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.

Tribological behavior of different films on Ti-6Al-4V alloy prepared by plasma-based ion implantation

The tribological behaviors of TiN coating and TiN+TiC+Ti(C, N)/diamond like carbon (DLC), TiN/DLC, TiC/DLC multilayers on Ti 6Al 4V alloy prepared by plasma based ion implantation (PBII) were compared. Under the test conditions of counterbody AISI 52100, load 1 N and speed 0.05 m/s, the tribological properties of the alloy are improved by these films in the order of TiN, TiC/DLC, TiN/DLC and TiN+TiC+Ti(C,N)/DLC. Tribological behavior is affected by the conditions of surface modification and triboexperiments. The appearance of “peaks” in the wear dynamic resistance profiles may be due or correspond to the process of formation and breaking apart of transition films. The breakthrough of the DLC coated samples may start from partially wearing out, and end with joining piece dilamination. There are transition films on all counterbodies AISI 52100. When AISI 52100 counterbody is changed to Ti 6Al 4V, the wear of most modified samples is changed from only disc to both disc and ball abrasive dominated.

COMPUTATIONAL SCHEME FOR SIMULATING PLASMA DYNAM-ICS DURING PLASMA-IMMERSION ION IMPLANTATION

Plasma-immersion ion implantation (PIII) is a technique for implanting ions into conducting, semiconducting and insulating objects. In PIII, the object being treated is immersed in a plasma and pulsed to a large negative voltage (=-1 to-100 kV). The resulting sheath expands into the ambient plasma, extracting ions and accelerating them to the target. PIII has advantages over beam-line implantation in that large surfaces can be rapidly implanted, irregularly-shaped objects can be implanted without target manipulation, and surfaces that are not line-of-sight accessible can be treated. A two-dimensional, self-consistent model of plasma dynamics appropriate for PIII is described. The model is a hybrid, with Boltzmann electrons and kinetic ions, where the ion Vlasov equation is solved using the particle-in-cell (PIC) method. Solutions of the model give the time dependence of the ion flux, energy and impact angle at the target surface, together with the evolution of the sheath.

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.

COMPARISON OF SURFACE PROPERTIES OF Ti-6Al-4V COATED WITH TITANIUM NITRIDE, TiN+TiC+Ti(C,N)/DLC, TiN/DLC AND TiC/DLC FILMS BY PLASMA-BASED ION IMPLANTATION

The surface properties of Ti-6Al-4V alloy coated with titanium nitride, TiN+TiC+Ti(C,N)/DLC (diamond like carbon), TiN/DLC and TiC/DLC films by plasma-based ion implantation (PBII) with nitrogen, PBII with nitrogen then acetylene, PBII with nitrogen then glow discharge deposition with acetylene plus hydrogen and PBII with acetylene then glow discharge deposition with acetylene plus hydrogen respectively were studied. The corresponding films are found getting dimmer, showing light gold or gold, smoky color (uneven), light red in black (uneven), and graphite black separately. The corresponding film resistivities are given. Antioxidation ability of the titanium nitride film is poor, while the existence of carbon (or carbide) improves the antioxidation ability of the films. Having undergone excellent intermediate transitional region of nitrogen and carbon implantation, the top DLC layer of the TiN+TiC+Ti(C,N)/DLC multilayer are formed after the carbon implantation has the best adhesion with the substrate among all the multilayers. Although microhardness of the samples increases in the order of coatings of titanium nitride, TiN/DLC, TiN+TiC+Ti(C,N)/DLC and TiC/DLC, the TiN/DLC and TiC/DLC multilayers have greater brittleness as compared with other films.

Effect of cathode composition on microstructure and tribological properties of TiBN nanocomposite multilayer coating synthesized by plasma immersion ion implantation and deposition

Nanocomposite multilayer TiBN coatings were prepared on Si(100) and 9Cr18Mo substrates using TiBN composite cathode plasma immersion ion implantation and deposition technique(PIIID). Synthesis of TiBN composite cathodes was conducted by powder metallurgy technology and the content of hexagonal boron nitride(h-BN) was changed from 8% to 40%(mass fraction). The as-deposited coatings were characterized by energy dispersive spectrometer(EDS), grazing incidence X-ray diffraction(GIXRD), Fourier Transform Infrared Spectroscopy(FTIR) and high resolution transmission electron microcopy(HRTEM). EDS results show that the B content of the coatings was varied from 3.71% to 13.84%(molar fraction) when the composition of the h-BN in the composited cathodes was changed from 8 % to 40%(mass fraction). GIXRD results reveal that the TiBN coatings with a B content of 8% has the main diffraction peak of TiN(200),(220) and(311), and these peaks disappear when the B content is increased. FTIR analysis of the multilayer coatings showed the presence of h-BN in all coatings. TEM images reveal that all coatings have the characteristics of self-forming nanocomposite multilayers, where the nanocomposites are composed of face-centered cubic Ti N or h-BN nanocrystalline embedded in amorphous matrix. The tribological tests reveal that the Ti BN coatings exhibit a marked decrease of coefficient at room temperature(~0.25). The improved properties were found to be derived from the comprehensiveness of the self-forming multilayers structure and the h-BN solid lubrication effects in the coatings.

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.

Tribological behavior of AISI302 austenitic stainless steel modified by elevated temperature nitrogen plasma immersion ion implantation

AISI302 stainless steel samples were modified by elevated temperature nitrogen plasma immersion ion implantation at temperature ranging from 330 ℃ to 450 ℃. The tribological behaviors of the implanted layers of the samples were investigated. The samples were characterized by Auger electron spectroscopy (AES), glancing angle X-ray diffraction (GXRD), and nanoindentation. The results show that the implantation temperature plays an important rule on the microstructure and surface properties of the implanted layers. The thickness of the modified layer implanted at 390 ℃ is about 9 μm. It is improved about two orders compared with that of the implanted at room temperature. The surface nanohardness and the wear resistance of elevated temperature implanted layers increase significantly, and the friction coefficient decreases obviously in comparison with the unimplanted one. These data suggests that the improvement results from the formation of new phases such as ε-(Fe, Cr, Ni)2+xN, or noncrystal phase.

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.

Temperature elevated N ion implantation of Ti6A14V alloys using the plasma source

Specimens of Ti6A14V alloy were implanted with nitrogen ions of 4× 1018 cm-2 at temperatures from 100 to 600℃. Auger Electron Spectroscopy (AES), microhardness measurements and pin-on-disk wear testing, Scanning Electron Mi- croscopy (SEM), and Glancing angle X-ray Diffraction. (XRD) were utilized to evaluate the surface property improvements. The thickness of implanted layers increased by about an order of magnitude when the temperature was elevated from 100 to 6000℃. Higher surface hardness and wear resistance were also obtained in the high tempera-ture implantation. The XRD image showed the presence of nitrides of titanium at the implanted surface.

Structure and tribological properties of modified layer on 2024 aluminum alloy by plasma-based ion implantation with nitrogen/titanium/carbon

aluminum alloy was implanted with nitrogen then titanium finally carbon by plasma-based ion implantatio to form a gradient layer. The structure and tribological properties of the layer were investigated. Its composition profiles and chemical states were analyzed with X-ray photoelectron spectroscopy(XPS). The surface carbon layer was analyzed by Raman spectrum. The appearances were observed by atomic force microscope (AFM). The surface hardness was measured with the mechanical property microprobe. The dry wear tests against GCr15 steel ball at various sliding loads were performed with a ball-on-disk wear tester in ambient environment. The results show that the thickness of the modified layer is 1 200 nm, the carbon layer is a smooth and compact diamond-like carbon(DLC) films, and the carbon-titanium interface is broadened due to carbon ions implantation, resulting in a good composition and structure transition between DLC films and titanium layer. Surface hardness is improved markedly, with a slow and uniform change. Tribological properties are improved greatly although they reduce with the increase of sliding loads because the modified layer becomes thin rapidly.

XPS INVESTIGATION OF NITROGEN IONS IMPLANTED INTO ALUMINUM ALLOY BY PLASMA BASED ION IMPLANTATION

Aluminum alloy 2024 has been implanted with nitrogen ions at various doses by plasma based ion implantation. The introduction of energetic ions causes structural change within the near surface region of the solid. The samples have been characterized by X-ray Photoelectron Spectroscopy at various depths. The chemical states of Al and N were identified by deconvolution of the recorded XPS spectra. After plasma based ion implanted nitrogen into aluminum, not only the AlN precipitates but also super saturated solution of nitrogen forms. The presence of aluminum in different chemical states is corresponding to Al, AlN and Al2O3. The majority of nitrogen is in the form of the supersaturated solution. With the increase of nitrogen dose, the amount of AlN precipitates increases.

Effect of target temperature on microstructure of aluminum surface layer modified by plasma based ion implantation

Aluminum (99.6% purity) was implanted with nitrogen ions to a total dose of 6×10 17 cm -2 at different temperatures (from 50 ℃ to 400 ℃) by plasma based ion implantation (PBII). The surface microstructure was investigated by glancing angle X ray diffraction (GXRD), X ray photoelectron spectroscopy (XPS) and cross sectional transmission electron microscopy (XTEM). The results of GXRD and XTEM showed that there was an amorphous layer on the outer surface, and fine dispersion of AlN precipitates was found under the amorphous layer. The size of AlN precipitates strongly depended on the target temperature, with the increase of the target temperature, the size of AlN precipitates became larger. The excess nitrogen atoms can diffuse or migrate to the lower nitrogen concentration regions by radiation enhanced diffusion. The results of XPS further indicated that it was easier to form AlN precipitates at a higher target temperature, and the depth profile of nitrogen broadened.

Analysis of current waveform in plasma based ion implantation processes

The output current waveform of the high voltage pulse modulator is an important information needed to control the plasma immersion ion implantation process, monitor the implantation parameters, for example, implantation dose and sheath condition, and to predict the target temperature as well as secondary electron emission. Our simulation results indicate that the total current peaks at the end of rise time of the applied voltage and this means that such data as dose, temperature and so on is perhaps overestimated from the current waveform because our experimental data acquired using a Rogowski coil and digital oscillator shows the highest current at the beginning of the voltage pulse. The discrepancy can be explained by a displacement current that may be attributed to the changing voltage, sheath capacitance, circuit loading effects, and so on. Our analysis of the current waveform in plasma immersion ion implantation process is accomplished through theoretical simulation and experiments.

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.

Plasma-based ion implantation of nitrogen into Ti-6Al-4V: effect of implantation time and pre-or post-implantation aging on nitrogen distribution and microhardness

Presents the investigation of the effect of implantation time and pre or post implantation aging on nitrogen distribution and microhardness with the following findings: the colour of the surface is modified after implantation and it gets darker with the increase of implantation time, and is not affected by pre or post implantation aging; for every implanted sample, a peak is found in the near surface region of the nitrogen concentration depth profile determined by X ray photoelectron spectroscopy (XPS); The position of the peak is not affected by implantation time and pre or post implantation aging used; With the increase of implantation time, the surface nitrogen concentration increases, and the peak is heightened, but the speed of heightening decreases; The surface structure formed after the implantation may be more unstable and more readily oxidized in its subsequent exposure to air; The implanted samples can be protected against oxidation by immersing them in pure alcohol; and the immersion causes the surface nitrogen concentration to increase somewhat and the surface oxygen concentration to decrease in comparison with the exposure to air. The implanted samples exhibit higher hardness improvement factor especially at low plastic penetrations. The exposure to air causes the hardness improvement factor to increase. As the implantation time is increased, the hardness improvement factor increases (but at a decreased speed). Over long implantation time can induce a softening process because the hardness improvement effects are then unable to follow the effect of strength loss.

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.

An All Solid-State Pulsed Power Generator for Plasma Immersion Ion Implantation (PⅢ)

An all solid-state pulsed power generator for plasma immersion ion implantation （PIII） is described. The pulsed power system is based on a Marx circuit configuration and semi- conductor switches, which have many advantages in adjustable repetition frequency, pulse width modulation and long serving life compared with the conventional circuit category, tube-based technologies such as gridded vacuum tubes, thyratrons, pulse forming networks and transformers. The operation of PIII with pulse repetition frequencies up to 500 Hz has been achieved at a pulse voltage amplitude from 2 kV to 60 kV, with an adjustable pulse duration from 1 μs to 100 μs. The proposed system and its performance, as used to drive a plasma ion implantation chamber, are described in detail on the basis of the experimental results.