Wetting modifications of uhmwpe surfaces induced by ion implantation

Ultra-high-molecular-weight-polyethylene (UHMWPE) surfaces are characterized in terms of roughness and wetting. Changes in the surface morphology of the polymer were induced macroscopically by mechanical friction and microscopically by ion implantation. The ion irradiation was obtained by using 300?keV Xe⁺ beams with doses ranging between 10¹⁴ and 10¹⁵?ions/cm².

Roughness and wetting measurements were performed in order to investigate the UHMWPE surface properties before and after the surface treatments. The wetting angle of the polymeric surface increases with the decrease of the roughness and with the increase of the absorbed dose. Results are discussed from the point of view of the biological reactions that could degrade the UHMWPE biocompatible surfaces employed in different mobile prostheses.     

Change of sheet resistance of high purity alumina ceramics implanted by Cu and Ti ions

High purity alumina ceramics (99% Al₂O₃) was implanted by copper ion and titanium ion in a metal vapour vacuum arc (MEVVA) implanter, respectively. The influence of implantation parameters was studied varying ion fluence. The samples were implanted by 68 keV Cu ion and 82 keV Ti ion with fluences from 1 × 10¹⁵ to 1 × 10¹⁸ ions/cm², respectively. The as-implanted samples were investigated by scanning electron microscopy (SEM), glancing X-ray diffraction (GXRD), scanning Auger microscopy (SAM), and four-probe method. Different morphologies were observed on the surfaces of the as-implanted samples and clearly related to implantation parameters. For both ion implantations, the sheet resistances of the alumina samples implanted with Cu and Ti ion fluences of 1 × 10¹⁸ ions/cm², respectively, reached the corresponding minimum values because of the surface metallization. The experimental results indicate that the high-fluence ion implantation resulted in conductive layer on the surface of the as-implanted high purity alumina ceramics.     

Tribological properties of chromium implanted silicon nitride ceramics correlated with microstructure

3 N₄ ceramic after chromium implantation were investigated for the dependence on implantation energy between 200 keV and 3 MeV at a fixed fluence of 10¹⁷ ions/cm². The wear of the modified material is reduced for a load of 2 N independent of ion energy accompanied by a slight increase of the friction coefficient. At higher loads only high-energy implantations result in improved wear behaviour. Structural investigations show the absence of any new phases formed by ion implantation. All energies result in an amorphous layer. For lower energies this amorphous layer reaches up to the surface whereas at higher energies it is covered by still-crystalline but damaged material. The observed wear behaviour can be explained with the amorphization of the near surface region and the stress generated by the volume swelling of the amorphous layer. Received: 25 November 1996/Accepted: 29 April 1997     

Changes in surface properties of nitrogen-implanted AISI316L stainless steel

The effect of nitrogen ion implantation with an energy of 125 keV and doses of 1 × 10¹⁷–1 × 10¹⁸ at/cm² on such tribological characteristics of AISI316L stainless steel as the friction coefficient, wear resistance, and microhardness was studied. The steel surface layer composition was studied by the methods of RBS, XRD, GXRD, SEM, and EDX. The friction coefficient and abrasion resistance of AISI316L stainless steel were measured in air, oxygen and argon atmospheres, and in vacuum. An increase in the abrasion resistance after implantation was detected, which was different for various media. The largest increase in the wear resistance was observed during testing in air. The largest decrease in the friction coefficient was observed for all implanted samples in argon atmosphere. Tribological tests resulted in an increase in nitrogen, carbon, and oxygen concentrations in worn sample fragments in comparison with their concentrations in surface layers immediately after implantation.     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

Modification of medical metals by ion implantation of copper

The effect of copper ion implantation on the antibacterial activity, wear performance and corrosion resistance of medical metals including 317 L of stainless steels, pure titanium, and Ti-Al-Nb alloy was studied in this work. The specimens were implanted with copper ions using a MEVVA source ion implanter with ion doses ranging from 0.5 × 10¹⁷ to 4 × 10¹⁷ ions/cm² at an energy of 80 keV. The antibacterial effect, wear rate, and inflexion potential were measured as a function of ion dose. The results obtained indicate that copper ion implantation improves the antibacterial effect and wear behaviour for all the three medical materials studied. However, corrosion resistance decreases after ion implantation of copper. Experimental results indicate that the antibacterial property and corrosion resistance should be balanced for medical titanium materials. The marked deteriorated corrosion resistance of 317 L suggests that copper implantation may not be an effective method of improving its antibacterial activity.     

Effect of copper ions implantation on corrosion behavior of zircaloy-4 in 1 M H2SO4

In order to study the effect of copper ion implantation on the aqueous corrosion behavior, samples of zircaloy-4 were implanted with copper ions with fluences ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source (MEVVA) operated at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the copper ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-4 in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-4 implanted with copper ions when the fluence is smaller than 5 × 10¹⁶ ions/cm². The corrosion resistance of implanted samples declined with increasing the fluence. Finally, the mechanism of the corrosion behavior of copper-implanted zircaloy-4 was discussed.     

Wear resistance of the ion-modified surface of zirconium-alloy tubes irradiated by He+ and Ar+ ion beams with wide energy spectra

The results of investigating the wear resistance of E110 alloy samples irradiated by a He⁺ + Ar⁺ beam with a wide energy spectrum are presented. Surface modification under irradiation by an Ar⁺ beam at doses higher than 2 × 10¹⁸ ion/cm² is shown to cause substantial enhancement of the wear resistance of samples because the structural homogeneity of near surface layers increases, the surface roughness decreases, and its microhardness increases. The application of a mechanical-geometrical wear model based on the experimental wear characteristics determined during accelerated tests indicates that the thinning of an alloy cladding can reach rates of 10⁻⁶–10⁻³ mm/s, which agree satisfactorily with data obtained in other simulation experiments. The presence of an oxide film changes a wear process characterized by an abrasive component.     

Corrosion behavior of tin ions implanted zirconium in 1N H2SO4

In order to study the effect of tin ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted with tin ions to a fluence ranging from 1 × 10²⁰ to 5 × 10²¹ ions/m², using a metal vapor vacuum arc source (MEVVA) at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer were analyzed by X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES) respectively. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the micro-morphology and microstructure of tin-implanted samples. When the fluence was greater than 1 × 10²⁰ ions/m², many small tin balls were produced in the implanted surface. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zirconium in a 1N H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zirconium implanted with 1 × 10²⁰ ions/m². When the fluence is higher than 1 × 10²⁰ ions/m², the corrosion resistance of zirconium implanted with tin ions decreased compared with that of the non-implanted zirconium. Finally, the mechanism of the corrosion behavior of the tin-implanted zirconium is discussed.     

Au5+ ion implantation induced structural phase transitions probed through structural,microstructural and phonon properties in BiFeO3 ceramics,using synergistic ion beam energy

Implanted Au⁵⁺-ion-induced modification in structural and phonon properties of phase pure BiFeO₃ (BFO) ceramics prepared by sol–gel method was investigated. These BFO samples were implanted by 15.8?MeV ions of Au⁵⁺ at various ion fluence ranging from 1?×?10¹⁴ to 5?×?10¹⁵?ions/cm². Effect of Au⁵⁺ ions’ implantation is explained in terms of structural phase transition coupled with amorphization/recrystallization due to ion implantation probed through XRD, SEM, EDX and Raman spectroscopy. XRD patterns show broad diffuse contributions due to amorphization in implanted samples. SEM images show grains collapsing and mounds’ formation over the surface due to mass transport. The peaks of the Raman spectra were broadened and also the peak intensities were decreased for the samples irradiated with 15.8?MeV Au⁵⁺ ions at a fluence of 5?×?10¹⁵?ion/cm². The percentage increase/decrease in amorphization and recrystallization has been estimated from Raman and XRD data, which support the synergistic effects being operative due to comparable nuclear and electronic energy losses at 15.8?MeV Au⁵⁺ ion implantation. Effect of thermal treatment on implanted samples is also probed and discussed.     

锆离子注入锆-4合金缺陷的慢正电子研究

采用慢正电子束多普勒展宽谱研究了Zr离子注入Zr-4合金产生的缺陷及其退火回复行为，发现经过大于离子注入剂量为1×10¹⁶cm^-2的样品所产生的缺陷在注入过程中已经回复，而对剂量为1×10¹⁵cm^-2样品做300℃退火处理，其缺陷基本回复，得出合金缺陷回复能较低的结论. 考虑到材料的缺陷含量越高，其抗腐蚀性能越差，在辐照环境下通过给材料保持一定温度，即可使其缺陷得到较好回复，从而提高材料的抗腐蚀性能.     

Microstructure and magnetooptics of silicon oxide with implanted nickel nanoparticles

Metallic nickel nanoparticles of various sizes are formed in a thin near-surface layer in an amorphous SiO₂ matrix during 40-keV Ni⁺ ion implantation at a dose of (0.25−1.0) × 10¹⁷ ions/cm². The micro-structure of the irradiated layer and the crystal structure, morphology, and sizes of nickel particles formed at various irradiation doses are studied by transmission electron microscopy and electron diffraction. The magnetooptical Faraday effect and the magnetic circular dichroism in an ensemble of nickel nanoparticles are studied in the optical range. The permittivity [^(e)]\hat \varepsilon tensor components are calculated for the implanted samples using an effective medium model with allowance for the results of magnetooptical measurements. The spectral dependences of the tensor [^(e)]\hat \varepsilon components are found to be strongly different from those of a continuous metallic nickel film. These differences are related to a disperse structure of the magnetic nickel phase and to a surface plasma resonance in the metal nanoparticles.     

Depth profiles of metal ions implanted in dielectrics at low energies

The depth profiles of Cu⁺, Ag⁺, and Au⁺ ions implanted into amorphous dielectric SiO₂, Al₂O₃, and soda-lime silicate glass (SLSG) are simulated by the DYNA program. The algorithm follows projectile-ion-substrate-atom pair collisions giving rise to a dynamic variation in the phase composition in the surface layer of the irradiated material and takes into account surface sputtering. Ion implantation up to doses of ≤10¹⁶ ion/cm² at low ion energies of 30, 60, and 100 keV is considered. The measured dynamic variation of the depth profiles of implanted ions as a function of the dose is compared with the standard statistical distribution calculated by the TRIM algorithm.     

Optical properties of metal nanoparticles synthesized in a polymer by ion implantation: A review

Polymer composite layers irradiated by 30-keV Ag⁺ ions with doses from 3.1×10¹⁵ to 7.5×10¹⁶ cm^?2 and an ion current of 4 µA/cm² are investigated. The composites were examined using Rutherford backscattering (RBS), transmission electron microscopy (TEM), and optical spectroscopy. As follows from electron microscopy and electron microdiffraction data, ion implantation is a promising tool for synthesizing silver nanoparticles in the surface region. The optical density spectra taken of these composites demonstrate that the silver nanoparticles exhibit unusually weak plasma resonance. The formation of silver nanoparticles in layers carbonized by ion implantation is considered. Based on the Mie theory, optical extinction spectra for silver particles in the polymer and carbon matrices are simulated and optical spectra for complex silver core-carbon sheath nanoparticles are calculated. The physics behind the experimental optical spectra of the composite is discussed.     

MWA and scanning-probe study of argon-ion irradiation effects on superconducting properties of Bi2Sr2CaCu2O8 thin films

Bi₂Sr₂CaCu₂O₈ films with thickness of 200 and 800 nm were irradiated with monovalent argon ions with an energy of 40 keV and a dose ranging between 10¹⁴ and 10¹⁷ ion/cm². The dose dependences of (i) the superconducting transition temperature, (ii) the critical current density value and (iii) the irreversibility line position on the magnetic field-temperature phase diagram were determined for two series of samples of different thickness. Atomic force microscopy images of the irradiated samples showed an appearance of defects in the form of surface holes. The obtained data were used to establish conditions for improving properties of thin-film superconducting materials. Firstly, the irradiation dose should be at least 10¹⁶ ion/cm² to form embedded gas bubbles and surface holes serving as artificial pinning centers. Secondly, the film thickness and the average depth of the defect formation should be of a comparable value and sufficiently exceed the thickness of the surface layer sputtered as a result of irradiation.     

Effect of hydrogen defects on nanocrystallite layers of Si solar cells by hydrogen implantation

The Si solar cells were irradiated with high energy hydrogen ions of 10, 30, 60 and 120?keV at the dose rate of 10¹⁷ H⁺ ions (proton)/cm². The structural, optical and electrical properties of the implanted samples and fabricated cells were studied. The implantation induced defects bringing structural changes before and after annealing was evidenced by the transmission electron microscopy. The Raman spectrum showed a change of crystalline to amorphous state at 480?cm^?1 when the sample was implanted by hydrogen ion of 30?keV energy. Formation of nanocrystallite layers were observed after annealing. The electroluminescence images showed that hydrogen-related defect centers were involved in the emission mechanism. The photoluminescence emission from the implanted cells was attributed to nanocrystallite layers. From current–voltage measurements, the conversion efficiencies of implanted Si solar cells were found lower than the un-implanted reference cell. The ion implantation did not passivate the defects rather acted as recombination centers.     

Features of FMR spectra observed in granular films formed by Fe+ implantation into PMMA

Magnetic phase consisting of α-Fe particles arranged in a thin near-surface layer has been synthesized in modified phosphorus-containing polymethylmethacrylate by Fe⁺ implantation at an energy of 40 keV with a dose of 1.2⊙10¹⁷ ion/cm². The spectrum of magnetic resonance of the obtained samples is a superposition of a wide anisotropic absorption line and a set of reproducible lowintensity noiselike signals registered in a wide range of magnetic field. It has been established that a wide absorption line is due to particle conglomerates (larger than 200 nm), each behaving as a thin ferromagnetic film. Noiselike lines can be explained as resonance signals from separate oblate/prolate nanoparticles (50–200 nm in size) randomly oriented with respect to the irradiated surface. Such complicated nanostructures can be formed at an appropriate combination of properties of a polymer matrix, types of bombarded ions and implantation regimes.     

Infrared optical properties of Li- and Xe-irradiated KTiOPO<Subscript>4</Subscript>

KTP was irradiated at 100 K and 295 K with Li ions and at 295 K with Xe ions. The infrared spectra of the Li-irradiated samples are consistent with a system consisting of a layer stack of undamaged KTP/amorphous KTP/undamaged substrate. Annealing of the samples leads to a growth of the covering layer at the expense of the amorphous layer. The damage yield of the sample irradiated at 100 K is noticeably higher, resulting in a greater thickness of the amorphous layer. The spectra show interference effects, indicating homogenous layer thicknesses. Such interference effects are absent for the Xe-irradiated samples. Spectral simulations revealed that there is no buried amorphous layer present in these samples. Instead, the latter samples consist of amorphous inclusions in undamaged crystalline KTP with a volume fraction depending on the energy dose. The spectra of the sample irradiated at an ion fluence of 3×10¹² cm^-2 are very similar to the spectrum of glassy KTP, indicating a strong structural relationship between ion-damaged amorphous KTP and glassy KTP. The dielectric function of amorphous KTP was determined and used, together with the principal dielectric functions of single-crystal KTP, to successfully simulate the spectra of a sample irradiated at an ion fluence of 2×10¹¹ cm^-2 by either the effective-medium approximation (EMA) or average-refractive-index theory (ARIT). PACS 42.70.Mp; 61.82 Ms; 78.30.-j     

Structure and tribological performance by nitrogen and oxygen plasma based ion implantation on Ti6Al4V alloy

Ti6Al4V alloy was implanted with nitrogen-oxygen mixture by using plasma based ion implantation (PBII) at pulsed voltage −10, −30 and −50 kV. The implantation was up to 6 × 10¹⁷ ions/cm² fluence. The changes in chemical composition, structure and hardness of the modified surfaces were studied by XPS and nanoindentation measurements. According to XPS, it was found that the modified layer was predominantly TiO₂, but contained small amounts of TiO, Ti₂O₃, TiN and Al₂O₃ between the outmost layer and metallic substrate. Surface hardness and wear resistance of the samples increased significantly after PBII treatment, the wear rate of the sample implanted N₂-O₂ mixture at −50 kV decreased eight times than the untreated one. The sample implanted N₂-O₂ mixture showed better wear resistance than that of the sample only implanted oxygen at − 50 kV. The wear mechanism of untreated sample was abrasive-dominated and adhesive, and the wear scar of the sample implanted at −50 kV was characterized by abrasive wear-type ploughing.     

Structure and micro-mechanical properties of helium-implanted layer on Ti by plasma-based ion implantation

The present paper concentrates on structure and micro-mechanical properties of the helium-implanted layer on titanium treated by plasma-based ion implantation with a pulsed voltage of −30 kV and doses of 3, 6, 9 and 12 × 10¹⁷ ions/cm², respectively. X-ray photoelectron spectroscopy and transmission electron microscopy are employed to characterize the structure of the implanted layer. The hardnesses at different depths of the layer were measured by nano-indentation. We found that helium ion implantation into titanium leads to the formation of bubbles with a diameter from a few to more than 10 nm and the bubble size increases with the increase of dose. The primary existing form of Ti is amorphous in the implanted layer. Helium implantation also enhances the ingress of O, C and N and stimulates the formations of TiO₂, Ti₂O₃, TiO, TiC and TiN in the near surface layer. And the amount of the ingressed oxygen is obviously higher than those of nitrogen and carbon due to its higher activity. At the near surface layer, the hardnesses of all implanted samples increases remarkably comparing with untreated one and the maximum hardness has an increase by a factor of up to 3.7. For the samples implanted with higher doses of 6, 9 and 12 × 10¹⁷ He/cm², the local displacement bursts are clearly found in the load-displacement curves. For the samples implanted with a lower dose of 3 × 10¹⁷ He/cm², there is no obvious displacement burst found. Furthermore, the burst width increases with the increase of the dose.