Effect of Ti-OH formation on bioactivity of vacuum plasma sprayed titanium coating after chemical treatment

The effect of Ti-OH groups on bioactivity of NaOH treated titanium coating was investigated in this paper. The NaOH-heat treatment was also applied to modify the titanium coating for comparison. The results show that the amount of Ti-OH groups was important to induce apatite formation on the treated titanium coating. When the NaOH treated titanium coating was exposed to SBF, it released Na⁺ ions from the sodium titanate layer on its surface into the SBF via exchanging with H₃O⁺ ions in the fluid and Ti-OH groups were rapidly formed on the surface. So the NaOH treated titanium coating has good bioactivity in simulated body fluid (SBF). The amount of Ti-OH groups on the titanium coating was reduced after heat treatment, so the bioactivity of NaOH-heat treated titanium coating was obviously affected.     

Bioactivity and cytocompatibility of plasma-sprayed titania coating treated by sulfuric acid treatment

Titania coatings were fabricated on titanium alloy substrate using atmospheric plasma spraying technology, and treated by sulfuric acid (H₂SO₄) at room temperature for 24 h. The as-sprayed and acid-treated titania coatings were soaked in simulated body fluid (SBF) to investigate the formation of apatite on their surfaces. Human mesenchymal stem cells (MSCs) were used to evaluate the cytocompatibility of titania coatings. The results indicated that bone-like apatite was formed on the surfaces of acid-treated titania coatings after soaked in SBF for a period of time. The concentration of sulfuric acid had an effected on the bioactivities of titania coatings. The bioactivity of titania coating could not be improved by 0.01 M sulfuric acid treatment. The MSCs could attach, grow and proliferate well on the surface of titania coatings. The results showed that plasma-sprayed titania coating after acid treatment exhibited favorable bioactivity and cytocompatibility.     

Y_2O_3对激光熔覆钛基复合涂层生物性能的影响

采用激光熔覆技术在Ti-6Al-4V基材表面制备了生物陶瓷复合涂层。利用急性毒性实验、动物体内埋植实验以及体外细胞培养实验对钛基生物陶瓷复合涂层的生物性能进行了研究。结果表明:添加0.6%(质量分数)Y_2O_3的预置粉末和激光熔覆后的生物陶瓷涂层均无明显的急性毒性反应;动物体内分别埋植45、180 d后,与未添加稀土氧化物的复合涂层相比较,添加0.6%Y_2O_3的激光熔覆生物陶瓷复合涂层具有更好的骨小梁生成能力,且细胞在其表面生长良好;添加0.6%Y_2O_3的激光熔覆生物陶瓷复合涂层具备良好的生物相容性。     

Preparation and Characterization of CaO-ZrO2-SiO2 Coating for Potential Application in Biomedicine

In this paper, chemically synthesized CaO-ZrO₂-SiO₂ (CZS) powder was plasma sprayed onto a Ti-6Al-4V alloy substrate for its potential applications in biomedicine. Surface morphology and phase composition were analyzed by scanning electron microscopy (SEM) and x-ray diffraction (XRD). The degradation behavior of the coating in biological environment was in vitro appraised in Tris-HCl buffer. The mass loss was much lower than that of the wollastonite coating (WC) and close to that of the hydroxylapatite coating (HC). The bond strength with titanium alloy substrate was 31.8 ± 4.7 MPa. In vitro bioactivity appraisement results showed that apatite could be formed on the surfaces after soaking in simulated body fluid (SBF) for 14 days. Canine marrow stem cells (MSCs) also showed well adhesion and proliferation on the coating surfaces. In summary, results suggest that the coating possesses well cytocompatibility and may be an appropriate candidate for application in biomedicine.     

Phase composition and in-vitro bioactivity of plasma sprayed calcia stabilized zirconia coatings

Zirconia coatings stabilized with different calcia content (12.8 mol%, 16 mol% and 30 mol%) were fabricated on titanium alloy substrates using atmospheric plasma spraying technology. The in-vitro bioactivity of coatings was evaluated by simulated body fluid (SBF) soaking test. The morphology and phase composition of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), micro Raman spectroscopy, energy dispersive spectrometry (EDS) and infrared spectroscopy (IR). The results showed that the apatite was formed on the surface of the calcia stabilized zirconia coatings soaked in SBF for 28 days and the formation ability of apatite decreased with the increase in calcia content of the coating. The bioactivity of zirconia coatings was thought to be related to the Zr-OH formed on their surfaces during the phase transformation in the presence of water. Osteoblast-like MG63 cells were cultured on the surfaces of the coatings to evaluate their cytocompatibility. Results showed that MG63 cell grew and proliferated well on all coating surfaces, indicating that plasma sprayed calcia stabilized ZrO₂ coatings were cytocompatible.     

悬浮液等离子喷涂制备FHA/CS复合涂层

目的 采用悬浮液等离子喷涂技术（SPS）在纯钛表面制备氟代羟基磷灰石/硅酸钙（FHA/CS）生物复合涂层。方法 利用X射线衍射仪（XRD）、傅里叶红外光谱仪（FT-IR）、扫描电子显微镜（SEM）及能谱仪（EDS）对复合涂层的物相组成、组织结构和显微形貌进行分析。通过动电位极化测试和体外生物活性测试,分析复合涂层在模拟体液（SBF）中的腐蚀行为和类骨磷灰石形成能力。通过电感耦合等离子体光谱仪（ICP）分析涂层中Ca2+的释放行为,评估复合涂层的化学稳定性。采用划痕法表征涂层的结合强度。结果 SPS制备的复合涂层具有粗糙的表面和层片堆叠结构。涂层中FHA和CS两相分布均匀,结晶性良好。复合涂层临界载荷达到111.43 N,比单一FHA涂层提高62.5%。与纯钛相比,涂层样品具有较高的腐蚀电位（Ecorr）和较低的腐蚀电流密度（Jcorr）。在SBF溶液中浸泡3天,涂层样品表面被类骨磷灰石完全覆盖。ICP结果表明,复合涂层中Ca2+释放速率低于单一CS涂层。结论 通过SPS在纯钛表面制备的FHA/CS复合涂层具有良好的生物活性、耐腐蚀性能和与基体的结合强度,复合涂层中FHA组分的存在有利于提高涂层的化学稳定性。     

激光熔覆SiO2/La2O3梯度生物陶瓷涂层生物活性研究

目的研究SiO_2含量对钛合金表面激光熔覆梯度生物陶瓷涂层生物活性的影响。方法利用激光熔覆技术,采用梯度成分设计思想,固定涂层中稀土氧化物La_2O_3的添加量,在钛合金TC4表面制备了掺杂不同含量SiO_2的梯度生物陶瓷涂层。采用金相显微镜(OM)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、噻唑蓝(MTT)及荧光素双醋酸酯(FDA)染色等测试手段,研究了SiO_2含量对激光熔覆制备梯度涂层的组织结构和生物活性的影响。结果 SiO_2在激光熔覆过程中可以降低梯度生物陶瓷涂层的开裂敏感性,并起到细化晶粒的作用。当SiO_2掺杂量为2.5%时,激光熔覆过程中诱导合成的HA+CaTiO_3数量最大;当SiO_2掺杂量为7.5%时,模拟体液(SBF)实验表明,涂层的矿化沉积能力最强。MTT测试表明,SiO_2掺杂量为7.5%的涂层细胞增殖数量的OD值最大,细胞能够紧贴涂层表面生长。FDA染色分析表明,SiO_2掺杂量为7.5%的涂层上细胞数量最多,且分布均匀。结论 SiO_2掺杂量深刻影响着生物活性陶瓷相HA和Ca_2SiO_4数量,进而影响生物陶瓷涂层的生物活性。SiO_2掺杂量为7.5%的涂层具有最佳的生物相容性及生物活性。     

Preparation and cell-materials interactions of plasma sprayed strontium-containing hydroxyapatite coating

The use of strontium-containing hydroxyapatite (Sr-HA) as a biomaterial has been reported recently. In vitro and in vivo studies have shown that Sr-HA promotes osteoblast response and stimulates new bone formation. In order to extend its usage to major load-bearing applications, such as artificial hip replacement, it has been proposed that the material could be used in the form of a coating on implant surfaces. This paper reports a preliminary study of biocompatibility of plasma sprayed Sr-HA coatings on a metallic substrate. Coatings of Sr-HA containing 10 mol% Sr²⁺ was produced on titanium alloy substrates. The coating exhibited good bonding with the substrate. The bioactivity of Sr-HA coating was evaluated in vitro by immersion in simulated body fluid (SBF). After immersion in SBF, Sr-HA coating exhibited great ability to induce apatite precipitation on its surface. The possible effects of cell-materials interactions of Sr-HA coating were examined by culturing osteoprecursor cells (OPC1) on coating surfaces. The effect of Sr-HA was also compared to a hydroxyapatite (HA) coating, which is widely used in orthopedics and dentistry. The results indicated that Sr-HA coating had good biocompatibility with human osteoblasts. OPC1 cells survived and proliferated well on the surface of coating. Sr-HA coating promoted OPC1 cells attachment, and more local contacts were produced on the surface. The presence of Sr stimulated OPC1 cell differentiation and ALP expression. No deleterious effect on ECM formation and mineralization was found with Sr-HA coating. The results indicated that Sr-HA coating had good mechanical properties and bioactivity in vitro.     

钛基体表面多级孔洞结构的制备和生物活性研究

目的通过调控钛基体表面的结构和特性,提高惰性钛基体表面的生物活性,改善其医用植入效果。方法采用碱热处理方法在钛基体表面构建多级孔洞结构,对改性后钛片的表面形貌、成分、结构、亲疏水性进行表征,评价钛片表面对类骨磷灰石的诱导能力。结果碱热处理使钛表面形成了多孔网状结构,孔洞包括微米级孔和200~300 nm的纳米孔,孔隙间隔介于微米至几百纳米之间。碱热处理后的钛片表面形成了含有大量羟基的氧化物层,主要成分为金红石型Ti O2和碱性钛酸盐,具有极好的亲水性,接触角仅约为12°。碱热处理钛片表面的三维多孔结构对磷灰石的生长有很好的诱导作用,矿化7天后,类骨磷灰石便完全覆盖表面,14天后的矿化效果更好。结论纯钛表面通过碱热处理法构建微纳多孔结构后,具有良好的诱导羟基磷灰石形成的能力,对其生物活性有促进作用。     

医用近β型钛合金TLM的碱液处理与生物活性

采用模拟体液浸泡法评价碱液处理TLM(Ti-25Nb-3Zr-2Sn-3Mo)合金的生物活性。钛合金TLM经过碱液处理后表面生成了钛(铌)酸钠凝胶层,凝胶层厚度随碱液浓度升高而增加。在模拟体液中浸泡43h后,碱液处理钛表面只有少量磷灰石晶核生成,而碱液处理TLM合金表面有五水磷酸八钙晶粒形成,磷灰石的形核也较多。钛合金TLM在碱液处理时生成的钛(铌)酸钠凝胶层厚于纯钛,而较厚的凝胶层使其生物活性提高。     

Effects of plasma treatment on bioactivity of TiO2 coatings

In this work, nano-TiO₂ powders were deposited on titanium alloy substrates by atmospheric plasma spraying, followed by plasma immersion ion implantation (PIII) using hydrogen, oxygen and ammonia gases. The bioactivities of PIII-treated TiO₂ coatings were evaluated by the formation of apatite on their surface after soaked in simulated body fluids (SBF) for a period of time. As-sprayed TiO₂ coating is composed of rutile, anatase and TiO_2−x (most of them is Ti₃O₅). After immersion in SBF for two weeks, the hydrogen PIII-treated TiO₂ coating can induce bone-like apatite formation on its surface but apatite cannot be formed on the surface of as-sprayed and oxygen, ammonia PIII-treated TiO₂ coatings. The results obtained indicated that a hydrogenated surface plays a very important role to induce bioactivity of TiO₂ coatings.     

等离子喷涂TiO2-CaF2复合涂层的结构及体外生物矿化能力

目的等离子喷涂TiO_2涂层是生物惰性材料,不能与骨组织很好地结合,制备TiO_2-CaF_2复合涂层以提高氧化钛涂层的体外生物矿化能力。方法利用等离子喷涂技术在医用Ti合金表面制备TiO_2-CaF_2复合涂层。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和拉曼光谱仪(Raman)对复合涂层的微观结构进行表征,利用接触角仪、三维轮廓仪和电化学工作站考察复合涂层的接触角、表面粗糙度和耐腐蚀性能。采用模拟体液(SBF)浸泡实验考察复合涂层的体外矿化能力。结果 TiO_2和TiO_2-20%CaF_2涂层主要由金红石型TiO_2构成,其中含有少量的锐钛矿型TiO_2成分。20%CaF_2的掺杂会促进金红石型TiO_2的形成。CaF_2的加入可改变TiO_2涂层的表面形貌,表面粗糙度Ra从4.96μm降低至0.94μm,亲水性也得到增强。TiO_2-CaF_2复合涂层在SBF中的耐腐蚀性能也较TiO_2涂层有所提高。经SBF浸泡28 d后,TiO_2-CaF_2复合涂层表面可沉积类骨磷灰石,显示了较好的体外矿化能力,而TiO_2涂层则无此能力。结论 CaF_2的掺杂可使TiO_2涂层的表面粗糙度下降,亲水性增强,耐腐蚀性增强。体外矿化实验结果表明,TiO_2-CaF_2复合涂层表面可沉积类骨磷灰石,显示了较好的生物活性。     

Influence of Electrolyte Composition on the Calcium-Phosphorus compound Coating on Titanium Substrate by Micro-arc Oxidation

In recent years the biomedical material has been widelydeveloped,and application that the implant materialssubstitute for hard organ has attracted much attention.Titanium alloys are frequently utilized as skeletonimplant and modification materials because of theirlight density,high strength and proper biocompatibility.However,titanium alloys are bioinertial materials,which are not beneficial to the performance of organiccoalescence,so they are not yet the ideal implantmaterials.Therefore,impro…     

碱液处理诱导钛合金基体表面沉积磷灰石层

改变碱液处理条件和基体材料,考察了这些参数对钛合金诱导磷灰石能力的影响。结果表明：经过碱液处理钛合金表面形成了多孔网状,带负电荷的二氧化钛水凝胶层,在过饱和的模拟体液中可沉积出骨状磷灰石层;随碱液浓度、温度和处理时间境加,凝胶层的孔径和厚度增加,诱导形成磷灰石的能力增强;不同基体材料的诱导能力为：Ｔｉ〉ＴＣ４,Ｔｉ７５〉ＴｉＺｒ。太合金碱液处理后可在模拟体液中沉积出磷灰石层,因此碱液处理使钛合金表     

NaOH浓度对NiTi形状记忆合金表面类骨磷灰石形成的影响

研究了不同浓度NaOH对NiTi形状记忆合金在模拟体液(SBF)中诱导磷灰石沉积的影响，用XRD，ESEM，FTIR及XPS等分析了碱处理前后试样表面的结构、形貌、基团和组元化合价的变化，结果表明，经1mol／L NaOH溶液处理的NiTi合金因为钛酸钠的生成而具有较高的生物活性，在SBF中浸泡3d后自然沉积含CO3^2-的类骨磷灰石，而且原子吸收光谱分析其在Hank’S溶液中的镍离子溶出量最少，随着碱处理浓度的提，NiTi合金表面除钛酸钠外，还有镍酸钠生成，使磷灰石形核的孕育期加长，在Hank’S溶液中的镍离子溶出量也明显增加。     

复合活化处理镍钛合金及磷灰石层的仿生沉积

利用H2O2和NaOH溶液对近等原子比NiTi记忆合金（SMA）进行复合活化处理,并采用XRD,SEM,XPS,FTIR等研究了活化处理后NiTi SMA的表面结构及其在模拟体液（SBF）中磷灰石涂层的仿生沉积过程.结果表明：复合活化处理后NiTi SMA表面为贫Ni、富含Ti-OH的蠕虫状活性层,由结晶度较低的TiO2,钛酸纳（Na2TiO3）及少量的Ni2O3组成,在SBF中表面活性层诱导磷灰石形核及生长,短期内在镍钛基体表面获得了理想的磷灰石层.     

Structure of calcium titanate/titania bioceramic composite coatings on titanium alloy and apatite deposition on their surfaces in a simulated body fluid

In this study, TiO₂-based coatings containing Ca and P ions were prepared on titanium alloy surfaces by microarc oxidation (MAO). After soaking in aqueous NaOH solution and subsequent heat treatment at 700 and 800 °C, calcium titanate/titania bioceramic composite (CTBC) coatings were obtained. The results show that the outer layers (0–1.5 μm) of the CTBC coatings are mainly composed of Ca, Ti, O and Na constituents with a uniform distributions with increasing the depth near the surfaces. The surface phase compositions of the CTBC coating formed at 700 °C are anatase, rutile and CaTi₂₁O₃₈ phases, as well as a few CaTiO₃, while those of the CTBC coating formed at 800 °C are anatase, rutile and CaTiO₃. When incubated in a simulated body fluid (SBF), apatite was deposited on the CTBC coatings probably via formation of hydroxyl functionalized surface complexes on the CTBC coating surfaces by ionic exchanges between (Ca²⁺, Na⁺) ions of the CTBC coatings and H₃O⁺ ions in the SBF. The CTBC coating formed at 800 °C seems to facilitate the deposition of Ca and P probably due to the good crystallographic match between perovskite CaTiO₃ and HA on specific crystal planes.     

On the Electrodeposition of Ca-P Coatings on Nitinol Alloy: A Comparison Between Different Surface Modification Methods

In this study, a combination of surface modification process and the electrochemical deposition of Ca-P coatings was used for the modification of the Nitinol shape memory alloy. DSC, SEM, GIB-XRD, FT-Raman, XPS, and FTIR measurements were performed for the characterization of the samples. Results indicated that chemical etching and boiling of the samples in distilled water formed TiO film on the surface. After the chemical modification, subsequent aging of the sample, at 470 °C for 30 min, converted the oxide film to a stable structure of titanium dioxide. In that case, the treated substrate indicated a superelastic behavior. At the same electrochemical condition, the treated substrate revealed more stable and uniform Ca-P coatings in comparison with the abraded Nitinol substrate. This difference was attributed to the presence of hydroxyl groups on the titanium dioxide surface. Also, after soaking the sample in SBF, the needle-like coating on the treated substrate was completely covered with the hydroxyapatite phase which shows a good bioactivity of the coating.     

Characterization of plasma-sprayed hydroxyapatite/TiO2 composite coatings

To enhance the bonding between hydroxyapatite (HA) coating and titanium alloy substrate, HA/TiO₂ composite coatings have been fabricatedvia plasma spraying. Bonding strength evaluation, simulated body fluid tests, and cell culturein vitro were carried out to characterize the composite coatings. The results obtained showed that the addition of TiO₂ to HA coating improved the bonding strength of the coating significantly. After being immersed in simulated body fluid (SBF) for a period, the surfaces of HA/TiO₂ composite coatings were completely covered by carbonate-containing apatite, which indicated that the coatings possess good bioactivity. Thein vitro cell culture indicated good cytocompatibility for HA/TiO₂ composite coatings.     

不同wCa/wP对宽带激光熔覆生物陶瓷涂层性能的影响

目的 对不同wCa/wP的宽带激光熔覆生物陶瓷涂层性能进行研究，探究wCa/wP对涂层硬度、生物相容性及生物活性的影响规律，寻求最优试验参数，为以后制备性能优良的涂层提供参考。方法 运用梯度设计思想，采用宽带激光熔覆技术，在钛合金表面分别制备wCa/wP为1.35、1.40、1.45的梯度生物陶瓷涂层。利用X射线衍射仪(XRD)、扫描电镜(SEM)、金相显微镜、显微硬度仪、模拟体液浸泡试验、体外细胞试验，研究不同wCa/wP对生物陶瓷涂层组织结构、生物相容性以及生物活性的影响。结果 XRD结果表明，涂层主要由CaTiO3、HA、Ca2SiO4、CaO、TCP等相组成。硬度测试表明，wCa/wP=1.45的涂层平均显微硬度最高，而wCa/wP=1.35的涂层平均硬度最低。体外细胞试验表明，所有涂层上的MG63分布均匀，细胞形态良好，wCa/wP=1.40的涂层上的OD值增长较快，共同培养至第5天时，测得的OD值远高于其他涂层，相较于第1天的OD值增加最多。SBF浸泡试验表明，3种wCa/wP的陶瓷涂层都在表面覆盖了类骨磷灰石，wCa/wP=1.40的涂层，经浸泡后表面覆盖了最多的类骨磷灰石。观察细胞生长形态，细胞的许多丝状伪足紧贴在涂层上，使得细胞可以粘附在涂层上并生长，呈现出正常的梭形形态，具备较完整的细胞膜，wCa/wP=1.40的涂层上粘附的细胞数量更多、分布更为均匀。结论 当wCa/wP=1.40时，Ca-P生物陶瓷涂层不仅拥有良好的生物矿化能力，能够形成更多类骨磷灰石，而且涂层上增殖吸附的细胞数量最多，涂层表现出良好的生物相容性和生物活性。