Modell zur Analyse des knöchernen Anwachsverhaltens auf bioaktiv beschichteten Implantatoberflächen

Model to analyse the bone on‐growth on bioactive coated implant surfaces Especially on the field of bone regeneration, transient and permanent implants are an important method of therapy in the Orthopaedic Surgery. In this context, bioactive surfaces on metallic implants provide an improved contact to the surrounding bone. The goal of our study was to establish an in‐vitro test system to evaluate the on‐growth of bone‐derived cells on different surface coatings. Therefore, we invented a special kind of clamps made of commercially‐pure (c‐p) titanium and blasted with hydroxyapatite particles followed by electrochemically coating with calcium phosphate (BONIT®‐HA, BONIT®). Definite pieces of human cancellous bone were attached to these clamps, inserted onto tissue culture plates and cultivated in DMEM for ten days. Finally, the contact area between human cancellous bone and the implant surface was analyzed and the spreading of osteoblast‐like cells evaluated by scanning electron microscopy (SEM). A well‐spread morphology of bone cells was observed on the implant surfaces coated with calcium phosphate (CaP). In comparison the clamps without CaP coatings showed only a marginal growth of bone cells on the clamp surface. The presented newly in‐vitro test setup using titanium clamps coated with bioactive layers attached to human cancellous bone represents a well‐functioning model for qualitative evaluation of bone on‐growth.     

钛合金表面生物活性涂层的发展历程及趋势研究

钛及钛合金表面经常被涂覆上羟磷灰石使其获得良好的生物学性能.指出了对钛及钛合金表面制备羟基磷灰石涂层的研究依次经历了单一羟基磷灰石涂层、复合涂层、纳米涂层、梯度涂层几个阶段,分别分析了不同的涂层所面临的问题,提出了纳米梯度涂层是将来钛和钛合金表面涂层发展的新方向.     

Hyrdoxyapatite Coatings on Titanium

Some ceramics, including calcium phosphates and certain glasses and glass‐ceramics, form an important class of bioactive materials that are used extensively in repair and reconstruction of diseased or damaged parts of the musculoskeletal system. The similarity between synthetic hydroxyapatite (HA) (Ca₁₀(PO₄)₆(OH)₂) and the mineral phase of bone and tooth made HA one of the earliest materials to be used to impart osteoconductive (bone‐bonding) properties to the surface of biocompatible, metallic implants. HA and other calcium phosphate surfaces are used primarily to cause early stabilization of the implant in the surrounding bone through the formation of a direct bond and enhanced bone apposition. Although bioactive ceramics are used in several compositions and forms, the focus here is on the use of HA coatings in metallic implants. The coatings made by commercially available plasma‐spray and other techniques are compared to those made recently by surface‐mediated biomimetic routes.     

Surface Engineering of Biodegradable Magnesium Alloys for Enhanced Orthopedic Implants

Magnesium (Mg) alloys have been promised for biomedical implants in orthopedic field, however, the fast corrosion rate and mode challenge their clinical application. To push Mg alloys materials into practice, a composite coating with biodegradable and high compatible components to improve anticorrosion property of an Mg alloy (i.e., AZ31) is designed and fabricated. The inner layer is micro‐nano structured Mg(OH)₂ through hydrothermal treatment. Then stearic acid (SA) is introduced to modify Mg(OH)₂ for better reducing the gap below a surface‐degradation polymer layer of poly(1,3‐trimethylene carbonate). Benefited by the SA modification effect, this sandwiched coating avoids corrosive medium penetration via enhancing the adhesion strength at the interface between outer and inner layers. Both in vitro and in vivo tests indicate that the composite coating modified AZ31 perform a better anticorrosion behavior and biocompatibility compared to bare AZ31. Strikingly, a 1.7‐fold improvement in volume of newly formed bone is observed surrounding the composite coating modified implant after 12 week implantation. The sandwiched biocompatible coating strategy paves a hopeful way for future translational application of Mg alloys orthopedic materials in clinics.     

Application of a Bioactive Coating on Resorbable,Neodymium Containing Magnesium Alloys,and Analyses of their Effects on the In Vitro Degradation Behavior in a Simulated Body Fluid

Whilst bioactive coatings are commonly used as layers for non‐resorbable implant materials, such as titanium or steel to improve cell adhesion, this study investigates the application of bioactive SiO₂–CaO–P₂O₅ on resorbable magnesium alloys (Nd2 and LANd442). The bioactive coating was applied to the magnesium alloys by a dip‐coating process, where a parameter set of 20 immersions and a 10 s drying time between each immersion generated a reproducible layer with regard to its thickness and homogeneity. In vitro mass loss, strength loss, and pH value measurements were used to determine the coating's effects on the degradation behavior in a simulated body fluid. Here, it could be observed that bioactive layers on magnesium alloys lead to an increased degradation in comparison to specimens in the uncoated states. In addition to this, pitting corrosion was determined for bioactive coated magnesium samples during comparatively early periods of the investigation. Due to the decreased corrosion resistance and induced pitting corrosion of bioactive coated magnesium alloys, it is suggested that one carefully tests if the enhanced cell adhesion, which occurs with bioactive coatings, warrants the increased degradation of magnesium based implant materials.     

Development of low‐melting‐point filler materials for laser beam brazing of aluminum alloys

In order to develop low‐melting‐point filler materials for laser beam brazing of aluminum alloys, Al–Si–Cu based alloys and Al–Si–Zn based alloys were produced via spray forming and associated deformation processes. The selected alloys were spray formed in the form of billet with a diameter around 160 mm and hot extruded into wire rods with a diameter of 8 mm. The extrusions were further cold worked into thin wires with a diameter of 1.2 mm via rotary swaging. Finally, the filler wires were applied in the laser beam brazing of AA6082 structures. It showed that the newly developed filler materials could meet the requirements of the laser beam brazing of aluminum alloys. Particularly, the laser beam brazing process using the spray‐formed filler materials required a significantly lower energy input and allowed for higher brazing speed as compared to the conventional AlSi12 filler material.     

Blood compatibility of zinc–calcium phosphate conversion coating on Mg–1.33Li–0.6Ca alloy

Magnesium alloys as a new class of biomaterials possess biodegradability and biocompatibility in comparison with currently used metal implants. However, their rapid corrosion rates are necessary to be manipulated by appropriate coatings. In this paper, a new attempt was used to develop a zinc-calcium phosphate (Zn-Ca-P) conversion coating on Mg-1.33Li-0.6Ca alloys to increase the biocompatibility and improve the corrosion resistance. In vitro blood biocompatibility of the alloy with and without the Zn-Ca-P coating was investigated to determine its suitability as a degradable medical biomaterial. Blood biocompatibility was assessed from the hemolysis test, the dynamic cruor time test, blood cell count and SEM observation of the platelet adhesion to membrane surface. The results showed that the Zn-Ca-P coating on Mg-1.33Li-0.6Ca alloys had good blood compatibility, which is in accordance with the requirements for medical biomaterials.     

Influence of strontium for calcium substitution in bioactive glasses on degradation,ion release and apatite formation

Bioactive glasses are able to bond to bone through the formation of hydroxy-carbonate apatite in body fluids while strontium (Sr)-releasing bioactive glasses are of interest for patients suffering from osteoporosis, as Sr was shown to increase bone formation both in vitro and in vivo. A melt-derived glass series (SiO₂–P₂O₅–CaO–Na₂O) with 0–100% of calcium (Ca) replaced by Sr on a molar base was prepared. pH change, ion release and apatite formation during immersion of glass powder in simulated body fluid and Tris buffer at 37°C over up to 8 h were investigated and showed that substituting Sr for Ca increased glass dissolution and ion release, an effect owing to an expansion of the glass network caused by the larger ionic radius of Sr ions compared with Ca. Sr release increased linearly with Sr substitution, and apatite formation was enhanced significantly in the fully Sr-substituted glass, which allowed for enhanced osteoblast attachment as well as proliferation and control of osteoblast and osteoclast activity as shown previously. Studying the composition–structure–property relationship in bioactive glasses enables us to successfully design next-generation biomaterials that combine the bone regenerative properties of bioactive glasses with the release of therapeutically active Sr ions.     

Bioactive composite gradient coatings of nano-hydroxyapatite/polyamide66 fabricated on polyamide66 substrates

Tightly bonding of bioactive coating is the first crucial need for orthopaedic implants. This study describes a novel and convenient technique to prepare bioactive coating with high adhesion on orthopaedic substitutes made of polymeric matrix. Here, a chemical corrosion method has been adopted to fabricate a coating on the surface of injection-moulded polyamide66 (PA66) substrates by corrosive nano-hydroxyapatite/polyamide66 (n-HA/PA66) composite slurry. Scanning electron microscopy observation shows that a porous chemical corrosion region presents between the coating and dense PA66 substrate. Energy-dispersive X-ray spectroscopy analysis indicates that the chemical corrosion region is mainly composed of PA66 matrix, and the coating layer is an n-HA-rich layer. Both the pore size and n-HA composition increase gradually from the polymeric substrate towards the coating surface. Mechanical testing shows the bonding strength can reach 13.7 ± 0.2 MPa, which is much higher than that fabricated on polymeric matrix by other coating methods. The gradual transition in coating structure and composition benefits for the interface bonding and for the surface bone-bonding bioactivity. Subsequent cell experiments corroborate n-HA-rich coating and a porous structure is benefitting for cell attachment and proliferation. The convenient coating method could be popularized and applied on similar polymer implants to produce a tightly and porous bioactive coating for bone tissue regeneration.     

Synthesis and characterization of biocompatible hydroxyapatite coated ferrite

Ferrite particles coated with biocompatible phases can be used for hyperthermia treatment of cancer. We have synthesized substituted calcium hexaferrite, which is not stable on its own but is stabilized with small substitution of La. Hexaferrite of chemical composition (CaO)_0.75(La₂0₃)_0.20(Fe₂O₃)₆ was prepared using citrate gel method. Hydroxyapatite was prepared by precipitating it from aqueous solution of Ca(NO₃)₂ and (NH₄)₂HPO₄ maintaining pH above 11. Four different methods were used for coating of hydroxyapatite on ferrite particles. SEM with EDX and X-ray diffraction analysis shows clear evidence of coating of hydroxyapatite on ferrite particles. These coated ferrite particles exhibited coercive field up to 2 kOe, which could be made useful for hysteresis heating in hyperthermia. Studies by culturing BHK-21 cells and WBC over the samples show evidence of biocompatibility. SEM micrographs and cell counts give clear indication of cell growth on the surface of the sample. Finally coated ferrite particle was implanted in Kasaulli mouse to test its biocompatibility. The magnetic properties and biocompatibility studies show that these hydroxyapatite coated ferrites could be useful for hyperthermia.     

Diffusionslöten von Aluminium mittels PVD applizierter Lotzusatzwerkstoffe

Diffusion brazing of aluminium by PVD applied filler metals Diffusion brazing of aluminium and aluminium alloys precoated with filler metal components enables fluxless wetting and obtains braze joints of high strength at moderate brazing temperatures. Previously deposited components of filler metals on the base materials as thin film, using Arc‐PVD‐process lead during a subsequently diffusion brazing process to the formation of a local liquid phase (transient liquid phase). The liquid phase is formed from the deposited thin film material and the base material and is solidified isotherm due to diffusion procedures. In doing so braze joints of higher melting point than brazing temperature can be realised. In this work, vacuum brazing of the two systems, Al‐Cu and Al‐Cu‐Si have been investigated. Cu and Al‐Cu‐Si were deposited on the base material using Arc‐PVD‐process. The base materials were pure aluminum and EN‐AW6060. Metallographic and scanning electron microscope analyses proved that the braze seam area after the completed diffusion brazing process shows similar structure and composition as the base material.     

Synthesis and characterization of functionally graded nickel‐nickel coated ZrO2 composite coating

Electroless‐nickel plated ZrO₂ (NCZ) particles have been used to produce a functionally graded nickel‐electroless‐nickel plated ZrO₂ composite coating. So, electroless‐nickel plated ZrO₂ particles concentration was continuously increased from 0 to an optimum value in the electroplating bath (Watt's bath). The substrate was ST37 steel and the thickness of the coating was approximately 50 μm. Also a uniformly distributed nickel‐electroless‐nickel plated ZrO₂ composite coating has been manufactured as comparison. The composite coatings were characterized by scanning electron microscopy and energy‐dispersive X‐ray spectroscopy. Structure and phase composition were identified by X‐ray diffraction analysis. Microhardness of the coatings was evaluated by employing a Vickers instrument. Three‐point bend test was carried out to compare the adhesion strength of the coatings. Dry sliding wear tests were performed using a pin‐on‐disk wear apparatus. The electrochemical behavior of the coatings was studied by electrochemical impedance spectroscopy. The microhardness measurements showed that, with increasing the co‐electrodeposited electroless‐nickel plated ZrO₂ particle content in the nickel matrix, the microhardness increases from interface towards the surface of the functionally graded composite coating. Bend, wear and electrochemical test results confirmed that the functionally graded composite coating has higher adhesion, wear resistance and corrosion resistance as compared with the uniformly distributed coating. This has been attributed to lower mechanical mismatch between coating and substrate in functionally graded composite coating with respect to the uniformly distributed one.     

智能涂层--类生物表面活性智能涂层

智能涂层是一种人造的、能够对某一外部刺激,如:温度、应力、应变或环境等有选择提供(作出)最佳反应的新型涂层系统.介绍了智能涂层的概念、范畴、特点和国内外研究动态.对自清洁、减流阻、抗菌除污智能涂层的原理和研究成果进行了分析和评述.     

Rapid prototyping and rapid manufacturing in medicine and dentistry

The fundamentals and latest developments of Rapid Prototyping (RP) and Rapid Manufacturing (RM) technologies and the application of most common biomaterials such as titanium and titanium alloy (Ti6Al4V) are discussed in this paper. The issues while fabricating pre-surgical models, scaffolds for cell growth and tissue engineering and concerning fabrication of medical implants and dental prostheses are addressed. Major resources related to RP/RM technology, biocompatible materials and RP/RM applications in medicine and dentistry are reviewed. A large number of papers published in leading journals are searched.

Besides the titanium and titanium alloys which were established as bio-compatible materials over five decades ago, other biocompatible materials such as cobalt-chromium and PEEK have also been increasingly used in medical implants and dental prosthesis fabrication. For over a decade RP technologies such as Selective Laser Sintering (SLS) and Selective Laser Melting (SLM) along with the Fused Depositing Modelling (FDM) are predominantly employed in the fabrication of implants, prostheses and scaffolds. Recently Electron Beam Melting (EBM) has been successfully employed for fabrication of medical implants and dental prostheses with complex features. In dentistry crown restoration, the use of thin copings of Ti6Al4V made by the EBM process is an emerging trend. This review is based upon the findings published in highly cited papers during the last two decades. However the major breakthrough in the field of RP/RM for medical implants and dental prostheses took place in the last decade. The fabrication of medical implants and prostheses and biological models have three distinct characteristics: low volume, complex shapes and they are highly customised. These characteristics make them suitable to be made by RM technologies even on a commercial scale. Finally, current status and methodology and their limitations as well as future directions are discussed.     

可降解聚酰胺类骨折内固定材料表面的HAP涂层

使用乙酸－聚甲基丙烯酸甲酯（PMMA）－羟基磷灰石（HAP）体系，采用低温浆料粘涂技术对可降解聚酰胺类骨折内固定材料进行表面涂数处理，得到了完全覆盖的，有一定粘结强度的均一的HAP涂层，XRD，SEM和FT－IR实验表明本方法得到的HAP涂层，其主要成分以HAP（Ca10(PO4)6(OH)2)的形式存在，保持了具有生物活性的结构形态，且结晶度良好，涂层具有一定的孔隙度，这有利于新骨组织的生长，同时还可吸附其他生物活性物质及药物，本方法是一种增加骨植入物生物活性的有效方法。     

TiO2 /chondroitin‐4‐sulphate nanocomposite coating on Ti–6Al–4V for implants and prostheses applications

Nano‐titania, chondroitin‐4‐sulphate, and titania/chondroitin‐4‐sulphate nanocomposite were separately deposited on Ti–6Al–4V alloys by repetitive spin coating. Surface characterisation techniques were used to find out the crystalline nature, chemical bonding, surface homogeneity, and elemental composition. Biological studies of nanocomposite‐coated alloys revealed the formation of stable hydroxyapatite (Ca/P = 1.678), superior corrosion resistance, and ∼12 mm zone of inhibition against Staphylococcus sp. However, the cell line studies revealed the better response on polymer‐coated alloy than the uncoated and composite‐coated alloy. It has been found that the nanocomposite coating can synergistically increase the thickness of the pre‐existing passive layer and thereby improve the corrosion resistance of Ti–6Al–4V implant in simulated body fluid. The nanocomposite coatings improved the corrosion resistance of the bare Ti–6Al–4V implant specimens by decreasing the i _corr. The formation of hydroxyapatite on nanocomposite‐coated alloy may have ability to inhibit the release of toxic substance to the adjacent tissues. In addition, the in vitro cell line study confers that the nanocomposite‐coated Ti–6Al–4V induces cell attachment and proliferation, and it eventually help to new bone cell formation than the uncoated one. Overall, this nanocomposite coating can be applied in orthopedic applications for effective biomimic bone regeneration.Inspec keywords: titanium compounds, nanocomposites, titanium alloys, aluminium alloys, vanadium alloys, nanomedicine, biomedical materials, prosthetics, X‐ray diffraction, Fourier transform spectra, infrared spectra, scanning electron microscopy, fluorescence, corrosion resistance, polymer films, calcium compounds, cellular biophysics, boneOther keywords: chondroitin‐4‐sulphate nanocomposite coating, implants, prostheses, nano‐titania, repetitive spin coating, surface characterisation, X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray fluorescence, TiAlV, TiO₂ , effective biomimic bone regeneration, orthopaedic applications, bone cell formation, osteoblast cells, cell proliferation, cell attachment, simulated body fluid solution, composite‐coated alloy, polymer‐coated alloy, Staphylococcus sp, corrosion resistance, hydroxyapatite, elemental composition, surface homogeneity, chemical bonding, crystalline nature     

Microstructure of brazed joints between mechanically metallized Si<Subscript>3</Subscript>N<Subscript>4</Subscript> and stainless steel

Brazing has been increasingly used to join metals to advanced ceramics. Brazing covalent materials requires either the use of active filler alloys or the previous metallization of the surface. To that end, a new and simple mechanical technique has been applied to metallize advanced ceramics, thus avoiding the use of costly Ti-based active filler alloys. The mechanical metallization of Si₃N₄ with Ti was employed as an alternative route to deposit active metallic films prior to brazing with stainless steel using 72% Ag--28% Cu or 82% Au—18% Ni eutectic alloys. The brazing temperatures were set to 40°C or 75°C above the eutectic temperature of each filler alloy. Ti-films of average thickness 4 μm produced adequate spreading of both filler alloys onto Si₃N₄ substrates, which were subsequently brazed to stainless steel. The interface of Si₃N₄/310 stainless steel basically consisted of a reaction layer, a precipitation zone and an eutectic microconstituent. Mechanically sound and vacuum-tight joints were obtained, especially upon brazing at relatively lower temperatures. Increasing the brazing temperature resulted in thermal cracking of the Si₃N₄, possibly due to increased thermal stress.     

用镍基薄带钎料真空熔结Cr3C2-NiCr涂层的组织和性能

提出了一种采用薄带钎料进行真空熔结的新方法，用BNi-2薄带钎料粘贴在Cr3C2-NiCr预置层表面进行了真空熔结处理，对涂层的组织和微动磨损性能进行了研究。结果表明，真空熔结涂层组织致密，涂层与基体、涂层内部硬质相与粘结相之间可形成良好的冶金结合。涂层主要由Cr3C2，Cr7C3，Cr23C6，Ni的硼化物、Cr的硼化物等硬质相和镍基固溶体韧性相组成。基于致密的组织、良好的结合和硬质相强化，真空熔结Cr3C2-NiCr涂层的抗微动磨损性能明显优于等离子喷涂Cr3C2-NiCr涂层和1Crl8Ni9Ti不锈钢。     

(WC-Co/NiCrBSi)钎焊涂层结合机制及磨损性能研究

采用真空钎焊工艺,将ＷＣ－Ｃｏ硬质合金粉和ＮｉＣｒＢＳｉ（ＡＷＳＢＮｉ－２）合金粉钎焊到４５＃钢表面,得到（ＷＣ－Ｃｏ／ＮｉＣｒＢＳｉ）钎焊涂层。不同钎焊工艺下,涂层及涂层／基体的拉伸强度分别达１００—１４０ＭＰａ和３００－３６０ＭＰａ。初步分析了钎焊涂层结合机制。涂层的磨料磨损性能远高于同配比的火焰堆焊涂层及Ｃｏ－Ｃｒ－Ｗ堆焊层     

Recent advances in synthesis, characterization of hydroxyapatite/polyurethane composites and study of their biocompatible properties

The development of engineered biomaterials that mimic bone tissues is a promising research area that benefits from a growing interest. Polymers and polymer–ceramic composites are the principle materials investigated for the development of synthetic bone scaffolds thanks to their proven biocompatibility and biostability. Several polymers have been combined with calcium phosphates (mainly hydroxyapatite) to prepare nanocomposites with improved biocompatible and mechanical properties. Here, we report the hydrothermal synthesis in high pressure conditions of nanostructured composites based on hydroxyapatite and polyurethane functionalized with carboxyl and thiol groups. Cell-material interactions were investigated for potential applications of these new types of composites as coating for orthopedic implants. Physical–chemical and morphological characteristics of hydroxyapatite/polyurethane composites were evaluated for different compositions, showing their dependence on synthesis parameters (pressure, temperature). In vitro experiments, performed to verify if these composites are biocompatible cell culture substrates, showed that they are not toxic and do not affect cell viability.