水热处理镁离子改性改善纯钛骨传导性的研究

在200℃,0.1mol/L的MgCl₂溶液中对纯钛进行了水热处理,以期改善其生物活性。采用多种分析手段对水热处理前后试样的形貌、粗糙度、润湿性能及表面化学成分进行了分析;采用模拟体液浸泡法评价了处理前后试样的体外骨传导性。水热处理在试样表面形成了纳米氧化钛颗粒,但并没有改变试样的微米尺度的形貌,经过水热处理的试样表现出了超亲水性。水热处理成功地将Mg元素复合至钛表面;在MgCl₂溶液中进行水热处理时,Mg元素主要以钛酸镁形式存在,而在pH为9.5的MgCl₂的溶液中进行水热处理时,Mg元素主要以Mg(OH)₂形式存在。在SBF中浸泡3天后,水热处理试样表面即可观察到典型的羟基磷灰石球状晶簇,而未经处理的试样表面则未能发现沉积,此外,过高的Mg复合量抑制了羟基磷灰石的形核长大。结果表明,水热处理在保持种植体宏观形貌不受影响的前提下可作为种植体生产的最后工序以提高其骨结合性。     

Characterization of thermally oxidized Ti6Al7Nb alloy for biological applications

Wear and biological performances of a thermally oxidized Ti6Al7Nb alloy were investigated. Thermal oxidation (TO) performed at 600 °C for 60 h in air formed a 0.6 μm thick and relatively rough (having an average surface roughness of 1.1 μm) oxide layer (OL) on the surface. The OL was identified as the rutile form of TiO₂ and there was an oxygen diffusion zone (ODZ) with an average thickness of 5 μm just beneath it. The applied TO process resulted in more than ten-fold increase in wear resistance in a simulated body fluid (SBF) solution. Additionally, the biological performance was also enhanced as revealed by SBF immersion and cell culture tests.     

Sol-gel derived HA/TiO2 double coatings on Ti scaffolds for orthopaedic applications

Hydroxyapatite/titania （HA/TiO2） double layers were coated onto Ti scaffolds throughout for orthopaedic applications by sol-gel method. Differential scanning calorimetry （DSC）, thermogravimetric analysis （TG） and X-ray diffractometry （XRD） were used for the characterisation of the phase transformations of the dried gels and coated surface structures. Scanning electron microscope （SEM） equipped with energy dispersive spectrometry （EDS） was used for the observation and evaluation of the morphology and phases of the surface layers and for the assessment of the in vitro tests. The in vitro assessments were performed by soaking the HA/TiO2 double coated samples into the simulated body fluid （SBF） for various periods. The TiO2 layer was coated by a dipping-coating method at a speed of 12 cm/min, followed by a heat treatment at 600 ℃ for 20 min. The HA layer was subsequently dipping-coated on the outer surface at the same speed and then heat-treated at difference temperatures. The results indicat that the HA phase begins to crystallize after a heat treatment at 560 ℃. The crystallinity increases obviously at 760 ℃. SEM observations find no delamination or crack at the interfaces of HA/TiO2 and TiO2/Ti. The HA/TiO2 coated Ti scaffolds displays excellent bone-like apatite forming ability when it is soaked into SBF. Ti scaffolds after HA/TiO2 double coatings can be anticipated as promising implant materials for orthopaedic applications     

Corrosion behaviors of hydroxyapatite coated by electrodeposition method of Ti6Al4V, Ti and AISI 316L SS substrates

Electrodeposition method was used to obtain hydroxyapatite (HAP) coatings on Ti6Al4V, Ti and AISI 316L SS substrates. Electrodeposition solution is prepared as Ca(NO₃)₂ · 4H₂O and (NH₄)H₂PO₄. Additionally, three different pretreatment surface operations (PTSO) (HNO₃, anodic polarization, baseacid) were applied to the substrates. Surface morphology of HAP coated substrates were characterized by SEM, EDS, XRD. HAP coatings were successfully deposited on Ti6Al4V, AISI 316L SS and Ti substrates Corrosion behavior of uncoated and HAP coated substrates were examined in the Ringer and 0.9% NaCl solutions. The XRD, SEM-EDS results supported that HAP formation on the substrates. i _cor values for all three HAP coated substrates are higher than uncoated substrates This showed that, electrochemical deposition HAP coating could not prevent the corrosion. The lowest corrosion rates were founded HNO₃ PTSO substrates.     

The effect of nitric acid surface treatment on CaP deposition of Ti6Al4V open-cell foams in SBF solution

The effect of nitric acid surface treatment on CaP deposition of an open-cell Ti6Al4V foam (60% porous and 300-500 ?m in pore size), prepared by means of the space holder method using 94 and 66 μm average particle size powders, was investigated in a simulated body fluid (SBF) solution up to 14 days. Although, nitric acid surface treatment did not change the foam flat surface roughness values significantly, it increased surface area difference greatly by introducing nano scale undulations on the surface. The increased surface area difference was found to be more pronounced in smaller particle size foam samples. A continuous relatively thin CaP coating layer formed after 5 and 14 days of SBF immersion in nitric acid surface treated small and larger average particle size foam specimens, respectively. Whereas, the cells of untreated foam specimen were observed to be filled with CaP precipitates and a continuous CaP layer development was found after 14 days of SBF immersion. These results were also confirmed with the grazing incidence XRD and FTIR analysis of SBF immersed specimens.     

New generation hopeite coating on Ti6Al4V (TC4) by radio frequency magnetron sputtering for prosthetic-orthopaedic implant applications: synthesis and characterisation

ABSTRACT

Bioceramic coatings with multifunctionality have emerged as an effective alternative to conventional coatings, owing to their combination of various properties that are essential for bio-implants, such as osseointegration and antibacterial character. In the present study, thin hopeite coatings were synthesised by radio frequency magnetron sputtering on TC4 substrates. The obtained hopeite coatings were thermally treated at 500°C in ambient air and characterised in terms of surface morphology, phase composition, surface roughness, adhesion strength, antibacterial efficacy, apatite forming ability, surface wettability and corrosion resistance by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Atomic Force Microscopy(AFM), Tensometer, Fluorescence-Activated Cell Sorting (FACS), Simulated Body Fluid (SBF) immersion, Contact Angle Goniometer and potentiostatic polarisation respectively. It was observed that the post-deposition annealing increases the crystallinity of the synthesised hopeite coatings. SEM analysis showed deposited particles are spherical in shape and small in dimensions (<1?μm in diameter). XRD results confirm the deposited coating is crystalline in nature. AFM analysis reveals deposited hopeite coating has an average surface roughness value of 8.66?nm. Tensile pullout experiments indicated that the adhesive strength of the hopeite coating is 21.75?±?2.1?MPa. FACS study confirms the deposited hopeite coating possesses antibacterial character. SBF immersion experiments clearly demonstrate apatite growth on the surface of the deposited hopeite coating. The surface wettability test showed that the deposited coatings are hydrophobic in character having an average contact angle value of 136.65°. Potentiodynamic polarisation experiments in SBF showed a significant improvement in corrosion resistance (R_p?=?7945.87?Ω?cm²) of hopeite coated samples. In summary, it can be concluded that the new generation multifunctional hopeite coating synthesised by an alternative new process route of radio frequency magnetron sputtering on TC4 substrates is an effective alternative to conventional coatings. This is largely attributed to the strong osseointegration and antibacterial character of deposited hopeite coating ensuring the overall stability of metallic orthopaedic implants.     

Influence of Alkali Treatment on Ti6Al4V Alloy and the HA Coating Deposited by Hydrothermal-Electrochemical Methods

Ti6Al4V基体经NaOH溶液恒温预处理不同的时间(12、24、36、48、60 h),然后分析了不同的碱预处理时间对Ti6Al4V基体及羟基磷灰石(HA)形态、物相的影响。经碱预处理后Ti6Al4V表面呈现三维网状结构,并检测到了钛酸钠凝胶的存在。随后采用水热电化学方法得到了HA涂层,水热反应电解质包括NaCl、K2HPO4·3H2O、CaCl2,在恒温120℃、电流密度为1.25 mA/cm2的条件下保持120 min。结果表明:HA的生长模式及形态均受预处理时间的影响:当基体经过12 h的预处理后,水热反应形成一层针状HA及少量蒲公英状HA。而蒲公英状HA的数量随预处理时间的增加而增多。但预处理时间大于48 h时,其数量稍有减小。HA在(002)晶面的取向指数、结晶度在预处理时间为48 h时分别达到了最小值、最大值。     

Effect of fluoride added artificial saliva solution on orthodontic wires

In this study, effect of fluoride added artificial saliva solution on NiTi and β-Ti alloys used for orthodontic wires was investigated. The orthodontic wires were immersed into fluoride added artificial saliva solution of pH 4.8 at 37°C. The characterization of metal surfaces after ten days of immersion was carried out using scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS). It is concluded that fluoride has an important effect on corrosion behavior of experimental wires that can be described as a type of wear. EDS analysis denotes the existence of a thin oxide film layer in addition to the Ti based oxide one on the surface of the metals.     

Effects of Duplex Nitriding and TiN Coating Treatment on Wear Resistance,Corrosion Resistance and Biocompatibility of Ti6Al4V Alloy

Ti6Al4V alloy substrates were nitrided at 900 °C. TiN coatings were then deposited on the nitrided substrates using a closed-field unbalanced magnetron sputtering system. The microstructure, hardness and adhesion properties of the TiN-N-Ti6Al4V substrates were evaluated and compared with those of an untreated Ti6Al4V sample, a nitrided Ti6Al4V sample and a TiN-coated Ti6Al4V sample, respectively. The tribological properties of the various samples were investigated by means of reciprocating sliding wear tests performed in 0.9 wt.% NaCl solution against 316L, Si₃N₄ and Ti6Al4V balls, respectively. In addition, the corrosion resistance was evaluated using potentiodynamic polarization tests. Finally, the biocompatibility of the samples was investigated by observing the attachment and growth of purified mouse leukemic monocyte/macrophage cells (Raw 264.7) on the sample surface after culturing periods of 24, 72 and 120 h, respectively. Overall, the results showed that the duplex nitriding/TiN coating treatment significantly improved the tribological, anti-corrosion and biocompatibility properties of the original Ti6Al4V alloy.     

多孔钛表面TiO2纳米管的阳极氧化制备及光催化性能（英文）

对多孔钛表面制备TiO2纳米管的阳极氧化工艺进行研究。在两种电解质溶液中采用阳极氧化法分别对多孔钛和钛箔进行表面处理。一种电解质溶液是含有0.5%HF的冰醋酸,另一种电解质溶液是含有0.5%NH4F(质量分数)的乙二醇溶液(醇水体积比4:1)。结果表明:两种方法在钛箔上都可以生成TiO2纳米管,而多孔钛表面只能在NH4F电解质溶液中生成纳米管,HF溶液中过高的电流密度是纳米管在多孔钛基体上难以生成的主要原因。采用扫描电子显微镜和X射线衍射仪对不同基体上的TiO2纳米管进行表征,相比钛箔基体上的纳米管管壁,多孔钛上的纳米管管壁更薄。对所制备的TiO2热处理研究表明,锐钛矿相在400°C时形成,并在700°C完全转变为金红石相。经450°C热处理样品的光催化性能最好。光催化性能也受到多孔钛孔隙率的影响,在孔隙率为60%时光催化性能最好。     

Development of 70/30 Poly-L-DL-Lactic Acid Filaments for 3D Printers (Part 2): Mechanical and Surface Properties of Bioabsorbable Printed Plates for Biomedical Applications

The mechanical, chemical, roughness and wettability properties of 70/30 poly (L,DL-lactide acid) three-dimensional (3D)-printed surgical plates made with extruded polymer filaments developed in the first part of this work were investigated. The plates were printed with horizontal (HRZ) and vertical (VRT) running layer orientations and evaluated by tensile, Fourier transform infrared (FTIR), optical perfilometry and wettability tests before and after degradation in simulated body fluid (SBF) for 21 days. The results show that the ultimate tensile strength (UTS) of HRZ plates before immersion in SBF was higher (34.1 MPa) than that of VRT plates (31.8 MPa). The Young’s modulus (E) of HRZ plates and VRT plates are similar (4 GPa). After immersion in SBF, the UTS of HRZ plates dropped to 20.5 MPa and E decreased to 3.3 GPa. VRT were not tested after SBF immersion due to the large degradation. FTIR analysis showed no evidence of chemical change in the plates after immersion in SBF. The roughness parameter R3z of VRT surfaces (19.54 µm) was higher than that of the HRZ surfaces (12.80 µm). The roughness parameters increased after degradation in SBF (p = 0.7048). The contact angles of HRZ surfaces before immersion in SBF (66.28°) were higher than after immersion in SBF (18.12°); the same behavior was also observed in VRT plates.     

Improved electromigration reliability of surface acoustic wave devices using Ti/Al-Mo/Ti/Al-Mo electrodes

In order to obtain both high electromigration (EM) reliability and fine-dimensional control in high-frequency surface acoustic wave (SAW) devices, 4-layered Ti/Al-Mo/Ti/Al-Mo electrode films were investigated on 128° Y-X LiNbO₃ substrates by sputtering deposition. The results indicated that the 4-layered films had an improved EM reliability compared to conventional Al-0.5wt.%Cu films. Their lifetime is approximately three times longer than that of the Al-0.5wt.%Cu films tested at a current density of 5 × 10⁷ A/cm² and a temperature of 200°C. Moreover, the 4-layered films were easily etched in reactive ion etching and fine-dimensional control was realized during the pattern replication for high-frequency SAW devices. For the 4-layered films, an optimum Mo quantity and sputtering parameters were very significant for high EM reliability.     

Fabrication of Mesoporous Hydroxycarbonate Apatite/Polyaniline Composite Coatings on Ti6Al4V Substrates

采用电泳沉积法在 Ti6Al4V 基体上形成碳酸钙/聚苯胺复合涂层,然后经磷酸缓冲溶液 37 ℃下浸泡处理得到介孔碳酸根型羟基磷灰石/聚苯胺复合涂层。无裂纹的碳酸钙/聚苯胺复合涂层通过溶解-沉积反应转化成具有片状结构的碳酸根型羟基磷灰石/聚苯胺复合涂层,介孔和大孔分别存在于片状磷灰石内部和之间。模拟体液浸泡实验表明,多孔结构可以提高涂层的体外磷灰石形成活性,类骨型磷灰石首先沉积在介孔上,然后随着浸泡时间的延长逐渐覆盖所有大孔。此外,碳酸根型羟基磷灰石/聚苯胺复合涂层的体外磷灰石形成活性与聚苯胺纳米线有关,聚苯胺上的官能团(H2PO4-)不仅可以提高局部过饱和度,而且可以促进类骨型磷灰石的形核和生长。     

Corrosion behavior of polypyrrole/hydroxyapatite nanocomposite thin films electropolymerized on NiTi substrates in simulated body fluid

Hydroxyapatite (HAp) nanoparticles synthesized via microwave irradiation. Polypyrrole (PPy)/HAp nanocomposite was obtained using electropolymerization on nitinol (Ni) titanium (Ti) substrates. Fourier transform infrared was employed to characterize the nanocomposite formation. Electrochemical properties of the nanocomposite were investigated using polarization and electrochemical impedance spectroscopy (EIS) in simulated body fluid (SBF, 37 ± 0.1 °C). It was concluded that the NiTi specimen coated with PPy/HAp nanocomposite, has higher corrosion resistance than the NiTi coated with pure PPy in the SBF; however, NiTi was better than both coated NiTi. EIS results confirmed corrosion properties. Also, EIS was used to predict the morphology of the coatings. It predicted fine and compact morphology of the nanocomposite that was confirmed using scanning electron microscopy.     

The examination of corrosion behaviors of hap coated Ti implant materials and 316L SS by sol-gel method

In this research, hydroxyapatite (HAP) coatings have been produced on Ti, Ti6Al4V alloy and 316L stainless steel substrates by sol-gel method. (NH₄) · H₂PO₄ is taken as P precursor and Ca(NO₃)₂ · 4H₂O is taken as Ca precursor to obtain HAP coating. Additionally, three different pretreatment processes (HNO₃, anodic polarization, base-acide (BA)) have been applied to Ti, Ti6Al4V alloy and 316L stainless steel substrates. The corrosion behaviors of bare and HAP coated samples are examined in Ringer and 0.9% NaCl. HAP coated Ti have showed over 87.85% inhibition. HAP coated Ti6Al4V alloys have showed over 87.33% inhibition. In Ringer solution, 99.24% inhibition has been showed in HAP coated anodic pretreatment for 316L stainless steel. All pretreatment processes are effective on clinging of HAP coating to the surface. It is seen that impedance values have increased in HAP coatings (Ti and Ti6Al4V). HAP coatings have raised the corrosion resistance of Ti and Ti6Al4V. The values of polarization resistance in HAP coated samples have increased for 316L stainless steel in 0.9% NaCl and Ringer solutions. It is seen in SEM images that open pores and attachments among pores have been observed in the coating, which increases osteointegration. It is noted in EDX analyses of the surfaces of the HAP coated samples that there is only Ca, O, and P on the surface. Ca/P ratio varies in 1.84–2.00 ranges. As Ca/P ratio increases, the inhibition increases too. It is seen in XRD images of HAP powder that there are HA ate structures. Additionally, it is seen in FTIR analysis, characteristic HA absorption bands have occurred in sintered powders.     

Effect of Ti content and nitrogen on the high-temperature oxidation behavior of (Mo,Ti)5Si3

The binary intermetallic compounds Mo₅Si₃ (T1) and Ti₅Si₃ are prone to rapid oxidation below 1000 °C. Recent investigations on (Mo,Ti)₅Si₃, however, revealed that macro-alloying with 40 at.% Ti can result in a very good oxidation resistance in a wide temperature range (750–1300 °C) due to the formation of a duplex layer composed of a silica matrix with dispersed titania. Additionally, Ti decreases density making (Mo,Ti)₅Si₃ a promising key constituent of quaternary Mo-Si-B-Ti alloys considered for ultrahigh temperature structural applications. The aim of this study is to obtain an in-depth understanding of the influence of different Ti concentrations as well as of nitrogen on the oxidation behavior of (Mo,Ti)₅Si₃ at intermediate and elevated temperatures. The microstructure and oxidation mechanisms were analyzed using various experimental techniques. The experimental results were supported by ab initio and thermodynamic calculations.     

Ferroelectric properties of dysprosium-doped Bi4Ti3O12 thin films crystallized in various atmospheres

Dysprosium-doped Bi4Ti3O12 （Bi3.4Dy0.6Ti3O12, BDT） ferroelectric thin films were deposited on Pt（111）/Ti/SiO2/Si（111） substrates by chemical solution deposition （CSD） and crystallized in nitrogen, air and oxygen atmospheres, respectively. X-ray diffraction （XRD） and scanning electron microscopy （SEM） were used to identify the crystal structure, the surface and cross-section morphology of the deposited ferroelectric films. The results show that the crystallization atmosphere has significant effect on determining the crystallization and ferroelectric properties of the BDT films. The film crystallized in nitrogen at a relatively low temperature of 650 ℃, exhibits excellent crystallinity and ferroelectricity with a remanent polarization of 2Pr = 24.9 ℃/cm^2 and a coercive field of 144.5 kV/cm. While the films annealed in air and oxygen at 650 ℃ do not show good crystallinity and ferroelectricity until they are annealed at 700 ℃. The structure evolution and ferroelectric properties of BDT thin films annealed under different temperatures （600-750 ℃） were also investigated. The crystallinity of the BDT films is improved and the average grain size increases when the annealing temperature increases from 600 ℃ to 750 ℃ at an interval of 50 ℃. However, the polarization of the films is not monotonous function of the annealing temperature.     

Brazing of TiBw/TC4 composite and Ti60 alloy using TiZrNiCu amorphous filler alloy

TiB_w/TC4 composite was brazed to Ti60 alloy successfully using TiZrNiCu amorphous filler alloy, and the interfacial microstructures and mechanical properties were characterized by SEM, EDX, XRD and universal tensile testing machine. The typical interfacial microstructure was TiB_w/TC4 composite/β-Ti + TiB whiskers/(Ti, Zr)₂(Ni, Cu) intermetallic layer/β-Ti/Ti60 alloy when being brazed at 940 °C for 10 min. The interfacial microstructure evolution was influenced strongly by the diffusion and reaction between molten fillers and the substrates. Increasing brazing temperature decreased the thickness of brittle (Ti, Zr)₂(Ni, Cu) intermetallic layer, which disappeared finally when the brazing temperature exceeded 1020 °C. Fracture analyses indicated that cracks were initialized in the brittle intermetallic layer when (Ti, Zr)₂(Ni, Cu) phase existed in the brazing seam. The maximum average shear strength of joints reached 368.6 MPa when brazing was conducted at 1020 °C. Further increasing brazing temperature to 1060 °C, the shear strength was decreased due to the formation of coarse lamellar (α+β)-Ti structure.     

纯钛TIG焊接接头的高温氧化行为

对纯钛氩弧焊焊接接头在550 ℃下氧化不同时间（2,4,6,8 h）以及在不同温度（650,750,850,950 ℃）下氧化4 h的氧化动力学、氧化形态和氧化产物进行了研究。结果表明,在550 ℃下,氧化时间对焊接接头氧化行为的影响有限,而氧化温度对纯钛焊接接头的氧化行为有显著影响,且温度越高,氧化越严重。在低温下,纯钛焊接接头的氧化动力学接近准线性定律,随着温度升高,氧化速率呈指数增长。此外,焊接接头表面产生的氧化产物是具有锐钛矿和金红石结构的TiO₂,温度对TiO₂的类型没有明显影响。纯钛焊接接头的氧化过程可描述为：氧气在表面被吸收;氧化物优先在缺陷区形核;氧化物横向生长、增厚。在较高温度下,氧化膜中出现裂纹或空隙,成为O原子传输通道,导致O和Ti原子的高扩散速率和氧化速率。     

以Ti6Al4V为基体制备介孔碳酸根型羟基磷灰石/聚苯胺复合涂层

采用电泳沉积法在Ti6Al4V基体上形成碳酸钙/聚苯胺复合涂层,然后经磷酸缓冲溶液37℃下浸泡处理得到介孔碳酸根型羟基磷灰石/聚苯胺复合涂层.无裂纹的碳酸钙/聚苯胺复合涂层通过溶解-沉积反应转化成具有片状结构的碳酸根型羟基磷灰石/聚苯胺复合涂层,介孔和大孔分别存在于片状磷灰石内部和之间.模拟体液浸泡实验表明,多孔结构可以提高涂层的体外磷灰石形成活性,类骨型磷灰石首先沉积在介孔上,然后随着浸泡时间的延长逐渐覆盖所有大孔.此外,碳酸根型羟基磷灰石/聚苯胺复合涂层的体外磷灰石形成活性与聚苯胺纳米线有关,聚苯胺上的官能团( H2PO4)不仅可以提高局部过饱和度,而且可以促进类骨型磷灰石的形核和生长.