Improvement in antibacterial ability and cell cytotoxicity of Ti-Cu alloy by anodic oxidation

Ti-Cu alloy has potential to be used in plastic surgery and dental implants due to its strong antibacterialproperties,high strength and good corrosion resistance.In this paper,Ti-5Cu was anodic-oxidized to enhance the surface compatibility.The influence of the oxidation on the corrosion resistance,antibacterial properties and biological properties was investigated.X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)results showed that a double-layer oxide coating with dense inner layer and porous outside layer was formed on Ti-Cu sample.The oxide coating consisted mainly of TiO2,CuzO and small amount of CuO,improved the corrosion resistance of Ti-Cu alloy by one order of magnitude due to the formation of the dense oxide inner layer,but high Cu ion release was detected.The plate count results showed that the antibac-terial activity of Ti-Cu sample was improved to≥99%due to the comprehensive function of CuO and Cu₂O in the coating and Cu²⁺release.Cell test results showed that thecoating exhibited good cell compatibility,the porous sur-face structure improved the adhesion of cells,and Cu ion release promoted the cell proliferation.     

Evolution of the Corrosion Product Film and Its Effect on the Erosion–Corrosion Behavior of Two Commercial 90Cu–10Ni Tubes in Seawater

The composition and structural evolution of the corrosion product film of two commercial 90Cu–10Ni tubes, namely Tube A and Tube B, after being immersed in natural seawater for 1, 3, and 6 months were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and its effect on the erosion–corrosion behavior of the tubes was determined through a rotating cylinder electrode system using various electrochemical techniques. For the freshly polished samples used as contrast samples, the flow velocity mainly enhanced the cathodic reaction at low flow velocities while both the anodic and the cathodic reactions were remarkably accelerated at higher flow velocities. The corrosion product films formed on the two commercial 90Cu–10Ni tubes after being immersed in seawater for up to 6 months are of a complex three-layer or multilayer structure. The structural evolution of the films is out of sync for the two tubes. A continuous residual substrate layer depleted of Ni was observed in the inner layer of the films on Tube B after 30, 90, and 180 days' immersion, while it was observed in the film on Tube A only after 180 days' immersion. The nature of the inner layer plays a crucial role in the erosion–corrosion resistance of the 90Cu–10Ni tubes at higher flow velocity. The film with a compact and continuous inner layer of Cu_2O doped with Ni~(2+)and Ni~(3+)which bonds firmly with the substrate could survive and even get repaired with the increased flow velocity. The film on Tube B possessing a hollow and discontinuous inner layer composed of the residual substrate was degraded rapidly with increasing rotation speed in spite of its quite good resistance at the stagnant or lower speed conditions.     

Dendritic Boundary Corrosion of AA2198 Weld Using Fiber Laser Welding with Al–Cu Filler Wire

The microstructures and corrosion behaviors of AA2198–T851 alloy and weld were analyzed under corrosive conditions.Weld was formed using an innovative fiber laser welding process with AA2319 Al–Cu filler wire. The metallurgic morphology and distribution of the chemical compositions were determined using imaging techniques such as optical micrograph, scanning electron micrograph, high-resolution transmission electron microscopy, energy-dispersive X-ray spectrometry and X-ray diffraction. Corrosion was evaluated using an immersion test and electrochemical impedance spectroscopy in 3.5% NaCl solution at room temperature. Results indicate that the parent alloy suffered from pitting corrosion during the initial 4-h immersion which was caused by the inhomogeneous distribution of its chemical components and the different intermetallics formed during the rolling process. The weld experienced dendritic boundary corrosion under the same conditions due to the addition of the Al–Cu filler and rapid solidification during laser welding, which led to the precipitates Cu enrichment along the grain boundary. When a welding joint was immersed in the solution for 5 days, a big crack was observed across the center of the weld. In comparison, there was good corrosion resistance in the heataffected zone with a compact protective film.     

Additive manufacturing technologies of porous metal implants

Biomedical metal materials with good corrosion resistance and mechanical properties are widely used in orthopedic surgery and dental implant materials,but they can easily cause stress shielding due to the significant difference in elastic modulus between the implant and human bones.The elastic modulus of porous metals is lower than that of dense metals.Therefore,it is possible to adjust the pore parameters to make the elastic modulus of porous metals match or be comparable with that of the bone tissue.At the same time,the open porous metals with pores connected to each other could provide the structural condition for bone ingrowth,which is helpful in strengthening the biological combination of bone tissue with the implants.Therefore,the preparation technologies of porous metal implants and related research have been drawing more and more attention due to the excellent features of porous metals.Selective laser melting（SLM）and electron beam melting technology（EBM）are important research fields of additive manufacturing.They have the advantages of directly forming arbitrarily complex shaped metal parts which are suitable for the preparation of porous metal implants with complex shape and fine structure.As new manufacturing technologies,the applications of SLM and EBM for porous metal implants have just begun.This paper aims to understand the technology status of SLM and EBM,the research progress of porous metal implants preparation by using SLM and EBM,and the biological compatibility of the materials,individual design and manufacturing requirements.The existing problems and future research directions for porous metal implants prepared by SLM and EBM methods are discussed in the last paragraph.     

Superparamagnetic CoFe_2O_4@Au with High Specific Absorption Rate and Intrinsic Loss Power for Magnetic Fluid Hyperthermia Applications

CoFe_2O_4 nanoparticles(NPs) and surface modified with gold(Au) have been synthesized by a thermal decomposition method. The obtained NPs and formation of CoFe_2O_4@Au core–shell(CS) were confirmed by characterizing their structural and optical properties using X-ray powder diffraction(XRD) patterns, Fourier transform infrared spectroscopy,Raman spectroscopy, UV–Visible and photoluminescence studies. Morphological and compositional studies were carried out using high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy, while the magnetic properties were determined using alternating gradient magnetometer and Mossbauer to define the magneto-structural effects of shell formation on the core NPs. Induction heating properties of CoFe_2O_4 and CoFe_2O_4@Au CS magnetic nanoparticles(MNPs) have been investigated and correlated with magneto-structural properties. Specific absorption rate and intrinsic loss power were calculated for these MNPs within the human tolerable range of frequency and amplitude,suggesting their potential in magnetic fluid hyperthermia therapy for possible cancer treatment.     

Effects of Y2O3 on the microstructure and wear resistance of cobait-based alloy coatings deposited by plasma transferred arc process

Cobalt-based alloys with different Y2O3 contents were deposited on Q235A-carbon steel using plasma transferred arc （PTA） welding machine. The effect of Y2O3 on the microstructure and wear resistance properties of the cobait-based alloys were investigated using an optical microscope, a scanning electron microscope （SEM）, X-ray diffraction （XRD）, and transmission electron microscopy （TEM）. It was found that a cobalt-based solid solution with a face-centered cubic crystal structure was presented accompanied by the secondary phase M7C3 with a hexagonal crystal structure in the Y2O3-free cobalt-based alloy coating. Several stacking faults exist in the cobalt-based solid solution. The addition of Y2O3 leads to the existence of the Y2O3 phase in the Y2O3-modified coatings. Though stacking fault exists in the Y2O3-modified coatings, its density increases. The addition of Y2O3 can refine the microstructure and can increase the wear resistance properties when its contents are less than or equal to 0.8 wt.%. However, further increase of its contents will lead to the agglomeration of undissolved Y2O3 particles at the γ-Co grain boundary, and will lead to a coarse microstructure and lower wear resistance properties.     

Effects of Y_2O_3 on the microstructure and wear resistance of cobalt-based alloy coatings deposited by plasma transferred arc process

Cobalt-based alloys with different Y2O3 contents were deposited on Q235A-carbon steel using plasma transferred arc (PTA) welding machine. The effect of Y2O3 on the microstructure and wear resistance properties of the cobalt-based alloys were investigated using an optical microscope, a scanning electron microscope (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). It was found that a cobalt-based solid solution with a face-centered cubic crystal structure was presented accompanied by the secondary phase M7C3 with a hexagonal crystal structure in the Y2O3-free cobalt-based alloy coating. Several stacking faults exist in the cobalt-based solid solution. The addition of Y2O3 leads to the existence of the Y2O3 phase in the Y2O3-modified coatings. Though stacking fault exists in the Y2O3-modified coatings, its density increases. The addition of Y2O3 can refine the microstructure and can increase the wear resistance properties when its contents are less than or equal to 0.8 wt.%. However, further increase of its contents will lead to the agglomeration of undissolved Y2O3 particles at the γ-Co grain boundary, and will lead to a coarse microstructure and lower wear resistance properties.     

Processing and mechanical properties of porous 316L stainless steel for biomedical applications

Highly porous 316L stainless steel parts were produced by using a powder metallurgy process, which includes the selective laser sintering（SLS） and traditional sintering. Porous 316L stainless steel suitable for medical applications was successfully fabricated in the porosity range of 40%-50% （volume fraction） by controlling the SLS parameters and sintering behaviour. The porosity of the sintered compacts was investigated as a function of the SLS parameters and the furnace cycle. Compressive stress and elastic modulus of the 316L stainless steel material were determined. The compressive strength was found to be ranging from 21 to 32 MPa and corresponding elastic modulus ranging from 26 to 43 GPa. The present parts are promising for biomedical applications since the optimal porosity of implant materials for ingrowths of new-bone tissues is in the range of 20%-59% （volume fraction） and mechanical properties are matching with human bone.     

Antibacterial ability and biocompatibility of fluorinated titanium by plasma-based surface modification

Biomaterial surfaces with satisfied antibacterial activity and appropriate cytocompatibility are a pressing clinical need for orthopedic and dental implants.Fluorinecontaining biomaterials have been demonstrated to obtain antibacterial activity and osteogenic property,while the effect of fluorine chemical compositions on antibacterial property and cytocompatibility is rarely studied.To this end,the coatings with different fluorine chemical compositions on titanium surface were prepared by plasma treatment to verify the antibacterial ability and cytocompatibility of fluorinated surfaces.Their antibacterial ability was evaluated by using Staphylococcus aureus,and the cell compatibility was investigated with MC3T3-E1 cells in vitro.The results show that both fluorocarbon coating and metal fluorides coating exhibited a hydrophilic and nano-scaled roughness.Rather than the fluorocarbon coating,the coating composed of metal fluorides presented satisfied bactericide effect and excellent cytocompatibility.The antibacterial mechanism is associated with the metal fluorides and released fluoride ion.This work would provide novel sight in optimizing the surface modification method of fluorinated biomaterials for biomedical applications.     

PECVD OF HARD AND ELASTIC BCN COATINGS

Compounds of the B-C-N system are very promising to produce superhard coatings with good tribological, chemical and thermal properties. Consequently, BCN films were prepared by plasma enhanced chemical vapor deposition (PECVD). The films were deposited from gaseous mixtures of BCl3-C2H4-N2-H2-Ar in different unipolar and bipolar pulsed glow discharges at 550℃ and analyzed with respect to composition, electronic structure and mechanical properties. The micro structure and composition of the BCN films were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and reflection electron energy loss spectroscopy (REELS). Mechanical properties were characterized using both the traditional Vickers method and nanoindentation. The films, that were deposited using a bipolar pulsed generator, were weak and had a sponge-like structure, whereas the films prepared using an unipolar generator were well adherent, had a hardness of more than 11GPa and very high e     

医用碳材料对骨组织的响应及其生物活化改性

对骨种植医用碳材料的种类、碳材料对骨组织间的响应及碳／碳复合材料表面生物活化改性研究现状进行了综述。提出了碳／碳复合材料表面生物活性改性涂层结构，认为碳／碳复合材料表面活性改性的结构应由硬质阻挡层和不降解生物活化层组成；根据目前已研究的生物活性陶瓷种类，提出了碳／碳复合材料表面生物活性涂层具体结构思路，同时展望了医用骨种植碳材料的前景。     

Low energy helium ion texturization of titanium and relevance to biomedical applications

Helium irradiation of metals has long been studied in efforts to understand the damaging aspects associated with applications in fusion reactors and tritium storage. This work examines the possibility of using low energy helium ion bombardment as a method of producing a beneficial surface texturization to promote bone growth on orthopedic implants. Using 300 eV helium ions, two unique porous titanium surfaces were created when substrates were held at temperatures of roughly 450 °C and 600 °C. The surfaces were physically characterized by scanning electron microscopy (SEM) and scanning white light interferometry. A week long hFOB 1.19 cell culture was performed using an untreated titanium control to evaluate the suitability of these surfaces for orthopedic implants. Cell health and viability were evaluated by calcein AM live cell staining, MTT assay, and SEM. The results show that helium texturizations promote cellular activity and have no detrimental effect on cell health.     

Surface morphology and in vitro bioactivity of biocompatible hydroxyapatite coatings on medical grade S31254 steel by RF magnetron sputtering deposition

Hydroxyapatite (HA) is popularly used as a biocompatible coating material for metallic implants, in view of its improved bone fixation property, leading to an increased life of the implant. However, the deposition of HA on medical grade UNS S31254 stainless steel (SS254) for orthopaedic implant applications by the radio-frequency magnetron sputtering technique is unreported in the literature so far. The surface morphology of the deposited HA coatings was characterised using scanning electron microscopy and atomic force microscopy, while their phase composition was determined using X-ray diffraction. The thickness and adhesive strength of the HA coatings were determined using an ellipsometer and a tensometer, respectively. Finally, the antibacterial efficacy and bioactivity of the deposited coatings were confirmed using fluorescence activated cell sorting and immersion testing in simulated body fluid environment. The results obtained showed that the HA coatings grown on SS254 using magnetron sputtering possess desirable surface properties as well as good adhesion and biocompatibility properties, ideally suited for potential applications in orthopaedic implants.     

Chemical and mechanical properties of anodized cp-titanium in NH4 H2PO4/NH4F media for biomedical applications

Potentiostatic anodizing of commercially pure titanium, using ammonium phosphate and ammonium fluoride solution as electrolyte is studied. The objective is to generate titanium oxides on the surface and phosphor compounds presenting good protective and mechanical properties, and proper adhesion to the metal substrate to remain during surgical orthopedic procedures (implants). Two different applied potentials were used to obtain different surface oxides morphologies (20 and 30 V). The characterization and quantification of the generated deposits is presented as a starting point for the future application of these composite types of materials. X-ray Photoelectron Spectroscopy (XPS) and Raman spectroscopy techniques showed the presence of phosphor compounds and anatase (TiO₂) as the main constitutive phases.     

等离子喷涂技术在骨植入体表面改性中的研究进展

金属植入体材料已广泛用于各种硬组织相关疾病的治疗,但金属植入体表面的骨整合和抗菌能力不足,往往导致临床植入手术失败。表面改性能够在保持金属材料优异力学性能的同时,针对性地改善其表面特性,目前广泛用于解决金属植入体存在的骨整合能力差和缺乏抗菌性能等问题。在众多表面改性技术中,等离子喷涂因性价比高、工艺成熟、原料可选择范围广及可大规模生产等优点,目前已在人工关节和牙种植体表面改性方面获得商业化应用。从提高植入体成骨活性、抗感染能力及骨免疫调节能力等方面介绍等离子喷涂技术的优势及其在金属植入体表面改性方面的研究进展,阐述等离子喷涂技术在优化骨科植入体表面化学性质方面的优势,并重点讨论等离子喷涂技术在制备和调控植入体表面纳米结构方面的潜在应用价值,为植入体表面设计提供借鉴。还结合课题组前期在等离子喷涂技术领域的相关工作,提出关于等离子喷涂技术在骨植入体表面改性方面的新思路。     

A comparative study of titanium nitrides, TiN, TiNbN and TiCN, as coatings for biomedical applications

A strategy used to reduce wear of the ultra high molecular weight polyethylene (UHMWPE) component of orthopedic joint implants has been to coat the metallic part with a hard ceramic layer. The advantage of this procedure is to reduce both wear and ion release of the metal while keeping a high mechanical resistance. In the present study, the performance of three titanium nitride coatings: TiN, TiNbN, and TiCN for biomedical applications was assessed in terms of their surface properties and cytotoxicity. The morphology, chemical composition, and wettability were determined through atomic force microscopy (AFM) imaging, X-ray photoelectron spectroscopy (XPS) and contact angle measurement, respectively. The tribological behaviour of the coatings rubbing against UHMWPE in lubricated conditions was investigated using a pin-on-disk apparatus. Albumin adsorption on the three coatings was studied with a quartz crystal microbalance with dissipation (QCM-D) and AFM scratching. Cytotoxicity was determined both in direct or indirect contact of the cells with the coating materials. The results demonstrate that the three coatings have similar surface properties and are not cytotoxic. TiNbN seems to have the best tribological performance in the presence of albumin, although albumin adsorption is slightly higher on TiN.     

Bone integration properties of antibacterial biomimetic porous titanium implants

A novel antibacterial biomimetic porous titanium implant with good osseointegration was prepared by freeze-casting and thermal oxidation. Bone integration properties of the porous titanium implant were evaluated by cell proliferation assay, alkaline phosphatase activity assay, X-ray examination and hard bone tissue biopsy. The in vitro cell proliferation and the level of differentiation of the group with a modified nano-porous implant surface were significantly higher than those in the group without surface modification and the dense titanium control group (P<0.05). In vivo, bone growth and osteogenesis were found in the experimental groups with modified and unmodified porous titanium implants; osteoblasts in the modified group had more mature differentiation in the pores compared to the unmodified group. Such implants can form solid, biologically compatible bone grafts with bone tissues, exhibiting good osseointegration.     

One-step modification of nano-hydroxyapatite coating on titanium surface by hydrothermal method

Since metallic biomaterials used for orthopedic and dental implants possess a paucity of reactive functional groups, bioactivity modification of these materials is challenging. To enhance osteoconductivity, sandblasted and acid etched titanium (SLA-Ti) discs were hydrothermally treated in simple suspension of hydroxyapatite (HA) by a one-step method in the present work. Change of surface chemistry, surface morphology of samples, and structure of formed nano-HA were investigated by X-ray photoelectron spectrometry (XPS), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray powder diffraction (XRD). The results demonstrated that the concentration of hydroxyl groups increased after hydrothermal treatment. The ability of the titanium surface to form nano-HA was enhanced by increasing the hydrothermal treatment temperature and time. The bonding strength of the formed nano-HA coating, examined by an ultrasonic cleaning process, was higher than that of HA coating generated directly by HA suspension deposition. Culturing of MC3T3-E1 cells on the SLA-Ti and HT-Ti discs in vitro showed that HT-Ti was more favorable for cell attachment and differentiation than SLA-Ti. Hence the one-step hydrothermal treatment with HA suspension was a simple, effective and promising method for HA coating modification of titanium implants.     

Novel nanostructured hydroxyapatite coating for dental and orthopedic implants

A novel hybrid coating process, combining NanoSpray® (built on electrostatic spray coating) technology with microwave sintering process, was developed for synthesizing hydroxyapatite- (HA-) based nanostructured coating with favorable properties for dental and orthopedic implants. Specifically, HA nanoparticles were deposited on commercially pure titanium substrates using NanoSpray technique to produce the HA coating, which was then sintered in a microwave furnace under controlled conditions. The study showed that the use of NanoSpray followed by microwave sintering results in nanoscale HA coating for dental/orthopedic application.     

Construction of Nanophase Novel Coatings-Based Titanium for the Enhancement of Protein Adsorption

In the recent years,biological nanostructures coatings have been incorporated into orthopedic and dental implants in order to accelerate osseointegration and reducing surgical restrictions.In the present work,chemical etching,anodization and metal doping surface modification methods were integrated in one strategy to fabricate innovative titanium surfaces denominated by titanium nanoporous,anodized titanium nanoporous,silver-anodized titanium nanoporous and gold-anodized titanium nanoporous.The stability properties of nanostructures-coated surfaces were elucidated using electrochemical impedance spectroscopy(EIS) after 7 days of immersion in simulated biological fluids.Morphology and chemical compositions of new surfaces were characterized by scanning electron microscope and energy-dispersive X-ray analysis.The EIS results and data fitting to the electrical equivalent circuit model demonstrated the influence of adsorption of bovine serum albumin on new surfaces as a function of protein concentration.Adsorption process was described by the very well-known model of the Langmuir adsorption isotherm.The thermodynamic parameter DGADS(-50 to 59 kJ mol~(-1)) is calculated,which supports the instantaneous adsorption of protein from biological fluids to new surfaces and refers to their good biocompatibility.Ultimately,this study explores new surface strategy to gain new implants as a means of improving clinical outcomes of patients undergoing orthopedic surgery.