The development of porous titanium products using slip casting

An optimized titanium slurry was developed from 43 vol.% of titanium powder, 0.3 dw.% of dispersant, 0.8 dw.% of plasticizer and 0.8 dw.% of binder, mixed with a balance of distilled water, which produced a viscosity of 40 cP. It was then poured into a plaster mold to form compacts with a green density of 45%. Thermal debinding was carried out at 320 °C with an argon flow for 2 h, followed by vacuum sintering different samples at 1000 °C and 1200 °C for 0.5 h, respectively. The porous sintered compacts had satisfactory tensile strength with some plastic deformation. The increase in oxygen and carbon content during processing was minor. An X-ray diffraction pattern showed pure alpha titanium peaks without any indication of contamination from organic additives. The results from this investigation suggested that slip casting is a potentially low-cost, simple production route for manufacturing porous titanium products.     

Mechanical properties and the structure of porous titanium obtained by sintering compacted titanium sponge

Mechanical properties and characteristics of the porous material obtained by sintering of compacted granules of titanium sponge of grade TG-OP-01 have been investigated with the purpose to develop a technology of production of biocompatible orthoimplants. The content of pores θ was from 20 to 60%. As θ increased from 20 to 50%, the Brinell hardness H _B, maximum bending strength σ_bend, and impact toughness K _c decreased, following the empirical dependences H _Bθ = const, σ_bend × θ² = const, and K _c × θ^1.5 = const, respectively. At θ > 50%, there was observed a stronger drop in these values. The experiments on the absorption of water by the pores and an analysis of the filtration properties of the material made it possible to establish that the basis of the system of pores connected with the surface is composed by the gaps between the pressed granules 0.1–0.2 cm sintered during annealing rather than by the small (～ 100 μm) pores in the granules.     

Warm die compaction and sintering of titanium and titanium alloy powders

A study has been made of the effect of non-lubricated warm die (200 °C) compaction on the densification of hydride–dehydride (HDH) Ti powder, pre-alloyed (PA) Ti-6Al-4V and Ti-10V-2Fe-3Al powders, and HDH Ti and V-Fe-Al master alloy powder blends, compared to cold die compaction. Depending on the compaction pressure, which was varied from 200 to 1000 MPa, non-lubricated warm die (200 °C) compaction was very effective for −100 mesh HDH Ti powder, increasing the green density by 5.0–9.4% theoretical density (TD). Die wall lubrication with stearic acid showed no influence on the green density when compacted at 800 MPa. With warm die (200 °C) compaction, achieving a green density of greater than 90%TD was straightforward for HDH Ti powder when compacted at ≥750 MPa. Accordingly, near pore-free (≥99.5%TD) Ti microstructures were obtained after sintering at 1300 °C for 120 min in vacuum when compacted at 1000 MPa. The resulting increment in the sintered density was between 2.0%TD and 4.4%TD. Warm die (200 °C) compaction showed no effect on PA Ti-10V-2Fe-3Al powder and only a small effect on PA Ti-6Al-4V powder when compacted at 1000 MPa. However, it was still virtually effective for Ti-10V-2Fe-3Al powder blends made of HDH Ti powder and V-Fe-Al master alloy powder. The observations were compared with literature data and discussed in accordance with the yield strength of Ti, Ti-6Al-4V, Ti-10V-2Fe-3Al and Al₃V as a function of temperature.     

Development of porous Ti6Al4V samples by microsphere sintering

Two differently sized microspheres were sintered at 1300 °C and 1400 °C from 2 to 8 h in stoneware, alumina, yttria and zirconia moulds. Selecting the appropriate material to be used as a mould remains a critical issue given titanium's high reactivity at elevated temperatures. Optimum mechanical properties were obtained when sintering the smallest microspheres in yttria-coated moulds. Stiffness of the samples was lower than 40% of that of the bulk solid material, which comes closer to that of human cortical bone. Open and interconnected porosity was observed in all the specimens.     

Nitridation of Ti-6Al-4V powder in thermal plasma conditions and sintering of obtained TiN powder

This study is devoted to plasma nitridation of a Ti-6Al-4V powder, and sintering of reaction products so-obtained.Ti-6Al-4V spherical particles (22-45 μm) were injected in a plasma jet using N₂ as plasma gas and collected in two spots: in a cold area located far from the torch and in a hot area submitted to the plasma thermal effect. After plasma nitridation, particles of substoichiometric titanium nitride (TiN_1−x) with no nitrogen gradient were obtained. The reduction of nitrogen concentration in plasma gas improved the massic output of gathered powders. These powders were not exclusively composed by TiN_1−x, since titanium alloy often remained, and a secondary phase β-Ti containing vanadium and aluminium was always present inside the grains. The nitridation rate depended on the collected area. Titanium oxide (rutile) was detected in powders collected in the hot area.Titanium nitride powders in which no rutile was detected were hot pressed up to 1450 °C under flowing nitrogen. In this case, the densification rate did not overload 83% of theoretical value. This fact can be explained by the nitridation of both TiN_1−x and titanium intermetallic phases during the heat treatment. In the case of inert atmosphere (argon), there was only the densification phenomenon which gave a density close to the theoretical value.This work has to be developed on the one hand to improve powder synthesis and its natural sintering, and on the other hand to approach hot pressing sintering mechanism.     

Magnetic properties of nanocrystalline Ni3Fe compacts prepared by spark plasma sintering

Nanocrystalline Ni₃Fe compacts were successfully prepared by spark plasma sintering starting from wet mechanically alloyed powders. The influences of the sintering conditions: sintering temperature, sintering time and particle size on the compact magnetic properties are investigated. It is found that high sintering temperature, increased sintering duration and larger particle size leads to compacts with improved soft magnetic properties. A contamination with carbon of the compacts during the sintering processes has been found to reduce their magnetic properties. It is found that a heat treatment at the temperature of 450 °C during 4 h, in hydrogen atmosphere, leads to an improvement of the compact coercivity and of the maximum relative permeability of the compact to up to 600% and 50% respectively. Spark plasma sintering can consequently be considered as promising compaction technique for processing Ni₃Fe nanocrystalline powder in particular and nanocrystalline soft magnetic alloys in general.     

颗粒尺寸对微波烧结多孔NiTi合金的显微结构及力学性能的影响

以不同颗粒尺寸的Ni/Ti粉末为原料,采用微波烧结技术制备了多孔NiTi合金,并系统考察了颗粒尺寸对多孔NiTi合金的显微结构和力学性能的影响。结果表明,随着颗粒尺寸的减小,多孔NiTi合金中的Ti2Ni和Ni3Ti第二相减少而单质Ni相消失。同时,多孔NiTi合金的孔隙形貌由带尖角的不规则形状向近球形转变。此外,多孔NiTi合金的孔隙率和孔径随着颗粒尺寸的增大而增大,而洛氏硬度、抗压强度和抗弯强度均下降。因此,减小颗粒尺寸有利于获得理想的显微结构(纯净的物相和均匀的孔隙结构)和提高微波烧结多孔NiTi合金的力学性能。     

Study of metal injection molding of highly porous titanium by physical modeling and direct experiments

The prospects of metal injection molding (MIM) technique for manufacturing of highly porous titanium parts was studied by physical modeling, based on feedstock warm compaction experiments. The space holder method and typical MIM binder were used in all cases of the study. The influence of the starting powder (dehydrided and atomized) in feedstock on resulting properties of porous titanium was investigated. The size of space holder particles and space holder amount were adjusted to obtain porosity and pore size desired for medical implants application. NaCl and KCl were studied and compared as prospective space holder materials. The porous samples were characterized regarding their microstructure, uptake of interstitial contents and mechanical properties. For comparison, same investigations have been conducted on samples, which were prepared by established space holder technology based on cold isostatic pressing (CIP) and sintering. Finally, first direct MIM experiments and attempts of feedstock optimization were carried out. The peculiarities and problems of metal injection molding of highly porous titanium have been discussed.     

低温冷轧工艺制备纳米晶纯钛及其力学性能

为研究低温冷轧工艺对商业纯钛(CP-Ti)组织和性能的影响,在液氮温区对商业纯钛TA2进行冷轧。利用X射线衍射(X-ray diffraction,XRD)、透射电镜(Transmission electron microscope,TEM)表征变形后的组织;使用纳米压痕技术研究其力学性能。结果表明,低温冷轧工艺能有效的将晶粒从57μm细化到75nm;细化后的纳米晶纯钛的硬度高达3.36GPa。     

Processing and characterization of porous titanium for implants by using NaCl as space holder

Porous samples of commercially pure titanium (CP Ti) were fabricated by using sodium chloride (NaCl) as space-holder with percentages between 40 and 70 vol%. The dissolution of NaCl in distilled water, the structural integrity of samples and the reproducibility of the procedure were studied as a step prior to sintering. All these parameters were evaluated in terms of the compaction pressure, temperature and agitation of water, and dissolution time. The characterization of samples included density, porosity and dynamic Young's modulus. The results indicate that the most efficient lixiviation, according to the desired balance of properties, was by immersion in hot water, without agitation and for prolonged cycles of immersion time.     

Porosity and mechanical properties of porous titanium fabricated by gelcasting

Porous Ti compacts with large size and complex shape for biomedical applications were fabricated in the porosity range from 40.5% to 53.8% by controlling gelcasting parameters and sintering conditions. The experimental results show that the total porosity and open porosity of porous titanium compacts gelcast from the Ti slurry with 34 vol.% solid loading and sintered at 1100℃ for 1.5 h are 46.5% and 40.7%, respectively, and the mechanical properties are as follows： compressive strength 158.6 MPa and Young＇s modulus 8.5 GPa, which are similar to those of human cortical bone and appropriate for implanting purpose.     

激光烧结制备CrFeNiAlSiCux多孔高熵合金组织与性能

在Cr、Fe、Ni、Al、Si纯粉末中添加非等摩尔比的Cu元素混合后压制成坯,采用激光自蔓延烧结制备CrFeNiAlSiCux（x=0-1.2）高熵合金。通过OM、XRD、SEM和EDS、维氏显微硬度计、磨粒磨损机及电化学工作站进行表征,分析物相结构、显微组织、密度和孔隙率、硬度、耐磨及耐蚀性能。结果表明：合金中BCC和FCC两相共存,随着Cu元素添加,FCC相增多,但BCC相仍多于FCC相,合金是典型树枝晶组织并伴有许多菊花状的组织,菊花状组织主要含有Cr、Fe、Si、Ni元素,枝晶间组织主要含有Cu元素。CrFeNiAlSiCu0.4综合性能最佳,显微硬度最大,为908.68 HV,单位面积磨损量最小,为48 mg·cm-2,腐蚀电流最小,为0.4100 μA/cm-2,腐蚀电位最大,为-149.264 mV。     

Effect of thermal cycling through the martensitic transition on the internal friction and Young’s modulus of a Ni50.8Ti49.2 alloy

The internal friction (IF) and Young’s modulus (E) of a Ni_50.8Ti_49.2 is affected by thermal cycling. With increasing the number n of thermal cycles, the IF peak P_AM (P_MA) occurring at the austenite/martensite transition temperature decreases to disappear almost completely. Meanwhile the associated E(T) minimum at the beginning (n<250) deepens and then becomes progressively shallower and wider (3×10³≤n<18×10³). The strong sensitivity of P_AM (P_MA) to thermal cycling and to impurity (hydrogen) contents suggests that this peak is predominantly associated with stress-assisted collective motions of twin boundaries located inside the martensite platelets embedded within the austenite phase, rather than with the martensitic transition itself. However, as the high temperature tail of P_AM starts at temperatures appreciably higher than the martensite start-temperature M_s, a premartensitic contribution to damping is also present. The widening of the E(T) minimum indicates that, for n≥3×10³, the direct transformation is to some extent hindered by the dislocation network introduced by thermal cycling. A not thermally activated IF peak P_TWM, which is believed to be due to stress-assisted motions of (001) compound twin boundaries in the homogeneous martensite state, grows with increasing n.     

Large-scale aluminum foam plate fabricated by enhanced friction powder compaction process based on sintering and dissolution process

An enhanced friction powder compaction (FPC) process was proposed for fabricating a large plate of aluminum foam by the sintering and dissolution process. In this process, the rotating tool plunged into the die filled with a powder mixture of aluminum and NaCl during the FPC process was made to traverse perpendicularly to the direction of plunging as in the case of friction stir welding. In the enhanced FPC process, no external heat source, such as an electric furnace or a spark plasma sintering, was necessary for fabricating aluminum foam, except for the friction heat generated by traversing the rotating tool. It was found that a long plate of aluminum foam can be fabricated with a length equal to the tool traversing length. By X-ray computed tomography (CT) and scanning electron microscopy (SEM) observations of the pore structures of the fabricated aluminum foam, it was found that the entire sample had a pore structures that was similar to the NaCl morphology, regardless of the position along the traversing direction. The fabricated aluminum foam had a similar stress–strain curve to that of aluminum foam fabricated by spark plasma sintering and exhibited ductile fracture. This is considered to be attributed to the good bonding between aluminum particles in the entire sample. The fabricated aluminum foam exhibited almost the same plateau stress regardless of the position along the traversing direction.     

烧结温度对多孑L钛组织结构与性能的影响

分别在1000、1100、1200、1300和1400℃下真空烧结制备了多孔钛试样,并对多孔钛试样进行孔结构、组织结构和性能检测,研究了烧结温度与多孔钛的结构和性能的关系。结果表明:随着烧结温度的提高,多孔钛中颗粒边缘由尖锐变圆滑,孔型由不规则形向圆形转变,烧结颈由细变粗进而出现颗粒表面熔化,孔隙率下降。硬度随烧结温度的提高,呈现先升后降的变化规律,抗压强度逐步提高。     

Mechanical properties of highly porous Ti49.5Ni50.5 biomaterials

Ti_49.5Ni_50.5 shape memory alloy fibers were prepared by a melt overflow process. The martensitic transformation starting temperature of B2 → B19′ in the rapidly solidified fibers was 19 °C. Cylindrical billets of Ni-rich Ti–Ni alloy with 75% porosity were produced by a vacuum sintering technology using as-cast alloy fibers. The mechanical properties and shape memory properties of the highly porous Ti–Ni alloy is investigated using a compressive test. The plateau of the stress–strain curve was observed at about 7 MPa and resulted in 8% elongation associated with stress-induced B2 → B19′ transformation. Because of the high porosity of this specimen, the elastic modulus of about 0.95 GPa could be obtained. It was also found that a recovered strain was 5.9% on heating after the compressive deformation. This recovery of the length is ascribed to the shape memory effect which occurs during the martensitic transformation.     

新型Ti-Fe-Mo-Mn-Nb-Zr系钛合金的力学性能

在纯钛中加入Fe,Mo,Mn,Nb和Zr强化元素制成新型Ti-Fe-Mo-Mn-Nb-Zr系钛合金,测定了该材料的硬度、压缩强度及弹性模量等性能,考察了加入元素对硬度、压缩强度的影响规律.实验结果表明该合金形成了等轴α+β组织,与其它现有牙科用钛合金相比,硬度、弹性模量更接近牙本质的,且压缩性能明显优于其它牙科用钛合金.