Influence of nickel ions on human multipotent mesenchymal stromal cells (hMSCs)

Nickel‐Titanium‐Shape‐Memory‐Alloys (NiTi‐SMA) are of biomedical interest due to an unusual range of pure elastic deformability (superelasticity) and the shape memory effect which allows this material to return to a predictable previously memorized shape after external changes in temperature. HMSCs (human multipotent mesenchymal stromal cells) are currently the most promising cell type for regenerative medicine and tissue engineering, due to the ability to differentiate into several tissues such as bone, tendon, cartilage or muscle. For tissue engineering newly developed porous NiTi‐SMA materials are evaluated preloaded with hMSCs. For biocompatibility testing the high nickel content (50 %at) of NiTi‐SMA plays a critical role. To analyse the influence of Ni‐ions on hMSCs viability and activation, cells were cultured with or without NiCl₂ for 24h and 7days. Cells were either seeded in media containing NiCl₂ or the NiCl₂ was later added to already adherent cells. Cell metabolism, proliferation and viability were analysed by alamarBlue^TM assay or fluorescence microscopy. Cytokine (IL‐6, 8, 11) release from hMSCs was determined by ELISA . NiCl₂ concentrations below 25 μg/ ml were well tolerated by the cells. A significant decrease in cell proliferation occurred at threshold values of 200 μg/ ml (24 h) and 25 μg/ ml (7 d). There was a significant, dose dependent increase in the release of IL‐8 from hMSCs cultured in the presence of sub toxic NiCl₂ concentrations. The present study demonstrates for the first time that high but non‐toxic concentrations of Ni²⁺ are capable to activate hMSCs. Thus high Ni²⁺ concentrations apart from allergen‐ or particle‐induced inflammation, may lead to tissue inflammation in the vicinity of a NiTi‐SMA implant in vivo and subsequently to implant failure e.g. due to implant loosening.     

Three‐Dimensional Printing of Complex‐Shaped Alumina/Glass Composites

Alumina/glass composites were fabricated by three‐dimensional printing (3DP?) and pressureless infiltration of lanthanum‐alumino‐silicate glass into sintered porous alumina preforms. The preforms were printed using an alumina/dextrin powder blend as a precursor material. They were sintered at 1600 °C for 2 h prior to glass infiltration at 1100 °C for 2 h. The influence of layer thickness and sample orientation within the building chamber of the 3D‐printer on microstructure, porosity, and mechanical properties of the preforms and final composites was investigated. The increase of the layer thickness from 90 to 150 µm resulted in an increase of the total porosity from ～19 to ～39 vol% and thus, in a decrease of the mechanical properties of the sintered preforms. Bending strength and elastic modulus of sintered preforms were found to attain significantly higher values for samples orientated along the Y‐axis of the 3D‐printer compared to those orientated along the X‐ or the Z‐axis, respectively. Fabricated Al₂O₃/glass composites exhibit improved fracture toughness, bending strength, Young's modulus, and Vickers hardness up to 3.6 MPa m^1/2, 175 MPa, 228 GPa, and 12 GPa, respectively. Prototypes were fabricated on the basis of computer tomography data and computer aided design data to show geometric capability of the process.     

Powder metallurgy of the porous Ti-13Nb-13Zr alloy of different powder grain size

The objective of the present project was to determine the effects of powder granulation (fraction of grain size) for the Ti-13Nb-13Zr alloy, produced by powder metallurgy, on its porosity, grain cohesion, compressive strength, and Young`s modulus. Two powder fractions, 45–105 µm, and 106–250 µm were applied. The 50 mass pct of NH<sub>4</sub>HCO<sub>3</sub> was added as a space holder. The specimens were in compaction stage uniaxially pressed at pressure 625 MPa for 120 s. The brown bodies were sintered at a temperature 1150°C for 3.5 h. The well-joined grains were observed for both powder granulations. The increase in powder granulation resulted in an increase of porosity from 51% to 59%, and it was only 30% with no space holder used. The compressive strength increased with decreased porosity from 57 to 236 MPa. Young`s modulus was measured as 4.8 GPa for finer powder and 0.9 GPa for coarser powder. It is evident from the results obtained that the applied process parameters, the space holder and its fraction, and the use powder granulation between 45 and 105 µm bring out the porous material fulfilling mechanical and biological requirements specific of load-bearing titanium implants.     

多孔NiTi形状记忆合金的制备及性能

采用球磨后的NiTi合金粉末为原料,添加尿素作为造孔剂,利用粉末烧结法制备多孔NiTi形状记忆合金.研究烧结温度、保温时间和预成型压力等条件对制备的多孔NiTi合金组织结构和力学性能的影响.结果表明:相对于传统的Ni粉和Ti粉近等原子比混合烧结方法,此方法制备的多孔NiTi合金的相组成更加纯净.且随烧结温度升高,多孔N...     

Nano‐porous Alumina Coatings for Improved Bone Implant Interfaces

A new method is proposed for coating implants that produces a metal implant covered in a layer of nano‐porous alumina ceramic. These layers are produced by first depositing a layer of aluminium on the implant surface and then anodising it in phosphoric acid to produce the nano‐porous structure. This process results in the conversion of the aluminium to alumina containing 6‐8wt% phosphate ions. The surface alumina layer is bonded to the substrate via an interfacial layer of fully dense anodised titanium oxide. Mechanical measurements have shown that the shear and tensile strength of this coating are in excess of 20MPa and 10MPa, respectively. The biological performance of nano‐porous alumina material has been assessed and shown to be highly favourable, supporting normal osteoblastic activity and maintaining the osteoblastic phenotype. The filling of the nano‐porous coating with bioactive material to achieve enhanced biological performance has been investigated using colloidal silica as an analogue for a Bioglass sol. The coating has been loaded with silica by dipping in colloidal silica with a pH of 5.6. Pore filling equivalent to 1.3 wt% SiO₂ in the coating as a whole has been achieved in this way.     

Characterization of porous, net-shaped NiTi alloy regarding its damping and energy-absorbing capacity

Porous NiTi alloys are highly attractive for energy absorbers, damping devices and biomedical implants. In the present work, metal injection moulding (MIM) in combination with the application of a suitable space holder material was used for the production of NiTi parts with well defined pore sizes and porosities in the range of 30-70 vol.%. For comparing the properties, porous titanium and Ti-6Al-4V samples were prepared in the same manner.Focus of the present work was a detailed investigation of the mechanical properties of porous NiTi to estimate its potential regarding the abovementioned applications. For a Ni-rich NiTi alloy with a porosity of 50 vol.%, fully pronounced pseudoelasticity after 6% compression was demonstrated. An energy dissipation of 1.5 MJ/m³ was measured, which could be directly related to the reversible austenite-martensite phase transformation. At higher deformations, pseudoelasticity becomes more and more superposed by the onset of plastic deformation. Nevertheless, even at deformations of up to 50%, a clearly pronounced amount of pseudoelastic shape recovery still remained. Fatigue of pseudoelasticity was investigated by conducting of up to 230,000 load cycles to 4% compression at a frequency of 1 Hz.     

Rotating bending fatigue response of laser processed porous NiTi alloy

Porous implants are known to promote cell adhesion and have low elastic modulus, a combination that can significantly increase the life of an implant. However, porosity can significantly reduce the fatigue life of porous implants. Very little work has been reported on the fatigue behavior of bulk porous metals, specifically on porous nitinol (NiTi) alloy. In this article, we report high-cycle rotating bending fatigue response of porous NiTi alloys fabricated using Laser Engineered Net Shaping (LENS?). Samples were characterized in terms of monotonic mechanical properties and microstructural features. Rotating bending fatigue results showed that the presence of 10% porosity in NiTi alloys can decrease the actual fatigue failure stress, at 10⁶ cycles, up to 54% and single reversal failure stress by ~ 30%. From fractographic analysis, it is clear that the effect of surface porosity dominates the rotating bending fatigue failure of porous NiTi samples.     

Effect of porous NiTi alloy on bone formation: A comparative investigation with bulk NiTi alloy for 15 weeks in vivo

The purpose of this study is to investigate the effect of porous NiTi alloy on bone formation with a bulk NiTi alloy as a contrast. The porous NiTi alloy prepared by element powder sintering under Ar protection has a porosity of 45% and a mean pore size of 130 μm, and the pores are highly interconnected. The porous and bulk NiTi alloys were bilaterally implanted into the femurs of rabbits for 15 weeks. The bone-implant interface and bone ingrowth were evaluated by undecalcified histological examination under light and fluorescent microscope as well as environmental scanning electron microscope (ESEM). The results show: osteoblasts are very active with fast proliferation and no adverse tissue reaction occurs for the porous NiTi alloy after 15 weeks implantation; porous NiTi alloy has better osteoconductivity and osteointegration than the bulk one; the osteoblasts can ingrow the pores of porous NiTi implant, and direct bone-implant interface can be observed by fluorescent light microscope.     

Shape memory response of porous NiTi shape memory alloys fabricated by selective laser melting

Porous NiTi scaffolds display unique bone-like properties including low stiffness and superelastic behavior which makes them promising for biomedical applications. The present article focuses on the techniques to enhance superelasticity of porous NiTi structures. Selective Laser Melting (SLM) method was employed to fabricate the dense and porous (32–58%) NiTi parts. The fabricated samples were subsequently heat-treated (solution annealing?+?aging at 350?°C for 15?min) and their thermo-mechanical properties were determined as functions of temperature and stress. Additionally, the mechanical behaviors of the samples were simulated and compared to the experimental results. It is shown that SLM NiTi with up to 58% porosity can display shape memory effect with full recovery under 100?MPa nominal stress. Dense SLM NiTi could show almost perfect superelasticity with strain recovery of 5.65 after 6% deformation at body temperatures. The strain recoveries were 3.5, 3.6, and 2.7% for samples with porosity levels of 32%, 45%, and 58%, respectively. Furthermore, it was shown that Young’s modulus (i.e., stiffness) of NiTi parts can be tuned by adjusting the porosity levels to match the properties of the bones.

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Tuning the mechanical properties of composites from elastomeric to rigid thermoplastic by controlled addition of carbon nanotubes

A commercial thermoplastic polyurethane is identified for which the addition of nanotubes dramatically improves its mechanical properties. Increasing the nanotube content from 0% to 40% results in an increase in modulus, Y, (0.4–2.2 GPa) and stress at 3% strain, σ_{? = 3%}, (10–50 MPa), no significant change in ultimate tensile strength, σ_B, (≈50 MPa) and decreases in strain at break, ?_B, (555–3%) and toughness, T, (177–1 MJ m^?3). This variation in properties spans the range from compliant and ductile, like an elastomer, at low mass fractions to stiff and brittle, like a rigid thermoplastic, at high nanotube content. For mid‐range nanotube contents (≈15%) the material behaves like a rigid thermoplastic with large ductility: Y = 1.5 GPa, σ_{? = 3%} = 36 MPa, σ_B = 55 MPa, ?_B = 100% and T = 50 MJ m^?3. Analysis suggests that soft polyurethane segments are immobilized by adsorption onto the nanotubes, resulting in large changes in mechanical properties.     

Processing of porous Ti and Ti5Mn foams by spark plasma sintering

Titanium and its alloys are one of the best metallic biomaterials to be used for implant application. In this study, porous Ti and Ti5Mn alloy with different porosities were successfully synthesized by powder metallurgy process with the addition of NH₄HCO₃ as space holder and TiH₂ as foaming agent. The consolidation of powder was achieved by spark plasma sintering process (SPS) at 16 MPa and pressureless conditions. The morphology of porous structure was investigated by using scanning electron microscopy (SEM) and X-ray micro-tomography (μ-CT). Nano-indentation tester was used to evaluate Young’s modulus of the porous Ti and Ti5Mn alloy. Experimental results showed that pure Ti sample, which sintered under pressure of 16 MPa, full relative density was achieved even at a relative low sintering temperature 750 °C; however, in the case of pressureless condition at sintering temperature 1000 °C the porosity was 53% and Young’s modulus was 40 GPa. The Ti5Mn alloy indicated a good pore distribution, and the porosity decreased from 56% to 21% by increasing the sintering temperature from 950 °C to 1100 °C. Young’s modulus was increased from 35 GPa to 51.83 GPa with increasing of the sintering temperatures from 950 °C to 1100 °C.     

Novel 3D porous multi-phase composite scaffolds based on PCL,thermoplastic zein and ha prepared via supercritical CO2 foaming for bone regeneration

The aim of this study was the design of novel biodegradable porous scaffolds for bone tissue engineering (bTE) via supercritical CO₂ (scCO₂) foaming process. The porous scaffolds were prepared from a poly(ε-caprolactone)-thermoplastic zein multi-phase blend w/o interdispersed hydroxyapatite particles (HA) and the porous structure achieved via the scCO₂ foaming technology. The control of scaffolds porosity was obtained by modulating materials formulation and foaming temperature (T_F). The scaffolds were subjected to morphological, micro-structural and biodegradation analyses, as well as in vitro biocompatibility tests. Results demonstrated that both HA concentration and T_F significantly affected the micro-structural features of the scaffolds. In particular, scaffolds with porosity and pore size distribution, mechanical properties and biodegradability adequate for bTE were designed and produced by selecting a T_F equal to 100 °C for all the compositions used. The biocompatibility of these scaffolds was assessed in vitro by using osteoblast-like MG63 and human mesenchymal stem cells (hMSCs).     

High-porosity NiTi superelastic alloys fabricated by low-pressure sintering using titanium hydride as pore-forming agent

Porous NiTi shape memory alloys (SMAs) were successfully fabricated by low-pressure sintering (LPS), and the pore features have been controlled by adjusting the processing parameters. The porous NiTi SMAs with high porosity (45%) and large pore size (200–350 μm) can be prepared by LPS using TiH_1.5 as pore-forming agent. These alloys exhibit isotropic pore structure with three-dimensional interconnected pores. The porous NiTi SMA produced by LPS exhibits superelasticity and mechanical properties superior to that by conventional sintering.     

The Effect of Porosity and Grain Size on the Phase Composition and Mechanical Properties of Zirconium-Dioxide-Based Ceramic

ZrO₂(Y) ceramic with embedded particles of a pore-forming agent—ultrahigh molecular weight polyethylene—has been studied. It has been shown that the porosity of samples after sintering changed from 2 to 42 vol % and the grain size changed from 0.5 to 1.55 μm depending on sintering regime. The strength of materials with minimum porosity was 3000 ± 200 MPa, while the strength of materials with maximum porosity was 100 ± 20 MPa, regardless of grain size. It has been shown that the tetragonal to monoclinic martensitic phase transformation related to mechanical stresses takes place in the material without any effect on the macrostrength of the material. Internal microscopic stresses decreasing with an increase in porosity and ceramic grain size are the main factor causing this transformation in a porous material.     

Asymmetrical Bending Model for NiTi Shape Memory Wires: Numerical Simulations and Experimental Analysis

Abstract: A detailed numerical and experimental study of a NiTi Shape Memory Alloy (SMA) wire subjected to bending is presented in order to provide a complete characterisation of the material under this load case. The beam model presented is based on the classic Euler‐Bernoulli theory and uses De la Flor one‐dimensional constitutive equations modified to take into account different material responses to tension and compression as well as the different elastic properties of austenite and martensite. All the necessary experimental techniques were designed to determine the bending behaviour of NiTi SMA wire over the entire range of transformation temperatures. These experimental bending results were then compared with the numerical results. The numerical model proposed agrees quantitatively and qualitatively with the experimental bending results obtained for NiTi wire, representing an effective tool for the analysis of one‐dimensional structural devices. A comparison of the numerical results that assume symmetrical behaviour between tension and compression with the results that assume asymmetrical behaviour has shown that the tension/compression asymmetry is more pronounced in the martensitic range and has little influence on the response of the SMA wire subjected to bending at temperatures above A_f. These results are analyzed and discussed.     

Functional Materials for Bone Regeneration from Beta‐Tricalcium Phosphate

Biodegradable ceramics of β‐tricalcium phosphate (β‐TCP, Ca₃(PO₄)₂) are widely used as bone regeneration materials. The goal is a complete regeneration of the bony defect (restitutio ad integrum = full recovery). Different bioceramics made of β‐TCP show fundamental differences in terms of phase purity, primary particle size, stability, porosity, solubility and therefore biodegradation of the material. Cerasorb® is a bioceramic consisting of phase pure β‐TCP. The primary particle size in connection with a stable sinter structure forms a porous biomaterial which is optimised in the functional surface, porosity and resorption/degradation behaviour. Different forms of Cerasorb® are available: granular materials with high and low porosity optimised for specific indications as well as block forms shapeable by the surgeon for various bony defects.     

High‐Performance Microwave‐Derived Multi‐Principal Element Alloy Coatings for Tribological Application

The authors report the development of Al_xCoCrFeNi (x = 0.1 to 3) high entropy alloy (HEA) coatings using a simple and straightforward microwave technique. The microstructure of the developed coatings is composed of a cellular structure and diffused interface with the substrate. The microstructure of the HEA coatings varies as a direct function of Al content. An increase in Al fraction shows structural transformation from FCC to BCC along with the evolution of σ and B₂ as the major secondary phases. The diffusion of Mo from the substrate enhances the mixing entropy and promotes σ‐phase formation. The HEA coatings show significantly high hardness compared to SS316L substrate steel (227 HV) with a maximum value of 726 HV observed for three‐molar composition. The fracture toughness exhibits an inverse correlation with the Al fraction with the highest value of around 49 MPa m^1/2 observed for Al_0.1CoCrFeNi coating. The equimolar coating composition shows lowest erosion rates among all the tested samples due to optimum combination of the mechanical properties. The erosion resistance of the equimolar coating is 2 to 5 times higher than steel substrate and around 1.5 times higher than the non‐equimolar counterparts depending upon the impingement angles.

     

Effects of binder system and processing parameters on formability of porous Ti/HA composite through powder injection molding

Porous titanium-hydroxyapatite (Ti/HA) composite is a developed composite material suitable for bio-medical applications. Powder injection molding (PIM) with space holder method is used to produce porous Ti/HA with mechanical properties, similar to human bone, and pores helps to initiate tissue growth. However, the differences in physical and mechanical properties of these composites are the main challenges during debinding and sintering. Therefore, the main objective is to determine effects of binder systems and processing parameters on formability of Ti/HA composite. In PIM, a binder system is necessary to produce green and ultimately sintered part. There are two binder systems and variation of sintering temperature has been used. Results revealed that Polyethylene glycol (PEG)-based binder system is applicable with NaCl space holder and optimum sintering parameters, including temperature, heating rate, and holding time of 1300 °C, 10 °C/min, and 5 h, respectively. The fabricated porous Ti/HA exhibits average porosity, pore size distribution, compressive strength, and roughness values of 55%, 60 μm to 170 μm, 370 MPa, and 0.323 μm, respectively. FESEM results showed that the pores are interconnected. It may be an appropriate material for future bio-medical applications.     

Uniform porous and functionally graded porous titanium fabricated via space holder technique with spark plasma sintering for biomedical applications

Porous materials with low stiffness and high strength are sought as implant materials to prevent stress shielding and fracture during in vivo use. This study proposes a powder metallurgy-based space holder technique to fabricate porous titanium with mechanical performance suitable for implant materials. Mixed powders of titanium and sodium chloride were sintered at low temperature using spark plasma sintering, and then the sodium chloride was dissolved in water. As a result, uniform porous titanium (UP-Ti) with a wide range of microstructures: porosity from 26% to 80% and average pore size from 75 μm to 475 μm was successfully fabricated. Also, functionally graded porous titanium (FGP-Ti) was successfully fabricated, in which porous titanium with high porosity and dense titanium were placed at the inside and surface, respectively. The stiffness of UP-Ti was comparable to that of natural bones, but its strength was lower than that of natural bones, which would be insufficient for use as an implant. In contrast, the mechanical performance of FGP-Ti was improved, compared with UP-Ti with the porosity comparable to the average porosity of FGP-Ti: its strength was higher than that of natural bones and its stiffness was comparable to that of natural bones. These results imply that porous titanium, especially functionally graded porous titanium, is a candidate metal for implants used to replace heavily loaded natural bone.     

表面多孔NiTi-羟基磷灰石/NiTi生物复合材料的制备与性能

利用放电等离子烧结技术制备了表面多孔NiTi-羟基磷灰石(HA)/NiTi生物复合材料,研究了烧结温度对复合材料宏观形貌、微观结构、表面孔隙特征、力学性能及体外生物活性的影响。结果表明:随着烧结温度从800℃提高到950℃,NiTi-HA/NiTi复合材料由复杂的Ti、Ni、Ti_2Ni、Ni_3Ti、HA混合相逐渐转变为单一的NiTi+HA相,内外层界面形成稳定的冶金结合且表面孔隙率与平均孔径呈缓慢减小趋势;同时抗压强度显著提高而弹性模量变化不明显。与传统NiTi、多孔NiTi及多孔NiTi-HA材料相比,950℃温度下制备的NiTi-HA/NiTi复合材料不仅具有良好的界面结合和表面孔隙特征(孔隙率45.6%、平均孔径393μm)、较高的抗压强度(1 301MPa)、较低的弹性模量(10.2GPa)以及优异的超弹性行为(超弹性恢复应变4%)的最佳匹配,而且还具有良好的体外生物活性。