Preparation of Titanium Oxide-containing Organic Film by Dipping Ti(OR)4 and Cold Plasma oxidizing on PET

Low temperature process to prepare titanium oxide film on the surface of PET was investigated in this study. The substrates were pre-treated by oxygen plasma activated procedure, and then spin coating of Ti(OR)₄ precursor solution was carried out to prepare Ti-containing organic films. Finally, O₂ plasma was employed to decompose organic compounds and oxidize Ti to form oxides. Oxygen plasma post treatment can oxidize the organic compounds to form titanium oxide carbon subsequently. From the IR and ESCA analysis could be observed that -CH bond decreases and Ti-O, C-O bonds increase after O₂ plasma treatment. Their surface hydrophilicity was enhanced by UV-irradiation, the degree of water contact angle decreased from 60° to 10°.     

锰和氟共修饰羟基磷灰石陶瓷涂层的制备与表征

由于钛及钛合金具有优越的理化性能,其已被广泛应用于各种植入体,例如骨科、牙科及心血管支架等。然而,钛基材表面具有生物惰性,其与周边骨组织形成骨整合的能力较弱,延缓了组织愈合的时间。因此,改善钛植入体表面生物性能具有重要的临床意义。钛基材表面羟基磷灰石(HAP)复合涂层的制备已成为一种重要的表面生物活性改良手段。在含有F-,Mn2+,Ca2+和PO3-₄的电解液中,用单电流阶跃沉积法,在钛金属(Ti)表面上涂覆锰和氟共修饰羟基磷灰石(FMnHAP)复合薄膜。采用扫描电子显微镜(SEM)、能量弥散X射线谱(EDS)、X-射线衍射(XRD)对涂层进行初步表征,用傅里叶变换红外光谱(FTIR)技术验证了氟离子和锰离子的共修饰对HAP分子构象和生物活性的影响。结果表明：锰部分取代磷灰石中的钙,氟部分取代磷灰石中的羟基,FMnHAP晶格常数变小,薄膜表面形貌由微米级的针状变为纳米级的绒毛状。FTIR技术验证显示,由于磷灰石晶体结构中F取代部分OH,致使改变了结构中OH的弯曲振动模式的对称性;模拟体液体外矿化表明,涂层表面有含碳酸根的类骨磷灰石形成,则涂层的体外生物活性较好。极化曲线测试表明,涂层提高了Ti在生理环境中的耐腐蚀性。     

X射线显微CT用于大鼠骨小梁结构分析的研究

应用X射线显微CT(X-μCT)对正常及骨质疏松大鼠的骨小梁结构进行了分析,并与骨组织形态计量法的测量值进行了比较,探讨了X射线光谱技术在骨结构分析中的应用。实验对大鼠骨样品进行X-μCT扫描,扫描条件为 80 kVp,80 μA,360°旋转,帧平均4帧,角度增益 0.4°,分辨率14 μm。三维重建并分析了骨小梁结构,结构参数包括骨体积分数(BV/TV)、骨小梁厚度(Tb.Th)、骨小梁数量(Tb.N)以及骨小梁间隔(Tb.Sp)。结果表明,采用X-μCT分析不同组大鼠的骨小梁结构参数值之间存在显著差异(P<0.05),测定值与传统骨组织形态计量法的测定值显著相关,其中胫骨骨小梁BV/TV,Tb.Th,Tb.N,Tb.Sp的相关系数r分别为0.984,0.960,0.995,0.988,腰椎骨小梁各结构参数的相关系数分别为0.938,0.968,0.877,0.951。因此,X-μCT可以较好地呈现并区分正常骨组织、骨质疏松骨组织以及经雌激素治疗后骨组织的微观结构,可以实现对骨小梁结构参数的分析测定,与骨组织形态计量法相比是一种更精确、立体、快速且无损测量骨微结构和评价骨质量的方法。     

Deposition of titanium nitride and hydroxyapatite-based biocompatible composite by reactive plasma spraying

Titanium nitride is a bioceramic material successfully used for covering medical implants due to the high hardness meaning good wear resistance. Hydroxyapatite is a bioactive ceramic that contributes to the restoration of bone tissue, which together with titanium nitride may contribute to obtaining a superior composite in terms of mechanical and bone tissue interaction matters.The paper presents the experimental results in obtaining composite layers of titanium nitride and hydroxyapatite by reactive plasma spraying in ambient atmosphere. X-ray diffraction analysis shows that in both cases of powders mixtures used (10% HA + 90% Ti; 25% HA + 75% Ti), hydroxyapatite decomposition occurred; in variant 1 the decomposition is higher compared with the second variant. Microstructure of the deposited layers was investigated using scanning electron microscope, the surfaces presenting a lamellar morphology without defects such as cracks or microcracks. Surface roughness values obtained vary as function of the spraying distance, presenting higher values at lower thermal spraying distances.     

Reproducibility of the quantitative assessment of cartilage morphology and trabecular bone structure with magnetic resonance imaging at 7 T

To assess the reproducibility of quantitative measurements of cartilage morphology and trabecular bone structure of the knee at 7 T, high-resolution sagittal spoiled gradient-echo images and high-resolution axial fully refocused steady-state free-precession (SSFP) images from six healthy volunteers were acquired with a 7-T scanner. The subjects were repositioned between repeated scans to test the reproducibility of the measurements. The reproducibility of each measurement was evaluated using the coefficient(s) of variation (CV). The computed CV were 1.13% and 1.55% for cartilage thickness and cartilage volume, respectively, and were 2.86%, 1.07%, 2.27% and 3.30% for apparent bone volume over total volume fraction (app.BV/TV), apparent trabecular number (app.Tb.N), apparent trabecular separation (app.Tb.Sp) and apparent trabecular thickness (app.Tb.Th), respectively. The results demonstrate that quantitative assessment of cartilage morphology and trabecular bone structure is reproducible at 7 T and motivates future musculoskeletal applications seeking the high-field strength's superior signal-to-noise ratio.     

Surface characterisation and electrochemical behaviour of porous titanium dioxide coated 316L stainless steel for orthopaedic applications

Porous titanium dioxide was coated on surgical grade 316L stainless steel (SS) and its role on the corrosion protection and enhanced biocompatibility of the materials was studied. X-ray diffraction analysis (XRD), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) were carried out to characterise the surface morphology and also to understand the structure of the as synthesised coating on the substrates. The corrosion behaviour of titanium dioxide coated samples in simulated body fluid was evaluated using polarisation and impedance spectroscopy studies. The results reveal that the titanium dioxide coated 316L SS exhibit a higher corrosion resistance than the uncoated 316L SS. The titanium dioxide coated surface is porous, uniform and also it acts as a barrier layer to metallic substrate and the porous titanium dioxide coating induces the formation of hydroxyapatite layer on the metal surface.     

Surface modification of Ti dental implants by Nd:YVO4 laser irradiation

Surface modifications have been applied in endosteal bone devices in order to improve the osseointegration through direct contact between neoformed bone and the implant without an intervening soft tissue layer. Surface characteristics of titanium implants have been modified by addictive methods, such as metallic titanium, titanium oxide and hydroxyapatite powder plasma spray, as well as by subtractive methods, such as acid etching, acid etching associated with sandblasting by either AlO₂ or TiO₂, and recently by laser ablation. Surface modification for dental and medical implants can be obtained by using laser irradiation technique where its parameters like repetition rate, pulse energy, scanning speed and fluency must be taken into accounting to the appropriate surface topography. Surfaces of commercially pure Ti (cpTi) were modified by laser Nd:YVO₄ in nine different parameters configurations, all under normal atmosphere. The samples were characterized by SEM and XRD refined by Rietveld method. The crystalline phases αTi, βTi, Ti₆O, Ti₃O and TiO were formed by the melting and fast cooling processes during irradiation. The resulting phases on the irradiated surface were correlated with the laser beam parameters. The aim of the present work was to control titanium oxides formations in order to improve implants osseointegration by using a laser irradiation technique which is of great importance to biomaterial devices due to being a clean and reproducible process.     

Effects of risedronate in a rat model of osteopenia due to orchidectomy and disuse: densitometric, histomorphometric and microtomographic studies

Dual energy X-ray absorptiometry (DXA), histomorphometry and X-ray microtomography (microCT) were used to assess effects of risedronate and testosterone in a combined rat model of orchidectomy (ORX) and local paralysis induced by botulinum neurotoxin (BTX). Four groups of mature rats were studied for 1 month: SHAM operated; ORX and right hindlimb immobilization (BTX); ORX+BTX+risedronate or testosterone. Changes in bone and body composition were measured by DXA (BMC, lean and fat mass), histomorphometry (BV/TV(2D), Tb.Th and microarchitectural parameters) and microCT (BV/TV(3D), SMI and cortical parameters). ORX and BTX had additive effects on bone loss since differences were maximized on the immobilized bone. The decrease in BMC on the tibial metaphysis reached -33.6% vs. -11.3% in the non-immobilized limb. BV/TV and Tb.N decreased and Tb.Sp increased in both hindlimbs whereas Tb.Th was significantly lower only in the immobilized limb. Decrease of tibial cortical area and thickness was greater in the immobilized limb. Risedronate prevented BMC, BV/TV and architecture loss but not reduction in Tb.Th. Cortical bone was preserved only in the non-immobilized limb. Testosterone was unable to prevent trabecular and cortical bone loss, but it prevents loss of whole body lean mass. In conclusion, ORX and BTX resulted in additive effects on bone loss. Risedronate had protective effects on trabecular bone loss but was less effective on cortical bone.     

Surface state of TiO2 treated with low ion energy plasma

The effect of low pressure radio frequency (rf) plasma treatment on TiO₂ surface states has been studied using X-ray photoelectron spectroscopy. Three different oxidation states of oxygen in untreated TiO₂ powder were observed, which suggests the existence of adsorbed water and carbon on the surface. The ratio of oxygen to titanium (O/Ti) was decreased for the low ion dose plasma treated samples due to desorption of water from the surface. In the case of Ti 2p about 20% of surface states were converted to Ti³⁺ 2p_3/2 state after plasma treatment with a very good stability, whereas untreated TiO₂ remained mostly as Ti⁴⁺ state. A rapid decrease in the ratio of carbon to titanium (C/Ti) at TiO₂ surface was also observed after plasma treatment and more than 90% of carbon atoms were removed from the surface. Therefore, the plasma treatment of TiO₂ has advantages to surface carbon cleaning, increasing O⁻ and Ti³⁺ surface states, hence improving the activity of TiO₂ for different environmental, energy and biological applications.     

Short-TE projection reconstruction NMR microscopy of trabecular bone.

The aim of this study was to assess the potential of projection reconstruction (PR) NMR microscopy in the quantitative evaluation of trabecular bone architecture. Short-TE PR spin-echo microimages were acquired at 7.05 T on normal bone explants. The main structural parameters such as bone volume fraction (BVF), trabecular thickness (Tb.Th.) and trabecular separation (Tb.Sp.) were obtained from the 3D microimages using the method of directed secants. Quantitative structural data were then compared with those derived from conventional spin-echo microimages. Our study indicates that projection reconstruction NMR microscopy promises to be more accurate than the conventional FTI method in the analysis of trabecular bone.     

Biological fixation of endosseous implants

Primary implant stability is ensured by a mechanical fixation of implants. However, during implant healing a biological anchorage is necessary to achieve final osseointegration.

Aim of this study was to investigate the histological aspects of biological fixation around titanium screws.

Forty-eight titanium screws with different surfaces (smooth, plasma sprayed, sand blasted) were inserted in tibiae and femura of sheep and analyzed by light microscope and SEM 1 hour, 14 and 90 days after implantation.

One hour after implantation the implant-bone gap was filled with a blood clot and host bone chips arising from burr surgical preparation or friction during implant insertion. Fourteen days after implantation new trabecular bone and enveloped bone chips were observed in the gap: no osteogenesis developed where implant threads were in contact with host bone. Ninety days after surgery all trabecular bone and most of the bone chips were substituted by a mature lamellar bone with few marrow spaces.

Our results suggest that the trabecular bone and bone chips represent a three-dimensional network ensuring a biological implant fixation in all different implant surfaces 2 weeks after surgery. Host bone chips could favour the peri-implant osteogenesis. Inter-trabecular and implant-trabecular marrow spaces of both trabecular and lamellar bone may favour the peri-implant bone turnover.     

The effects of non-thermal atmospheric pressure plasma jet on cellular activity at SLA-treated titanium surfaces

Titanium (Ti) is a primary material used for dental implants, and the sandblasted, large-grit, and acid-etched (SLA) surface treatment is commonly used on titanium to promote early osseointegration. Despite their benefits, SLA-treated Ti surfaces are disadvantaged by their hydrophobic property, and much research has been performed to address this problem. In current study, we hypothesized the effects of a nitrogen-based non-thermal atmospheric pressure plasma jet (NTAPPJ) treatment on SLA-treated Ti would increase hydrophilicity and cellular activity. Samples with and without the NTAPPJ treatment were analyzed using a field emission scanning electron microscope, optical surface roughness system, X-ray photoelectron spectroscope, and water contact angle measuring system. MC3T3-E1 cells (murine osteoblastic cell line) attachments and proliferations were examined by the MTT and BrdU colorimetry assay. Cell immunofluorescent microscopic images were observed by a confocal laser scanning microscope for a morphological analysis. This study found that the nitrogen-based NTAPPJ treatment on SLA-treated Ti significantly increased the hydrophilicity and MC3T3-E1 cell attachments and proliferations. Hence, it was concluded that an additional procedure of nitrogen-based NTAPPJ treatment just prior to implantation of SLA-treated Ti into oral defect sites could improve the success of dental implant surgery.     

Synthesis of composite calcium-phosphate coatings via pulsed photon processing

The phase composition and mechanical properties of coatings generated on a Ti surface via the ion sputtering of a hydroxyapatite (HA) target and a compound (hydroxyapatite and Ti) target with subsequent pulsed photon processing (PPP) with incoherent xenon lamp radiation are investigated. It is found for the first time that pulsed photon processing accelerates the crystallization of amorphous films of Ca–P–O–H and Ca–P–O–H–Ti compositions, during which tricalcium phosphate Ca₃(PO₄)₂, titanium oxide TiO₂ (rutile, anatas), and perovskite CaTiO₃ are formed, depending on the radiation dose and the ratio between Ti and Ca phases (Ti/Ca) with hydroxyapatite structure. It is found that pulsed photon processing of initial amorphous coatings greatly increases their hardness (up to 10.9 GPa) and adhesion (up to 29.0 MPa).     

Ti/Ti-类金刚石多层膜的制备与表征

采用电子回旋共振-化学气相沉积结合中频磁控溅射的真空镀膜技术, 以99.99%Ti为靶材, 乙炔为碳源制备了Ti/Ti-类金刚石(DLC)多层膜. 利用X射线衍射仪、扫描电子显微镜、X射线光电子能谱仪 对Ti/Ti-DLC多层膜进行了相结构、组织、成分及形态分析. 采用显微硬度仪、摩擦磨损仪、表面粗糙度仪对Ti/Ti-DLC多层膜进行了力学性能考察. 结果表明: Ti/Ti-DLC多层膜中主要含有TiC晶相; Ti层和Ti-DLC层中未出现柱状晶体生长模式, 分层中均以岛状模式生长; 当调制周期Λ≤ 50 nm时, 分层结构变模糊; 调制周期Λ对Ti/Ti-DLC多层膜的复合硬度、摩擦系数、表面形貌、表面粗糙度都有影响, 当调制周期Λ较小时表现出纳米增硬效应, 表面出现大颗粒, 表面粗糙度和摩擦系数均变大.     

Improved biological performance of low modulus Ti-24Nb-4Zr-7.9Sn implants due to surface modification by anodic oxidation

Dental implants are usually made from commercially pure titanium or titanium alloys. The purpose of this study was to evaluate the influence of surface treatment to low modulus Ti-24Nb-4Zr-7.9Sn (TNZS) on cell and bone responses. The TNZS alloy samples were modified using anodic oxidation (AD). Surface oxide properties were characterized by using various surface analytic techniques, involving scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS), X-ray diffractometry (XRD) and surface profilometer. During the AD treatment, porous titanium oxide layer was formed and Ca ions were incorporated into the oxide layer. The viability and morphology of osteoblasts on Ca-incorporated TNZS were studied. The bone responses of Ca-incorporated TNZS were evaluated by pull-out tests and morphological analysis after implantation in rabbit tibiae. The non-treated Ti and TNZS samples were used as the control. Significant increases in cell viability and pull-out forces (p < 0.05) were observed for Ca-incorporated TNZS implants compared with those for the control groups. Porous structures supplied positive guidance cues for osteoblasts to attach. The enhanced cell and bone responses to Ca-incorporated TNZS implants could be explained by the surface chemistry and microtopography.     

原位DRIFTS研究CH4部分氧化和CO2重整的耦合

8%Ru-5?/γ-Al2O3催化剂对于甲烷的低温活化具有较好的催化活性,在500℃下甲烷、二氧化碳和氧气的耦合反应中,吸热反应二氧化碳重整和放热反应甲烷部分氧化进行耦合强化,使得耦合反应中的甲烷转化率为38.8%。用原位漫反射傅里叶红外光谱法对钌系催化剂耦合甲烷部分氧化和二氧化碳重整反应体系机理进行研究。CO在8%Ru-5?/γ-Al2O3上吸附,表明CO在催化剂表面上波数为2 167 cm-1(2 118 cm-1)和2031 cm-1(2 034 cm-1)处形成孪生态Ru(CO)2和Ce(CO)2吸附物种,而且高温下CO吸附物种很容易从催化剂表面脱附出来。原位漫反射红外实验结果表明甲烷部分氧化反应时催化剂表面上有吸附物种碳酸根、甲酰基(甲酸盐)和一氧化碳的形成,其中表面的甲酰基和甲酸盐物种是甲烷部分氧化反应的主要活性中间物,这些中间活性中间体由甲烷吸附态CHx和催化剂表面的氧吸附态结合而形成的,随后这种中间物种再分解为CO产物;甲烷和二氧化碳重整反应时没有新的吸附物种产生,由此提出重整反应的机理是吸附态的甲烷和二氧化碳在催化剂活性中心上进行活化解离而生成合成气;甲烷、二氧化碳和氧气耦合反应过程中出现新的羟基物种(桥式羟基Ru-(OH)2),耦合反应机理复杂可能是由部分氧化和重整两类反应机理的复合,其中桥式羟基Ru-(OH)2参与了反应的进行。     

Characterization of bioactive RGD peptide immobilized onto poly(acrylic acid) thin films by plasma polymerization

Plasma surface modification can be used to improve the surface properties of commercial pure Ti by creating functional groups to produce bioactive materials with different surface topography. In this study, a titanium surface was modified with acrylic acid (AA) using a plasma treatment and immobilized with bioactive arginine-glycine-aspartic acid (RGD) peptide, which may accelerate the tissue integration of bone implants. Both terminals containing the -NH₂ of RGD peptide sequence and -COOH of poly(acrylic acid) (PAA) thin film were combined with a covalent bond in the presence of 1-ethyl-3-3-dimethylaminopropyl carbodiimide (EDC). The chemical structure and morphology of AA film and RGD immobilized surface were investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), atomic force microscopy (AFM), and scanning electron microscopy (SEM). All chemical analysis showed full coverage of the Ti substrate with the PAA thin film containing COOH groups and the RGD peptide. The MC3T3-E1 cells were cultured on each specimen, and the cell alkaline phosphatase (ALP) activity were examined. The surface-immobilized RGD peptide has a significantly increased the ALP activity of MC3T3-E1 cells. These results suggest that the RGD peptide immobilization on the titanium surface has an effect on osteoblastic differentiation of MC3T3-E1 cells and potential use in osteo-conductive bone implants.     

Formation of the Si/Ti interface

The formation of the Si/Ti interface during the deposition of silicon on titanium polycrystalline substrates has been studied at room temperature (RT) using X-ray photoelectron spectroscopy (XPS), angle-resolved XPS (ARXPS), ultraviolet photoelectron spectroscopy (UPS) and ion scattering spectroscopy (ISS). The experimental results are consistent with a two-stage mechanism for Si growth: a first stage characterized by the simultaneous formation of a uniform titanium silicide layer, that reaches a limiting thickness of ∼3 monolayer (ML), and pure silicon islands 1 ML thick that grow on top of this layer up to coalescence, followed by a second stage in which pure silicon islands, with an average thickness of 9 ML, grow on top of the uniform titanium silicide layer + pure silicon ML structure formed during the first stage. As a whole, pure silicon species grows according to a Stranski-Krastanov mechanism, where the first ML is formed during the first stage and the islands during the second stage. The comparison of Ti/Si and Si/Ti interfaces shows that the structure and composition of the interface do not depend substantially on the deposition sequence, suggesting that the bulk chemistry of the compound formed at the interface dominates over the surface kinetics and the bulk substrate chemistry in determining the composition and structure of the interface.     

Studies by imaging TOF-SIMS of bone mineralization on porous titanium implants after 1 week in bone

Anodic oxidation was used to grow porous layers on titanium discs. Six different oxidation procedures were used producing six different surfaces. The implants were inserted in rat bone (tibia) for 7 days. After implant retrieval, mineralization (hydroxyapatite formation) on the implant surfaces was investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Bone tissue around the implants was sectioned and stained. The amount of bone in close apposition to the implant was calculated. The porosity showed great variation between the surfaces. Hydroxyapatite was detected on all surfaces. A slight positive correlation between porosity and mineralization was found, although the most porous surface was not the best mineralized one. Bone had formed around all implants after 7 days. The bone-to-metal contact for the porous implants did not differ significantly from the non-porous control. Porosity is known to influence cellular events. The results indicate that porosity could have an initial, positive influence on bone integration of implants, by stimulating the mineralization process. The methods used were found to be suitable tools for investigation of initial healing around implants in bone.     

Surface modification of titanium by nano-TiO2/HA bioceramic coating

A nano-TiO₂/hydroxyapatite composite bioceramic coating was developed and applied to the surfaces of pure titanium discs by the sol-gel method. A TiO₂ anatase bioceramic coating was utilized in the inner layer, which could adhere tightly to the titanium substrate. A porous hydroxyapatite (HA) bioceramic coating was utilized in the outer layer, which has higher solubility and better short-term bioactivity. Conventional HA coatings and commercially pure titanium were used as controls. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed to characterize the crystallization, surface morphology, and thickness of the coatings. The bioactivities of the coatings were evaluated by in vitro osteoblast cultures. Results showed that the nano-TiO₂/HA composite bioceramic coating exhibited good crystallization and homogeneous, nano-scale surface morphology. In addition, the nano-TiO₂/HA coating adhered tightly to the substrate, and the in vitro osteoblast cultures exhibited satisfactory bioactivity.