Modifications induced by swift heavy ions

On their way through matter, energetic heavy ions induce a continuous trail of ionization and excitation. A narrow path of irreversible physical, chemical and structural changes, the latent track, is formed. In this report, some of the most important techniques (transmission electron and atomic force microscopy, small-angle X-ray scattering, chemical etching) to study and to characterize ion induced modifications will be presented. Furthermore, selected examples for application oriented projects will be given.     

Variation of crystal structure of hydroxyapatite in calcium phosphate cement by the substitution of strontium ions

New routes were used to introduce strontium into calcium phosphate cement in the present article. The study showed that by mixing 50 wt% amorphous calcium phosphate + amorphous strontium phosphate and 50 wt% dicalcium phosphate dihydrate, hydroxyapatite and Sr-hydroxyapatite precipitated separately in the hydrated cement; whereas, by mixing 50 wt% Sr- amorphous calcium phosphate and 50 wt% dicalcium phosphate dihydrate, strontium can be doped into hydroxyapatite lattice and increase the lattice dimensions and lattice volume. The strontium substituted calcium phosphate cement has potential for use in orthopedic surgeries.     

Modifications in thin film structures by swift heavy ions

We review older and more recent work concerning modification of thin films during irradiation with heavy ions in the electronic energy deposition regime: loss of H₂ and N₂ from the bulk of several thin film materials, electronic sputtering of SiO₂ and oxygen diffusion across an interface in SiO₂.     

Interaction of hydroxyapatite with titanium nickelide and titanium

It has been established that the interaction of hydroxyapatite with titanium nickelide and titanium results in the formation of new phases whose physicomechanical properties and biocompatibility are unknown. After hydroxyapatite has been resorbed, these phases come in contact with tissue and near-tissue fluids and influence the result of the implant. Pis’ma Zh. Tekh. Fiz. 24, 41–44 (December 26, 1998)     

Formation of highly oriented hydroxyapatite in hydroxyapatite/titanium composite coating by radio-frequency thermal plasma spraying

Highly oriented hydroxyapatite (HA) coatings with excellent adhesion were successfully obtained on titanium (Ti) and titanium alloy through a radio-frequency thermal plasma spraying method. The ratio of HA and Ti powders supplied into the plasma was precisely controlled by two microfeeders so as to change the composition from Ti-rich to HA-rich toward the upper layer of the formed coatings. The bond (tensile) strength of the HA/Ti composite coatings was ca. 40–50 MPa. XRD patterns showed that the topmost HA layer of the coatings had an apatite structure with (00l) preferred orientation. The degree of this orientation showed a tendency to increase with an increase in the substrate temperature during spraying.     

Nano-Ag-loaded hydroxyapatite coatings on titanium surfaces by electrochemical deposition

Hydroxyapatite (HA) coatings on titanium (Ti) substrates have attracted much attention owing to the combination of good mechanical properties of Ti and superior biocompatibility of HA. Incorporating silver (Ag) into HA coatings is an effective method to impart the coatings with antibacterial properties. However, the uniform distribution of Ag is still a challenge and Ag particles in the coatings are easy to agglomerate, which in turn affects the applications of the coatings. In this study, we employed pulsed electrochemical deposition to co-deposit HA and Ag simultaneously, which realized the uniform distribution of Ag particles in the coatings. This method was based on the use of a well-designed electrolyte containing Ag ions, calcium ions and l-cysteine, in which cysteine acted as the coordination agent to stabilize Ag ions. The antibacterial and cell culture tests were used to evaluate the antibacterial properties and biocompatibility of HA/Ag composite coatings, respectively. The results indicated the as-prepared coatings had good antibacterial properties and biocompatibility. However, an appropriate silver content should be chosen to balance the biocompatibility and antibacterial properties. Heat treatments promoted the adhesive strength and enhanced the biocompatibility without sacrificing the antibacterial properties of the HA/Ag coatings. In summary, this study provided an alternative method to prepare bioactive surfaces with bactericidal ability for biomedical devices.     

Preparation and structure of carbonated calcium hydroxyapatite substituted with heavy rare earth ions

Calcium hydroxyapatite (CaHap) particles substituted five types of heavy rare earth ions (Ln: Y³⁺, Gd³⁺, Dy³⁺, Er³⁺ and Yb³⁺) were synthesized using a precipitation method and characterized using various means. These Ln ions strongly affected the crystal phases and the structures of the products. With increasing Ln/(Ln + Ca) in the starting solution ([X_Ln]), the length and the crystallinity of the particles first increased and then decreased. The rare earth metal-calcium hydroxyapatite (LnCaHap) solid solution particles were obtained at [X_Y] ≤ 0.10 for substituting Y system and at [X_Ln] ≤ 0.01–0.03 for substituting the other Ln systems. LnPO₄ was mixed with LnCaHap at higher [X_Ln] for all Ln systems. A series of yttrium-calcium hydroxyapatite (YCaHap) solid solutions with [X_Y] = 0–0.10 were investigated using XRD, TEM, ICP-AES, IR and TG–DTA in detail.     

A functionally graded titanium/hydroxyapatite film obtained by sputtering

A functionally graded film of titanium/hydroxyapatite (HA) was prepared on a titanium substrate using a radio frequency magnetron sputtering. The ratio of titanium to HA was controlled by moving the target shutter. The film was composed of five layers, with overall film thickness of 1 m. The HA was concentrated close to the surface, while the titanium concentration increased with proximity to the substrate. The bonding strength between the film and the substrate was 15.2 MPa in a pull-out test and the critical load from a scratch test was 58.85 mN. The corresponding values of a pure HA sputtered film were 8.0 MPa and 38.47 mN, respectively. The bonding strength of a pure HA plasma spray coating was 10.4 MPa in the pull-out test. The graded film and the pure HA film were sputter-coated to a thickness of 1 m on titanium columns (10 mm in length and 4 mm in diameter). These columns were implanted in diaphyses of the femora of six adult dogs and a push-out test was carried out after 2, 4, and 12 weeks. After 12 weeks, the push-out strengths of the graded film, the pure HA film and the non-coated columns were 3.7, 3.5, and 1.0 MPa.     

Synthesized silicon-substituted hydroxyapatite coating on titanium substrate by electrochemical deposition

Silicon-substituted hydroxyapaptite (Si-HA) coatings were prepared on titanium substrates by electrolytic deposition technique in electrolytes containing Ca²⁺, PO₄ ³⁻ and SiO₃ ²⁻ ions with various SiO₃ ²⁻/(PO₄ ³⁻ + SiO₃ ²⁻) molar ratios(η_si). The deposition was all conducted at a constant voltage of 3.0 V, with titanium substrate as cathode and platinum as anode, for 1 h at 85°C. The coatings thus prepared were characterized with inductively coupled plasma (ICP), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), field-emission-type scanning electron microscope (FSEM). The results show that the silicon amount in the coatings increases linearly to about 0.48 wt% at first with increasing η_si between 0 and 0.03, then increases slowly to about 0.55 wt% between 0.03 and 0.10 and finally maintains almost at a level around 0.55 wt% between 0.10 and 0.30. The tree-like Si-HA crystals are observed in the coatings prepared in the electrolyte of η_si = 0.20. And the presence of silicon in electrolytes decreases the thickness of the coatings, with effect being more significant as η_si increased. Additionally, the substitution of Si causes some OH⁻ loss and changes the lattice parameters of hydroxyapatite (HA).     

ZrO2/hydroxyapatite coating on titanium by electrolytic deposition

In this study, hydroxyapatite (HA) was coated on a titanium (Ti) substrate over a ZrO(2) layer by the electrolytic deposition method, this double layer coating was then compared with a single layer coating of HA. The HA layer was used to increase the bioactivity and osteoconductivity of the Ti substrate, and the ZrO(2) layer was intended to improve the bonding strength between the HA layer and Ti substrate, and to prevent the corrosion of the Ti substrate. The electrolytic deposition formed an HA layer with a thicknesses of approximately 20 mum, which adhered tightly to the Ti substrate. The bonding strength of the HA/ZrO(2) double layer coating on Ti was markedly improved when compared to that of the HA single coating on Ti. The improvement in bonding strength with the use of a ZrO(2) base layer was attributed to the resulting increase in chemical affinity of the ZrO(2) to the HA layer and to the Ti substrate. The osteoblast-like cells cultured on the HA/ZrO(2) coating surface, proliferated in a similar manner to those on the HA single coating and on the pure Ti surfaces. At the same time, the corrosion resistance of Ti was improved by the presence of the ZrO(2) coating, as shown by a potentiodynamic polarization test.     

Effects of titanium surface modifications on bonding behavior of hydroxyapatite ceramics and titanium by hydrothermal hot-pressing

In order to improve the interface strength in the bonded body of hydroxyapatite (HA) ceramics and Ti disks prepared by a hydrothermal hot-pressing (HHP) method, the effects of Ti surface modification on the bonding behavior were investigated. The reaction layer composed of titanium dioxide and sodium titanate was formed on the Ti surface using a 5 M NaOH solution with the objective of increasing the interface strength between the Ti substrate and HA ceramics to be formed by the HHP method. Three conditions with different temperature and treatment times were tested to modify the Ti surface. A mixture of calcium hydrogen phosphate dihydrate and calcium hydroxide was used as a starting powder material for solidifying HA. Solidification of HA and its bonding with Ti were achieved simultaneously by using the HHP method at the low temperature as low as 323 K. 3-point bending tests were conducted to obtain an estimate of the interface fracture toughness of HA/Ti. The Ti surface modification conducted at 323 K for 2 h using the hydrothermal NaOH solution was shown to be most effective among the three conditions tested. The hydrothermal Ti surface modification enabled us to increase significantly the interface fracture toughness. The enhancement of the interface fracture toughness was possibly due to the presence of anatase formed on the Ti surface and the good adhesion in the bioactive layer.     

Microstructural characterization of hydroxyapatite coating on titanium

The microstructure of hydroxyapatite plasma sprayed onto titanium alloy has been studied by using transmission electron microscopy. It has been shown that while substantial portions of the coating are crystalline hydroxyapatite, regions of amorphous calcium phosphate with Ca/P ratios of 0.6–1.0 are also present, both in the coatings and at the metal-ceramic interface. The microstructures observed have also been found to be consistent with devitrification of the amorphous calcium phosphates producing regions of very fine grained hydroxyapatite. A calcium titanate phase has also been detected at the metal-ceramic interface produced by the chemical reaction of hydroxyapatite to titanium.     

Incorporation of fluorine ions into hydroxyapatite by a pH cycling method

Fluorine ions were incorporated into hydroxyapatite (HA) using a pH cycling method and the resulting materials were studied using transmission electron microscopy (TEM), X-ray diffraction (XRD), and electrochemical analysis. TEM observations showed that fluoridated hydroxyapatite (FHA) nanoparticles with a narrow particle size distribution were obtained at several different levels of fluorine incorporation. Significant particle growth was observed following calcining at 1200°C. The TEM data revealed that, instead of forming laminated structures, a mixture of HA and FA was obtained, and that this mixture transformed into a single homogeneous FHA phase upon heating. It was found that the efficiency of fluorine incorporation did not vary significantly with the initial HA particle size, but increased as the fluorine content of the initial solution was increased. A relatively low fluorine incorporation efficiency, ~60%, was attained for most of the FHA samples and this was attributed to the short holding time at each pH cycle and the limited number of pH cycles employed in the current study.     

Surface modification and chemical sputtering of graphite induced by low-energy atomic and molecular deuterium ions

The surface morphology, and chemical/structural modifications induced during chemical sputtering of ATJ graphite by low-energy (<200 eV/D) deuterium atomic and molecular ions are explored by Scanning Electron Microscopy (SEM), Raman and Auger Electron Spectroscopy (AES) diagnostics. At the lowest impact energies, the ion range may become less than the probe depth of Raman and AES spectroscopy diagnostics. We show that such diagnostics are still useful probes at these energies. As demonstration, we used these surface diagnostics to confirm the characteristic changes of surface texture, increased amorphization, enhanced surface reactivity to impurity species, and increased sp³ content that low-energy deuterium ion bombardment to steady-state chemical sputtering conditions produces. To put these studies into proper context, we also present new chemical sputtering yields for methane production of ATJ graphite at room temperature by impact of D₂⁺ in the energy range 10-250 eV/D, and by impact of D⁺ and D₃⁺ at 30 eV/D and 125 eV/D, obtained using a Quadrupole Mass Spectroscopy (QMS) approach. Below 100 eV/D, the methane production in ATJ graphite is larger than that in HOPG by a factor of ∼2. In the energy range 10-60 eV/D, the methane production yield is almost independent of energy and then decreases with increasing ion energies. The results are in good agreement with recent molecular dynamics simulations.     

Mechanics of molecular collagen is influenced by hydroxyapatite in natural bone

As often seen in biological structural materials, bone exhibits complex hierarchical structure. The primary constituents of bone are collagen and hydroxyapatite (HAP). HAP mineralizes at specific locations at collagen, in such a way that the c-axis of HAP aligns parallel to collagen molecule. The collagen molecule is helical overall with non-helical ends that are N- or C-telopeptides. The collagen molecule with telopeptides interacts with specific surfaces of mineralized HAP. When subjected to load, the interactions at the interface between HAP and collagen may significantly affect the overall mechanics of the collagen molecule. Here, we have performed molecular dynamics (MD) and steered MD (SMD) simulations in order to understand the load carrying behavior of collagen in the proximity of HAP. Our simulations indicate that the load-deformation response of collagen is different when it interacts with HAP as compared to its response in the absence of HAP. The interface between HAP and collagen affects the overall load-deformation response of collagen. Further, bone also has considerable amount of water and we have observed that water significantly influences the load-deformation response of collagen due to collagen-water-HAP interactions.     

Removal of lead ions in aqueous solution by hydroxyapatite/polyurethane composite foams

We have prepared hydroxyapatite/polyurehthane (HAp/PU) composite foams with two different HAp contents of 20 and 50 wt.% and investigated their removal capability of Pb2+ ions from aqueous solutions with various initial Pb2+ ion concentrations and pH values of 2-6. HAp/PU composite foams synthesized exhibited well-developed open pore structures which provide paths for the aqueous solution and adsorption sites for Pb2+ ions. With increasing the HAp content in the composites, the removal capability of Pb2+ ions by the composite foams increases owing to the higher adsorption capacity, whereas the removal rate is slower due to the less uniform dispersity of HAp in composite foams. The removal rate of Pb2+ ions is also slower with increasing the initial Pb2+ ion concentration in aqueous solutions. The removal mechanism of Pb2+ ion by the composites is varied, depending on the pH value of aqueous solution: the dissolution of HAp and precipitation of hydroypyromorphite is dominant at lower pH 2-3, the adsorption of Pb2+ ions on the HAp/PU composite surface and ion exchange reaction between Ca2+ of HAp and Pb2+ in aqueous solution is dominant at higher pH 5-6, and two removal mechanisms compete at pH 4. The equilibrium removal process of Pb2+ ions by the HAp/PU composite foam at pH 5 was described well with the Langmuir isotherm model, resulting in the maximum adsorption capacity of 150 mg/g for the composite foam with 50 wt.% HAp content.     

Effect of titanium and zirconium substitutions for calcium on the formation and structure of tricalcium phosphate and hydroxyapatite

The effect of Ti and Zr substitutions for Ca cations on the formation of tricalcium phosphate and hydroxyapatite has been studied in a wide concentration range: from 0.1 to 20 mol %. Upon the incorporation of Ti and Zr cations into tricalcium phosphate, the major forming phase is β-tricalcium phosphate. On the addition of low substituent concentrations to hydroxyapatite, we observe the formation of a single-phase material with the apatite structure. Increasing the substituent concentration to 10–20 mol % Ti or 20 mol % Zr leads to the formation of tricalcium phosphate. The unit-cell volume of the cation-substituted tricalcium phosphates has been shown to decrease with increasing substituent concentration. In the zirconium-containing hydroxyapatites, the unit-cell volume decreases with increasing zirconium concentration, whereas the titanium-containing hydroxyapatites exhibit an opposite tendency.     

Effect of supersaturation on the morphology of hydroxyapatite crystals deposited by electrochemical deposition on titanium

Cathodic deposition of calcium phosphate coating on titanium using electrochemical method was investigated in our study and well-defined hexagonal rod-like hydroxyapatite (HAp) crystals were synthesized. Scanning electron microscopic photographs of HAp coatings under different deposition durations revealed the morphology change of the HAp crystals in the coating film with the experimental process: from cone-like structure to hexagonal prism with sharp-angled tip, and finally turns to rod-like one with regular hexagonal cross section. It was suggested that both morphology and longitudinal length of the HAp crystals in the coating could be regulated by an accurate control of the degree of supersaturation of the aqueous system.