Review on the Fabrication of Surface Functional Structures for Enhancing Bioactivity of Titanium and Titanium Alloy Implants

Titanium and its alloys have been widely applied in many biomedical fields because of its excellent mechanical properties,corrosion resistance and good biocompatibility.However,problems such as rejection,shedding and infection will occur after titanium alloy implantation due to the low biological activity of titanium alloy surface.The structures with specific functions,which can enhance osseointegration and antibacterial properties,are fabricated on the surface of titanium implants to improve the biological activity between the titanium implants and human tissues.This paper presents a comprehensive review of recent developments and applications of surface functional structure in titanium and titanium alloy implants.The applications of surface functional structure on different titanium and titanium alloy implants are introduced,and their manufacturing technologies are summarized and compared.Furthermore,the fabrication of various surface functional structures used for titanium and titanium alloy implants is reviewed and analyzed in detail.Finally,the challenges affecting the development of surface functional structures applied in titanium and titanium alloy implants are outlined,and recommendations for future research are presented.

Effect of Different Titanium Surface Treatments on the Adhesion Test Result:Dental Application

The aim of the study was to investigate the effect of different surface treatment of titanium(Ti)on the adhesion test results for dental application.Ti substrates roughened by 400 to 1500-grit SiC polish papers and alumina blasting,alkali treated by 5 molar(M)NaOH and KOH solutions and heat treated at the temperature range of 400-800℃were used in this study.The treated samples were subjected to the adhesion test.According to the results of the adhesion test,the adhesive strength showed the highest value for the blasted titanium among all polished and blasted samples.The Ti samples heated at 650℃showed the highest adhesive strength among all heat-treated samples.Further,the adhesion test results indicated the higher adhesive strength of chemically treated samples treated by NaOH rather than that by KOH.The polished and heated Ti samples showed the highest adhesive strength among all samples.

Influence of high-speed milling parameter on 3D surface topography and fatigue behavior of TB6 titanium alloy

High-speed milling of titanium alloys is widely used in aviation and aerospace industries for its high efficiency and good quality.In order to optimize the machining parameters in high-speed milling TB6 titanium alloy,experiments of high-speed milling and fatigue were conducted to investigate the effect of parameters on 3D surface topography and fatigue life.Based on the fatigue fracture,the effect mechanism of surface topography on the fatigue crack initiation was proposed.The experiment results show that when the milling speed ranged from 100 m/min to 140 m/min,and the feed per tooth ranged from 0.02 mm/z to 0.06 mm/z,the obtained surface roughness were within the limit（0.8 μm）.Fatigue life decreased sharply with the increase of surface equivalent stress concentration factor.The average error of fatigue life between the established model and the experimental results was 6.25%.The fatigue cracks nucleated at the intersection edge of machined surface.

Effects of surface nanocrystallization on corrosion resistance of β-type titanium alloy

Surface mechanical attrition treatment (SMAT) was performed on biomedicalβ-type TiNbZrFe alloy for 60 min at room temperature to study the effect of surface nanocrystallization on the corrosion resistance of TiNbZrFe alloy in physiological environment. The surface nanostructure was characterized by TEM, and the electrochemical behaviors of the samples with nanocrystalline layer and coarse grain were comparatively investigated in 0.9% NaCl and 0.2% NaF solutions, respectively. The results indicate that nanocrystallines with the size of 10-30 nm are formed within the surface layer of 30 μm in depth. The nanocrystallized surface behaves higher impedance, more positive corrosion potential and lower corrosion current density in 0.9%NaCl and 0.2%NaF solutions as compared with the coarse grain surface. The improvement of the corrosion resistance is attributed to the rapid formation of stable and dense passive film on the nanocrystallized surface of TiNbZrFe alloy.

Deformation and fracture behavior of commercially pure titanium with gradient nano-to-micron-grained surface layer

Titanium with gradient nano-to-micron scale grains from surface to matrix was fabricated by surface mechanical grinding treatment(SMGT) at room temperature.The SMGT-treated titanium shows higher strength than that of as-received one,but moderate ductility between those of ultra-fine grained(UFG) and coarse-grained titanium.Tensile stress-strain curves of SMGT-treated titanium show double strain hardening regimes.The strain hardening rate(dσ/dε) decreases with increasing strain in tensile deformation.The high strain hardening rate at initial yielding is attributed to nano-to-micron-grained surface layer.The low strain hardening rate at large plastic strain regime primarily results from coarse-grained matrix.The SMGT-treated titanium shows a ductile fracture mode with a large number of dimples.The small size of dimples in the treated surface layer is due to the combination of the high strength and strain hardening exponent.The difference between dimple size in nano-to-micron-grained surface layer and coarse-grained matrix is discussed in terms of plastic zone size at the tip of crack in the SMGT-treated titanium.

Adsorption of fluorine and chlorine on Mg(0001) surface:A density functional theory investigation

The adsorption of low-coverage of F and Cl adatoms on the Mg（0001） surface was investigated using first-principles calculations based on the density functional theory（DFT）.The stability of the（2×2） structures formed by halogen atoms adsorbed at different sites was determined.The difference between the adsorption of F and Cl on Mg（0001） surface was also discussed.The calculation results show that hollow sites are the energetically most favorable at the low-coverage.It can be concluded from the Mulliken charges and density of states that electrons transfer from the substrate Mg atoms to the adatoms,which leads to the formation of adsorbate bond and further causes the stronger interaction between Mg atom and adatom.The interaction between Cl and Mg atoms is weaker than the interaction between F and Mg.

Microstructure and texture evolution in titanium subjected to friction roll surface processing and subsequent annealing

Commercial purity and high purity titanium sheets were initially strained by a new technique, named as friction roll surface processing （FRSP）. Severe strain was imposed into the surface layer and strain gradient was formed through the thickness of the sheet. The microstructure and texture in as-strained state were investigated by optical microscopy and X-ray diffraction technique On the surface of the sheets, ultra-fine grains were found to have a sharp texture with a preferred orientation strongly related to the FRSP direction. The evolution of microstructure and crystallographic texture of FRSPed samples during recrystallization were also studied by electron back-scattered diffraction （EBSD） technique after being annealed at selected temperatures and time. The results indicated that the preferred orientations resulting from FRSP and annealing in the surface layer were formed during rolling and its recrystallization textures were reduced by FRSP. In addition, the texture evolved stably without change in main components during the annealing.

Surface modification of titanium plate enhanced fibronectin-mediated adhesion and proliferation of MG-63 cells

An understanding of osteoblast adhesion and proliferation on biomaterials is crucial to optimizing the surfaces of artificial implants used in clinical practice. Polished, anodic oxidation （AO） and micro-arc oxidation （MAO） treated titanium （Ti） plates were used as model surfaces to study the adhesion of MG-63 cells. Cells were monitored for 0.5 and 4 h; faster adhesion and spreading of MG-63 ceils were observed on the AO and MAO modified samples. Stimulated secretion of fibronectin （FN） influenced the adhesion rates. In addition, AO and MAO modified surfaces promoted cell proliferation through apparent up-regulation of FN and integrin a5 transcription via outside-in signaling. This strongly suggests that FN secretion by osteoblasts plays an essential role in enhanced cell adhesion, spreading and proliferation on these modified Ti surfaces.

DFT Study of the Effect of Temperature on ZnO Adsorbed on α-AI_2 O_3(0001)Surface

The adsorption and the growth of ZnO on α-Al2O3（0001） surface at various temperatures were theoretically calculated by using a plane wave pseudopotentials （USP） method based on density functional theory.The average adsorption energy of ZnO at 400, 600 and 800 ℃ is 4.16±0.08, 4.25±0.11 and 4.05±0.23 eV respectively. Temperature has a remarkable effect on the structure of the surface and the interface of ZnO/α-Al2O3（0001）. It is found that the Zn-hexagonal symmetry deflexion does not appear during the adsorption growth of ZnO at 400 ℃, and that the ZnO[10^-10] is parallel with the [10^-10] of the α-Al2O3（0001）, which is favorable for forming ZnO film with the Zn-terminated surface. It is observed from simulation that there are two kinds of surface structures in the adsorption of ZnO at 600 ℃： one is the ZnO surface that has the Zn-terminated structure, and whose [10^-10] parallels the [10^-10] of the substrate surface, and the other is the ZnO[10^-10] //sapphire [11-20] with the O-terminated surface. The energy barrier of the phase transition between these two different surface structures is about 1.6 eV, and the latter is more stable. Therefore,the suitable temperature for the thin film growth of ZnO on sapphire is about 600 ℃, and it facilitates the formation of wurtzite structure containing Zn-O-Zn-O-Zn-O double-layers as a growth unit-cell. At 600 ℃, the average bond length of Zn-O is 0.190±0.01 nm, and the ELF value indicates that the bond of （substrate）-O-Zn-O has a distinct covalent character, whereas the （Zn）O-Al （substrate） shows a clear character of ionic bond. However, at a temperature of 800 ℃, the dissociation of Al and O atoms on the surface of the α-Al2O3（0001） leads to a disordered surface and interface structure. Thus, the Zn-hexagonal symmetry structure of the ZnO film is not observed under this condition.

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.

Surface modification of titanium using steel slag ball and shot blasting treatment for biomedical implant applications

Surface modification is often performed using grit or shot blasting treatment for improving the performances of biomedical implants. The effects of blasting treatments using steel slag balls and spherical shots on the surface and subsurface of titanium were studied in this paper. The treatments were conducted for 60-300 s using 2-5 mm steel slag bails and 3.18 mm spherical shots. The surface morphology, roughness, and elemental composition of titanium specimens were examined prior to and after the treatments. Irregular and rough titanium surfaces were formed after the treatment with the steel slag balls instead of the spherical shots. The former treatment also introduced some bioactive elements on the titanium surface, but the latter one yielded a harder surface layer. In conclusion, both steel slag ball and shot blasting treatment have their own specialization in modifying the surface of metallic biomaterials. Steel slag ball blasting is potential for improving the osseointegration quality of implants; but the shot blasting is more appropriate for improving the mechanical properties of temporary and load bearing implants, such as osteosynthesis plates.

First-principles Calculations of H_2O Adsorption Reaction on the GaN(0001) Surface

The adsorption and decomposition of H2O on GaN（0001） surface have been explored employing density functional theory （DFT）. Two distinct adsorption features of H2O on GaN（0001） corresponding to molecular adsorption and H-OH dissociative adsorption are revealed by our calculations. The activities of the surface reactions of H2O on GaN（0001） surface are investigated. For the stepwise processes of H2O decomposition into H2 in gas phase and adsorbed O atom （H2O（g）→H2O（chem）→OH（chem） ＋ H（chem）→2H（chem） ＋ O（chem）→H2（g） ＋ O（chem））, the first and second steps are facile and can even occur at room temperature; while the last two have high barriers and thus are difficult to proceed, especially the fourth step is endothermic. In short, H2O adsorption and decomposition into H2 in gas phase and adsorbed O atom on GaN（0001） surface are exothermic by -43.98 kcal/mol.

Fabrication of titanium-based alloys with bioactive surface oxide layer as biomedical implants:Opportunity and challenges

Titanium and its alloys have long been used as implant materials due to their outstanding mechanical properties and apparent biocompatibility.Despite this,the search for better alloys has continued to be active by researchers and industries alike,as there are still pressing issues that require attention.These include(1)a large mismatch in the elastic modulus of the implant material,which causes a stress shielding problem;(2)the release of harmful ions from Ti alloys after long-term use;(3)a low bioactivity of the Ti alloy surface,which prolongs the healing process.More research has been directed toward finding new generation Ti alloys composed of more biocompatible phases and modifying the surface of Ti alloys from naturally bio-inert to bioactive in order to circumvent the problems.This review examines recent work reported on the fabrication of Ti alloys,and based on the survey,major characteristics highlighted the importance of elastic modulus and the use of non-toxic metal elements to improve biocompatibility.In terms of surface modification of Ti alloys,numerous studies have found that a nano-scaled surface oxide layer grown on the surface is always beneficial to improving the bioactivity of Ti alloys for rapid recovery after implantation.This comprehensive review focuses on the appropriate phase and composition for new Ti alloys intended for use as biomedical implants,emphasizing both fabrication and surface modification methods.

Surface Analysis of Chemical Stripping Titanium Alloy Oxide Films

The chemical stripping method of titanium alloy oxide films was studied. An environment friendly solution hydrogen peroxide and sodium hydroxide without hydrofluoric acid or fluoride were used to strip the oxide films. The morphologies of the surface and cross-section of the oxide films before and after the films stripping were characterized by using scanning electron microscopy （SEM）. The microstructure and chemical compositions of the oxide films before and after the films stripping were investigated by using Raman spectroscopy （Raman） and X-ray photoelectron spectroscopy （XPS）. It was shown that the thickness of the oxide film was in the range of 5-6 μm. The oxide films were stripped for 2 to 8 min in the solution. Moreover, the effect of the stripping time on the efficiency of the film stripping was investigated, and the optimum stripping time was between 6-8 min. When the stripping solution completely dissolved the whole film, the α/β microstructure of the titanium alloy Ti-10V-2Fe-3Al was partly revealed. The stripping mechanism was discussed in terms of the dissolution of film delamination. The hydrogen peroxide had a significant effect on the dissolution of the titanium alloy anodic oxide film. The feasibility of the dissolution reaction also was evaluated.

Water adsorption on the Be(0001) surface:from monomer to trimer adsorption

In this paper, the density functional theory has been used to perform a comparative theoretical study of water monomer, dimer, trimer, and bilayer adsorptions on the Be（0001） surface. In our calculations, the adsorbed water molecules are energetically favoured adsorbed on the atop sites, and the dimer adsorption is found to be the most stable with a peak adsorption energy of - 437 meV. Further analyses have revealed that the essential bonding interaction between the water monomer and the metal substrate is the hybridization of the water 3al-like molecular orbital with the （s, P2） orbitals of the surface beryllium atoms. While in the case of the water dimer adsorption, the lbz-like orbital of the H2O molecule plays a dominant role.

Study on Surface Modification of Titanium Dioxide Using Polymethyl Methacrylate

The polymerization of methyl methacrylate (MMA) at the surface of titanium dioxide (TiO 2) particles was carried out by using soapless emulsion polymerization method. In this process, composite particles with TiO 2 core and polymer shell were obtained and thus the surface of titanium dioxide was modified. The encapsulating polymer was characterized by TEM, DTA and IR. In addition, the surface properties of the original and modified TiO 2 were studied by Zeta potential measurement and determination of contact angle and dispersability.

Determination of efficient superfinishing conditions for mirror surface finishing of titanium

To determine mirror surface finishing conditions and efficient and economical superfinishing conditions for pure titanium and titanium alloys, an abrasive film is used when superfinishing is performed under varying conditions. These conditions include the workpiece rotation speed, the oscillation speed, the contact pressure of the roller, the hardness of the roller, and the type of abrasive film. The superfinishing device is applied to polishing a thin and long cylindrical bar. A micro-finishing film and a lapping film were used as abrasive films. A1203 grains or SiC grains were used as abrasives. The surface roughness of a polished workpiece was measured using a stylus-type surface-roughness measuring instrument. As a result, the conditions to improve the polishing surface efficiently include high values for the workpiece rotation speed, oscillation speed and contact pressure. The roller hardness has no effect on the efficient polishing conditions. The mirror finish of a surface can be created using lapping film of 3 μm with Al2O3 grains after polishing to a steady surface roughness under the efficient polishing conditions.

The First-principles Calculations of H_2S Adsorption and Decomposition on the ZnO(0001) Surface

The adsorption and decomposition of H2S on the ZnO（0001） surface have been investigated with first-principles calculations.The results reveal that H2S is dissociatively adsorbed on the clean ZnO（0001） surface to generate HS-and hydrogen species.To our interest,as indicated by Mulliken charge and density of states of the configuration calculation,the bonding mechanism of H2S on the ZnO（0001） surface can involve the donation of charge from the ＂s lone pairs＂ into the surface and the back donation of surface electrons to H2S.Therefore,the electrons should play an important role in decomposition.Furthermore,the reactivity of H2S adsorption and further thermal decomposition reactions on the ZnO（0001） surface have also been discussed by calculating the possible reaction pathways.As expected,H2 will be easily generated during the decomposition process.

Plasma Niobium Surface Alloying of Pure Titanium and its Oxidation at 900 ℃

A niobium-modified layer on pure titanium surface was obtained by means of double glow plasma surface alloying technique. The modified layer was uniform, continuous, compact and well adhered to the substrate. The niobium composition in the modified layer decreased gradually from the surface to the substrate. The oxidation behavior of the niobium-modified layer was investigated and com- pared with the untreated surface at 900 ~C for 100 h. Characterization of the layers was performed using X-ray diffraction and scanning electron microscope, respectively. The test results show that the oxidation behavior of pure titanium was improved by niobium alloying process. Niobium has a positive influence on the oxidation resistance.

Surface nanocrystallization of commercial pure titanium by shot peening

The surface nanostructures of commercial pure titanium was realized by the modified shot peening equipment commonly used in industry through the special treatment process. The results show that high-energy-shot-peening(HESP) commonly used to prepare nanostructured surface layers can be achieved by the increase of pill size, pill speed, and treatment time in the commercial shot peening equipment. XRD, SEM and TEM were used to characterize the surface layer microstructure of treated specimens. The analytic results show that the main deformation mode of commercial pure Ti is twinning. At the beginning of deformation, the dislocations are formed and twins occur within or on plane, then twins in intersection plane appear, and at last the twin characteristics disappear in the surface layer after longer treatment time. The deformation layer depth increases with treatment time in a certain period when the pill size and speed are unchanged. And in the severe plastic deformation (SPD) layer in which the twins are not identified easily by using SEM, the nanocrystalline microstructures are found under TEM. The finest grain size in the surface layer is about 40 nm, and the depth of nanostructured layers is over 60 μm. The microhardness of the nanostructured surface layers is enhanced significantly after shot peening compared with that of the initial simple.