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Linhard et al. [32,33] proposed a theory (Linhard, Scharff and Shigtt theory abbreviated as LSS the- ory) that developed a comprehensive concept of atomic stopping. By using a differential cross-section based on Thomas-Fermi potential between the atoms, LSS theory gives a relationship for nuclear stop- ping in terms of dimensionless length p, and energy ¢. These two quantities are defined as: where do(E, T) is the differential scattering cross-section at energy E, involving an energy transfer be- tween the transfer limits Tand T+ dT. Tin is the minimum energy transfer whereas T,, represents the upper limit for energy transfer. T and do(E, T) depend upon the interaction potential V (Tr) between the two particles.

Figure 4 Linhard et al. [32,33] proposed a theory (Linhard, Scharff and Shigtt theory abbreviated as LSS the- ory) that developed a comprehensive concept of atomic stopping. By using a differential cross-section based on Thomas-Fermi potential between the atoms, LSS theory gives a relationship for nuclear stop- ping in terms of dimensionless length p, and energy ¢. These two quantities are defined as: where do(E, T) is the differential scattering cross-section at energy E, involving an energy transfer be- tween the transfer limits Tand T+ dT. Tin is the minimum energy transfer whereas T,, represents the upper limit for energy transfer. T and do(E, T) depend upon the interaction potential V (Tr) between the two particles.

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Mechanical properties of several materials. Table 1 AC dAPPUd IC€s, suUleICd! LOOIS dllG OUICL SCHUSIUVE TICCICdl COMIPOMEIIUS, SUCII dS Medill VdIVes, This technique can provide modification of titanium surface for HA synthesis or property improve ment. HA is synthesized by implantation of Ca and P [8]. Improvements in wear resistance an Xiocompatibility are achieved by implantation of other ions [9]. Ion implantation technique [10 enables to inject any element into the near-surface region of any substrate. It is a non-equilibriun orocess and therefore, is capable of producing materials with compositions and structures unattain able by other conventional equilibrium methods (such as thermal diffusion or alloying). Ion bean systems are characterized by having a preferred direction, i.e., the direction of ion beam propagatior in the ion beam method, a beam of high energy (>10 keV) ions is allowed to fall on a target, kept in. vacuum chamber. The incident ions lose their energy due to collisions with the target atoms and com ‘o rest in the near-surface region.
Mechanical properties of several materials. Table 1 AC dAPPUd IC€s, suUleICd! LOOIS dllG OUICL SCHUSIUVE TICCICdl COMIPOMEIIUS, SUCII dS Medill VdIVes, This technique can provide modification of titanium surface for HA synthesis or property improve ment. HA is synthesized by implantation of Ca and P [8]. Improvements in wear resistance an Xiocompatibility are achieved by implantation of other ions [9]. Ion implantation technique [10 enables to inject any element into the near-surface region of any substrate. It is a non-equilibriun orocess and therefore, is capable of producing materials with compositions and structures unattain able by other conventional equilibrium methods (such as thermal diffusion or alloying). Ion bean systems are characterized by having a preferred direction, i.e., the direction of ion beam propagatior in the ion beam method, a beam of high energy (>10 keV) ions is allowed to fall on a target, kept in. vacuum chamber. The incident ions lose their energy due to collisions with the target atoms and com ‘o rest in the near-surface region.
Properties influenced by ion implantation (given under different categories). Table 3
Properties influenced by ion implantation (given under different categories). Table 3
Advantages of ion implantation. Table 2
Advantages of ion implantation. Table 2
Alloying elements of titanium and their effects. Table 4
Alloying elements of titanium and their effects. Table 4
Fig. 1. Illustration of various processes in ion-solid interactions.
Fig. 1. Illustration of various processes in ion-solid interactions.
Fig. 2. Depth distribution of ions inside the solid.
Fig. 2. Depth distribution of ions inside the solid.
Chronological developments of ion implantation processes. Table 5
Chronological developments of ion implantation processes. Table 5
Fig. 3. Variation of the nuclear and electronic contributions to the specific energy loss dE/dx as a function of ion velocity v.
Fig. 3. Variation of the nuclear and electronic contributions to the specific energy loss dE/dx as a function of ion velocity v.
Fig. 4. Basic processes during ion implantation. (a) Implantation of dopant atoms (implantation profile); (b) contribution of energy to nuclear subsystem (nuclear energy losses); (c) contribution of energy to electronic subsystem (electron energy losses). T.R. Rautray et al./ Progress in Materials Science 56 (2011) 1137-1177
Fig. 4. Basic processes during ion implantation. (a) Implantation of dopant atoms (implantation profile); (b) contribution of energy to nuclear subsystem (nuclear energy losses); (c) contribution of energy to electronic subsystem (electron energy losses). T.R. Rautray et al./ Progress in Materials Science 56 (2011) 1137-1177
Fig. 5. Projected range R, and the distribution of the implanted atoms AR, and AR,. Also shown is the range R of the ions.
Fig. 5. Projected range R, and the distribution of the implanted atoms AR, and AR,. Also shown is the range R of the ions.
Fig. 7. Schematic diagram of beam scanner. T.R. Rautray et al./Progress in Materials Science 56 (2011) 1137-1177
Fig. 7. Schematic diagram of beam scanner. T.R. Rautray et al./Progress in Materials Science 56 (2011) 1137-1177
Fig. 9. Suppressor with target holder. Each ion is typically one atom and the actual amount of material implanted in the target is the inte- gral over time of the ion current. This amount is called dose. The current (ion current and secondary
Fig. 9. Suppressor with target holder. Each ion is typically one atom and the actual amount of material implanted in the target is the inte- gral over time of the ion current. This amount is called dose. The current (ion current and secondary
Fig. 8. Schematic diagram of an ion implantation chamber.
Fig. 8. Schematic diagram of an ion implantation chamber.
Fig. 10. Depth of penetration an straggle of ions inside the substrate. The ion beams are generated from an ion source in high vacuum conditions as in the case of con- ventional ion beam techniques [51]. In the first of the two actions, an inert-gas ion beam is used to controllably sputter atoms from a target (HA in the present case) for getting the supply of target atoms. These are impinged on the substrate (titanium in the present context) and form a film. In the second action, inert (e.g. Ar*) or reactive gas ions (e.g. O;) are directly focused at the substrate (titanium in the present context) for modifying the properties of the growing film by some combina- tion of bombardment, reaction, or burial within it.
Fig. 10. Depth of penetration an straggle of ions inside the substrate. The ion beams are generated from an ion source in high vacuum conditions as in the case of con- ventional ion beam techniques [51]. In the first of the two actions, an inert-gas ion beam is used to controllably sputter atoms from a target (HA in the present case) for getting the supply of target atoms. These are impinged on the substrate (titanium in the present context) and form a film. In the second action, inert (e.g. Ar*) or reactive gas ions (e.g. O;) are directly focused at the substrate (titanium in the present context) for modifying the properties of the growing film by some combina- tion of bombardment, reaction, or burial within it.
Fig. 11. Schematic diagram of IBAD system and process. The technology combines evaporation with concurrent ion bear bombardment to produce adherent dense coatings with virtually any substrate/coating material combination.
Fig. 11. Schematic diagram of IBAD system and process. The technology combines evaporation with concurrent ion bear bombardment to produce adherent dense coatings with virtually any substrate/coating material combination.
Fig. 12. XRD pattern of coating layer after heat treatment in vacuum at 630 °C. Ion beam currents are (A) 0 A, (B) 0.6 A, (C) 0.8 A, (D) 1.0 A, (@) TCP, (C1) HA and (<) the Ti peak [51].
Fig. 12. XRD pattern of coating layer after heat treatment in vacuum at 630 °C. Ion beam currents are (A) 0 A, (B) 0.6 A, (C) 0.8 A, (D) 1.0 A, (@) TCP, (C1) HA and (<) the Ti peak [51].
Fig. 13. SEM of the coating layer (A) before and (B) after the heat treatment. Similar morphology was obtained for all the four beam currents of 0, 0.6, 0.8 and 1 A [51].
Fig. 13. SEM of the coating layer (A) before and (B) after the heat treatment. Similar morphology was obtained for all the four beam currents of 0, 0.6, 0.8 and 1 A [51].
Fig. 14. Schematic diagram of a DIBAD system. Objective of surface modification is to improve the macroscopic surface properties such as hard- ness, wear resistance and corrosion resistance for enhanced applications. As a surface modification technique, ion implantation was first used in the semiconductor industry to introduce controlled dopants into the semiconductor materials [54,55]. Its application to metals and alloys began in the
Fig. 14. Schematic diagram of a DIBAD system. Objective of surface modification is to improve the macroscopic surface properties such as hard- ness, wear resistance and corrosion resistance for enhanced applications. As a surface modification technique, ion implantation was first used in the semiconductor industry to introduce controlled dopants into the semiconductor materials [54,55]. Its application to metals and alloys began in the
Fig. 15. Schematic illustration of cross-sections of surface-modified layers of titanium specimens with and without calcium-ion implantation [59]. is believed to improve the hard-tissue compatibility. In another study treatment of the Ca** ion-implanted titanium surfaces in physiological solution produced needle-like HA whereas no such feature was observed on the control non-implanted tita- nium surface [62]. In vitro culturing of bone cells on the Ca ion implanted Ti samples showed that the cell-material interaction increased. But bioactivity was dependent on the ion implantation dosage 63-65] as high dose of Ca ions (10'” ions/cm?) significantly enhanced cell spreading, formation of fo- cal adhesion plaques, and expression of integrins. Another benefit of this high dose is increase of cor- rosion resistance under stationary conditions [66]. Fig. 16 shows the SEM of Ca-ion-implantec titanium surface after (a) implantation and (b) 3000h of exposure to simulated body fluid (SBF) [66]. There is a network of calcium on the implanted surface and this network is widened and spread after long-term exposure. Fig. 17 shows the SEM of the cells cultured on the surface of Ca ion im- planted Ti after 4 days exposure to SBF [66]. Cell extension and attachment are clearly visible in this figure indicating cell acceptance on the surface. Figs. 16 and 17 have been obtained under the Ca” dose rate of 10!” ions/cm? with ion energy of 25 keV. The implanted sample was exposed fo! 3000 h in SBF before the surface was inspected (Fig. 16).
Fig. 15. Schematic illustration of cross-sections of surface-modified layers of titanium specimens with and without calcium-ion implantation [59]. is believed to improve the hard-tissue compatibility. In another study treatment of the Ca** ion-implanted titanium surfaces in physiological solution produced needle-like HA whereas no such feature was observed on the control non-implanted tita- nium surface [62]. In vitro culturing of bone cells on the Ca ion implanted Ti samples showed that the cell-material interaction increased. But bioactivity was dependent on the ion implantation dosage 63-65] as high dose of Ca ions (10'” ions/cm?) significantly enhanced cell spreading, formation of fo- cal adhesion plaques, and expression of integrins. Another benefit of this high dose is increase of cor- rosion resistance under stationary conditions [66]. Fig. 16 shows the SEM of Ca-ion-implantec titanium surface after (a) implantation and (b) 3000h of exposure to simulated body fluid (SBF) [66]. There is a network of calcium on the implanted surface and this network is widened and spread after long-term exposure. Fig. 17 shows the SEM of the cells cultured on the surface of Ca ion im- planted Ti after 4 days exposure to SBF [66]. Cell extension and attachment are clearly visible in this figure indicating cell acceptance on the surface. Figs. 16 and 17 have been obtained under the Ca” dose rate of 10!” ions/cm? with ion energy of 25 keV. The implanted sample was exposed fo! 3000 h in SBF before the surface was inspected (Fig. 16).
Fig. 17. SEM of the cells cultured on the surface of Ca ion implanted Ti after 4 days exposure. Dose rate was 1 x 10!” ions/cm? with ion energy of 25 keV [66]. Fig. 16. SEM of titanium surface (a) Ca ion implanted Ti (b) 3000 h of exposure in SBF. Dose rate was 1 x 10!” ions/cm? with io1 energy of 25 keV [66].
Fig. 17. SEM of the cells cultured on the surface of Ca ion implanted Ti after 4 days exposure. Dose rate was 1 x 10!” ions/cm? with ion energy of 25 keV [66]. Fig. 16. SEM of titanium surface (a) Ca ion implanted Ti (b) 3000 h of exposure in SBF. Dose rate was 1 x 10!” ions/cm? with io1 energy of 25 keV [66].
Fig. 18. SEM of the Ti surface (a) P-ion implanted (b) after 1700 h exposures in SBF. Dose rate was 1 x 10!” ions/cm? with ion energy of 25 keV [67].
Fig. 18. SEM of the Ti surface (a) P-ion implanted (b) after 1700 h exposures in SBF. Dose rate was 1 x 10!” ions/cm? with ion energy of 25 keV [67].
Fig. 19. XRD pattern of TiGAI4V implanted with Ca, (a) without implantation, (b) Ca* - 50 keV, 3 x 10” ions/cm? (c) Ca* - 195 keV, 5 x 10!” ions/cm”, (d) and (c) annealed at 500 °C/1 h in vacuum [68].
Fig. 19. XRD pattern of TiGAI4V implanted with Ca, (a) without implantation, (b) Ca* - 50 keV, 3 x 10” ions/cm? (c) Ca* - 195 keV, 5 x 10!” ions/cm”, (d) and (c) annealed at 500 °C/1 h in vacuum [68].
Fig. 20. XRD pattern of TiGAI4V implanted with P*: (a) without implantation, (b) P* - 30 keV, 3 x 10!” ions/cm, (c) P* - 195 keV, 5 x 10!” ions/cm?, (d) as (c) annealed at 500 °C/1 h [68]. T.R. Rautray et al./ Progress in Materials Science 56 (2011) 1137-1177
Fig. 20. XRD pattern of TiGAI4V implanted with P*: (a) without implantation, (b) P* - 30 keV, 3 x 10!” ions/cm, (c) P* - 195 keV, 5 x 10!” ions/cm?, (d) as (c) annealed at 500 °C/1 h [68]. T.R. Rautray et al./ Progress in Materials Science 56 (2011) 1137-1177
Fig. 21. XRD pattern of TiGAI4V implanted with P+ and subsequently with Ca*: (a) without implantation, (b) P* - 30 kev, 3 x 10!” ions/cm? + Ca* - 50 keV, 3 x 10!” ions/cm? [68].
Fig. 21. XRD pattern of TiGAI4V implanted with P+ and subsequently with Ca*: (a) without implantation, (b) P* - 30 kev, 3 x 10!” ions/cm? + Ca* - 50 keV, 3 x 10!” ions/cm? [68].
Fig. 22. XRD spectra of Ti after Na ion implantation (implanted and heat-treated) which shows the presence of NazTiO3. Na ior dose rate ranged from 8 x 10'® to 4 x 10!” ions/cm. Ion energies were in the range of 18-22 keV. Heat treatment was done fo1 1 hat 600 °C [95]. T.R. Rautray et al./Progress in Materials Science 56 (2011) 1137-1177
Fig. 22. XRD spectra of Ti after Na ion implantation (implanted and heat-treated) which shows the presence of NazTiO3. Na ior dose rate ranged from 8 x 10'® to 4 x 10!” ions/cm. Ion energies were in the range of 18-22 keV. Heat treatment was done fo1 1 hat 600 °C [95]. T.R. Rautray et al./Progress in Materials Science 56 (2011) 1137-1177
Fig. 23. FTIR spectrum of a Ca-P precipitate on Na-implanted Ti. PO4, P-OH, P-O and C03” bands are present in it. Na ion dose rate ranged from 8 x 10!° to 4 x 10" ions/cm?. Ion energies were in the range of 18-22 keV [96]. untreated surface. The thickness of this layer depends on the implantation energy. This treated surface is immersed in SBF to form HA. During the SBF treatment Na is leached out as NaOH. A TiO3- - -nH20 hydrogel remains at the surface with more number of Ti-OH groups. Ti-OH groups act as nucleation sites for the HA precipitation from the SBF [96]. FT-IR shows that the precipitates occur as carbonated HA with its characteristic PO}-, P-OH and P-O bands along with as the CO3~ band [95] as shown in Fig. 23. HA formed by the SBF treatment is either amorphous or microcrystalline [95]. On non-implanted Ti, the density of precipitates was much lower indicating that bioactivity of the sodium-implanted titanium surface was better than the unmodified surface [97,98]. Microscopic
Fig. 23. FTIR spectrum of a Ca-P precipitate on Na-implanted Ti. PO4, P-OH, P-O and C03” bands are present in it. Na ion dose rate ranged from 8 x 10!° to 4 x 10" ions/cm?. Ion energies were in the range of 18-22 keV [96]. untreated surface. The thickness of this layer depends on the implantation energy. This treated surface is immersed in SBF to form HA. During the SBF treatment Na is leached out as NaOH. A TiO3- - -nH20 hydrogel remains at the surface with more number of Ti-OH groups. Ti-OH groups act as nucleation sites for the HA precipitation from the SBF [96]. FT-IR shows that the precipitates occur as carbonated HA with its characteristic PO}-, P-OH and P-O bands along with as the CO3~ band [95] as shown in Fig. 23. HA formed by the SBF treatment is either amorphous or microcrystalline [95]. On non-implanted Ti, the density of precipitates was much lower indicating that bioactivity of the sodium-implanted titanium surface was better than the unmodified surface [97,98]. Microscopic
Fig. 24. Light microscopy images after 24 h incubation in SBF of (a) and (b) titanium without implantation; (c) and (d) Na ion- implanted and heat-treated, titanium surface. Na ion dose rate ranged from 8 x 10'° to 4 x 10!” ions/cm?. Ion energies were in the range of 18-22 keV. Heat treatment was done for 1 h at 600 °C [96].
Fig. 24. Light microscopy images after 24 h incubation in SBF of (a) and (b) titanium without implantation; (c) and (d) Na ion- implanted and heat-treated, titanium surface. Na ion dose rate ranged from 8 x 10'° to 4 x 10!” ions/cm?. Ion energies were in the range of 18-22 keV. Heat treatment was done for 1 h at 600 °C [96].
Fig. 25. Reflection electron micrograph of marrow bone cells on (a) Ti surface, (b) HA surface layer produced on dual ‘Calcium (fluence of 5 x 10!” ions/cm? at 30 keV) and Phosphorus (fluence of 3 x 10!” ions/cm? at 23 keV)’ ion-implanted titanium [70]. Oe EE ee Post-implantation treatments (heat- or hydrothermal-treatments) could augment the bioactivity. Calcium and phosphorus ions were implanted on a titanium surface and then this surface was heated at 500 °C in an oxygen atmosphere. The surface layer was enriched with CaO and P20s. Exposed to a SBF solution, this surface showed a higher ability to nucleate HA than the control non-implanted tita- nium [100]. The two-step implantation of calcium and phosphorus ions onto titanium has also been combined with various post-implantation treatments with the aim to produce continuous HA layers. Pham et al. [100] subjected implanted titanium to hydrothermal heating, whereas Baumann et al. [70] heated the samples at 600 °C. The HA layers obtained by these investigators showed good adhesion to the substrate.
Fig. 25. Reflection electron micrograph of marrow bone cells on (a) Ti surface, (b) HA surface layer produced on dual ‘Calcium (fluence of 5 x 10!” ions/cm? at 30 keV) and Phosphorus (fluence of 3 x 10!” ions/cm? at 23 keV)’ ion-implanted titanium [70]. Oe EE ee Post-implantation treatments (heat- or hydrothermal-treatments) could augment the bioactivity. Calcium and phosphorus ions were implanted on a titanium surface and then this surface was heated at 500 °C in an oxygen atmosphere. The surface layer was enriched with CaO and P20s. Exposed to a SBF solution, this surface showed a higher ability to nucleate HA than the control non-implanted tita- nium [100]. The two-step implantation of calcium and phosphorus ions onto titanium has also been combined with various post-implantation treatments with the aim to produce continuous HA layers. Pham et al. [100] subjected implanted titanium to hydrothermal heating, whereas Baumann et al. [70] heated the samples at 600 °C. The HA layers obtained by these investigators showed good adhesion to the substrate.
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EngineeringIon ImplantationSurface Current
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