, dose and deposition rate of the ions (Cu +, Ar +). The metal plasma based ion implantation of Cu into Si substrate is favored by selecting higher U p (60 kV) and larger d s-t (200 mm). [

Nanomodificated Surface CoCr Alloy for Corrosion Protection of MoM Prosthesis

Problems in metal-on-metal (MoM) hip replacement systems still persist due to high wear rates, low corrosion resistance and release of toxic ions and nanoparticles. As a consequence of these effects, failure, infections, loosening or bone resorption is the typical problems in the hip prosthesis. In order to reduce failure due to corrosion and/or releasing ions and particles, this study presents some works in a novel nanoscale surface modification of cobalt-chromium alloy (CoCr) for obtaining improved surface conditions in these alloys for these applications. Improving corrosion resistant of these alloys and achieving a low wear rate are possible to reduce the total released ions and particles released from the surface of this material. According to it, three different treatments using oxygen at temperatures of 300&degC, 350&degC and 400&degC were carried out by plasma immersion ion implantation technique (PI3). X-ray diffraction (XRD) analysis shows an increase in the formation of chromium oxides in the outer surface of the CoCr alloy. It allows improving in corrosion resistant in CoCr alloys. Moreover, total quantity of released Co, Cr and Mo ions have been reduced. Wear rate studies showed a very similar behaviour after the treatments in relation to untreated CoCr alloy and release rate from the treated surface of CoCr alloys was reduced in comparison with untreated CoCr alloy.

Electrochemical Corrosion Behavior of the DLC Coated and Uncoated NiTi Alloys

A dense and well-adhered diamond-like carbon （DLC） coating was prepared on the nickel-titanium （NiTi） alloys by plasma immersion ion implantation and deposition （PIIID）. Potentiodynamic polarization tests indicated the corrosion resistance of the NiTi alloys was markedly improved by the DLC coating. The Ni ions release of the NiTi alloys was effectively blocked by the DLC coating.

Co-implantation of magnesium and zinc ions into titanium regulates the behaviors of human gingival fibroblasts

Soft tissue sealing around implants acts as a barrier between the alveolar bone and oral environment,protecting implants from the invasion of bacteria or external stimuli.In this work,magnesium(Mg)and zinc(Zn)are introduced into titanium by plasma immersed ion implantation technology,and their effects on the behaviors of human gingival fibroblasts(HGFs)as well as the underlying mechanisms are investigated.Surface characterization confirms Mg and Zn exist on the surface in metallic and oxidized states.Contact angle test suggests that surface wettability of titanium changes after ion implantation and thus influences protein adsorption of surfaces.In vitro studies disclose that HGFs on Mg ion-implanted samples exhibit better adhesion and migration while cells on Zn ion-implanted samples have higher proliferation rate and amounts.The results of immunofluorescence staining and real-time reverse-transcriptase polymerase chain reaction(RT-PCR)suggest that Mg mainly regulates the motility and adhesion of HGFs through activating the MAPK signal pathway whereas Zn influences HGFs proliferation by triggering the TGF-βsignal pathway.The synergistic effect of Mg and Zn ions ensure that HGFs cultured on co-implanted samples possessed both high proliferation rate and motility,which are critical to soft tissue sealing of implants.

Development of tropoelastin-functionalized anisotropic PCL scaffolds for musculoskeletal tissue engineering

The highly organized extracellular matrix(ECM)of musculoskeletal tissues,encompassing tendons,ligaments and muscles,is structurally anisotropic,hierarchical and multi-compartmental.These features collectively contribute to their unique function.Previous studies have investigated the effect of tissue-engineered scaffold anisotropy on cell morphology and organization for musculoskeletal tissue repair and regeneration,but the hierarchical arrangement of ECM and compartmentalization are not typically replicated.Here,we present a method for multi-compartmental scaffold design that allows for physical mimicry of the spatial architecture of musculoskeletal tissue in regenerative medicine.This design is based on an ECM-inspired macromolecule scaffold.Polycaprolactone(PCL)scaffolds were fabricated with aligned fibers by electrospinning and mechanical stretching,and then surface-functionalized with the cell-supporting ECM protein molecule,tropoelastin(TE).TE was attached using two alternative methods that allowed for either physisorption or covalent attachment,where the latter was achieved by plasma ion immersion implantation(PIII).Aligned fibers stimulated cell elongation and improved cell alignment,in contrast to randomly oriented fibers.TE coatings bound by physisorption or covalently following 200 s PIII treatment promoted fibroblast proliferation.This represents the first cytocompatibility assessment of novel PIII-treated TE-coated PCL scaffolds.To demonstrate their versatility,these 2D anisotropic PCL scaffolds were assembled into 3D hierarchical constructs with an internally compartmentalized structure to mimic the structure of musculoskeletal tissue.

In vitro and in vivo antibacterial performance of Zr&O PIII magnesium alloys with high concentration of oxygen vacancies

The effects of dual Zr and O plasma immersion ion implantation(Zr&O PIII)on antibacterial properties of ZK60 Mg alloys are systematically investigated.The results show that a hydrophobic,smooth,and ZrO_(2)-containing graded film is formed.Electrochemical assessment shows that the corrosion rate of the plasma-treated Mg alloy decreases and the decreased degradation rate is attributed to the protection rendered by the surface oxide.In vitro and in vivo antibacterial tests reveal Zr&O PIII ZK60 presents higher antibacterial rate compared to Zr PIII ZK60 and untreated control.The hydrophobic and smooth surface suppresses bacterial adhesion.High concentration of oxygen vacancies in the surface films are determined by X-ray photoelectron spectroscopy(XPS),UV-vis diffuse reflectance spectra(UV-vis DRS)and electron paramagnetic resonance(EPR)and involved in the production of reactive oxygen species(ROS).The higher level of ROS expression inhibits biofilm formation by down-regulating the expression of icaADBC genes but up-regulating the expression of icaR gene.In addition,Zr&O PIII improves cell viability and initial cell adhesion confirming good cytocompatibility.Dual Zr&O PIII is a simple and practical means to expedite clinical acceptance of biodegradable magnesium alloys.