Background technology
Titanium or titanium alloy has high specific strength, good corrosion resistance, enough wearability and good biocompatibility, is considered at present the most rising biomedical metal material.But, the elastic modelling quantity of fine and close titanium or titanium alloy (55~110GPa) with natural bone (3.21~30GPa) do not mate, so that load can not be delivered to adjacent bone tissue well by implant, " stress shielding " phenomenon namely appears, the bone stress absorption appears around causing implant, cause implant to become flexible or fracture, and make the implant surgery failure.The metal material of loose structure, because the existence of hole, not only can effectively reduce its elastic modelling quantity and intensity, the biomechanical property of itself and natural bone is complementary, and can also promote cell to grow into, and the passage of providing convenience for the exchange of the transportation of nutriment and body fluid, be a kind of more preferably biological implantation material.
Ti-6Al-4V is that using the most extensive at present also is the titanium alloy that is used to the earliest biomedical sector, along with research deepens continuously, find that Al and V are harmful in recent years, Al can cause abalienation and bring out senile dementia, V can react with tissue, forms Heisui River.Therefore, the novel titanium alloy material of research and development seems more and more important.Mo is the β phase stable element of Ti, and belong to isomorphism structure with Ti, can form unlimited solid solution with Ti, not only reduce temperature and elastic modelling quantity that α-Ti changes to β-Ti, and can improve intensity and the wearability of Ti, preparation Ti-Mo porous embedded material is a kind of very attractive selection.
The porous metal material of bio-medical is complex-shaped, and its size varies with each individual, and needs personalized designs and makes fast.At present, traditional powder metallurgy die pressing, slurry foaming and the gel injection-moulding method of the many employings of the technology of preparing of porous titanium alloy.Wherein, die pressing adopts the titanium valve compacting of adding pore creating material to form, and preparation technology is simple, and institutional framework is even, but hole dimension is little, and porosity is low; Slurry foaming, though can obtain the POROUS TITANIUM of high porosity, only the addition by blowing agent is difficult to control hole gap structure (such as pore radiuses and distribution); The gel injection-moulding method has added the multiple additives such as organic matter, defoamer and dispersant when the preparation POROUS TITANIUM, not only contaminated environment increases cost, and brings a lot of problems for follow-up removing process.In a word, traditional preparation method of POROUS TITANIUM all needs particular manufacturing craft, high and the forming accuracy of cost can't guarantee, be not suitable for single-piece or small lot batch manufacture, can't obtain especially complex-shaped loose structure implant, RP technique can effectively address this problem.
RP technique (Rapid Prototyping is called for short the RP technology) starts from the eighties in 20th century, is a kind of new manufacture that integrates CAD, laser processing technology, Numeric Control Technology and new material technology.By mapping softwares such as CAD, Pro E, or the medical image that CT scan, MRI technology and additive method obtain carried out calculation system, obtain threedimensional model; Adopt discrete/stack shaping principle, laser beam is processed according to pre-designed machined parameters and according to the two-dimensional silhouette information of each synusia, and this series of layers sheet is deposited in together the generating three-dimensional entity by the shaping order under computer control.Selective laser sintering (selective laser sintering is called for short SLS) is a kind of important RP technique, adopts CO
2Laser instrument is thermal source, in forming process, the pressure that powder is subject to is very little, so the material of SLS technique preparation is loose structure normally, and rough surface, and this just biological and medicinal implant material for promoting cell to grow into and adhere to needed, the face shaping of implant can change arbitrarily by three-dimensional modeling, can realize the personalized designs of implant and fast manufacturing, and have that raw material are selected extensively, technical process is simple, forming efficiency is high, need not the advantage such as support, the using value at medical domain is more and more come into one's own in recent years.
Adopting the multiporous biological medical material majority of SLS technology preparation is composite (the Tan K H of polymeric material or polymer/ceramic, Chua C K, Leong K F, et al.Selective laser sintering of biocompatible polymers for applications in tissue engineering[J] .Biomedical materials and engineering, 2005,15(1-2): 113-124; Zhang Y, Hao L, Savalani M M, et al.Characterization and dynamic mechanical analysis of selective laser sintered hydroxyapatite filled polymeric composites[J] .Journal of Biomedical Materials Research Part A, 2008,86(3): 607-616; Eosoly S, Brabazon D, Lohfeld S, et al.Selective laser sintering of hydroxyapatite/poly-ε-caprolactone scaffolds[J] .Acta Biomaterialia, 2010,6(7): 2511-2517), these material mechanical performances are generally on the low side, can not satisfy the mechanical compatibility requirement of bio-medical material, and titanium maxter alloy has good biocompatibility and mechanical property, does not also see the relevant report that the SLS technology is applied to prepare the POROUS TITANIUM molybdenum alloy material at present.
Summary of the invention
The object of the present invention is to provide a kind of method of making the bio-medical porous titanium alloy implant of any complicated shape, to remedy the deficiency of traditional technology of preparing, enlarge the application of Selective Laser Sintering, efficiently prepare the titanium alloy implant of the complicated shape that satisfies medical material biocompatibility and mechanical compatibility requirement.
A kind of method for preparing complicated shape bio-medical porous titanium molybdenum alloy implant, it is characterized in that: at first adopt Auto CAD, Pro/E mapping software, maybe will carry out datumization by the medical photography figure that CT scan, MRI technology obtain, design the threedimensional model of implant; Ti, Mo elemental metalpowder are carried out mechanical uniform with the organic polymer powder mix, Mo content is 2~15wt% in the elemental metalpowder, and surplus is Ti, and organic macromolecule content accounts for the 3wt%-15wt% of metal dust total amount; Under argon shield, adopt CO
2Laser beam carries out selective laser sintering (SLS) with mixed-powder, obtains having the preform of the Ti-Mo alloy material implant of given shape; Under vacuum or argon shield, the shaping base is carried out hot degreasing and high temperature sintering, sintering temperature is 800~1500 ℃, namely obtains bio-medical porous Ti-Mo alloy implant.
Concrete technology flow process and parameter are as follows:
(1) adopt ball-milling technology that material powder is carried out mechanical mixture, its technological parameter is: ratio of grinding media to material is 3:1~1:1, Ball-milling Time 3~12h, rotating speed 30~100r/min;
(2) according to different patients' needs, adopt Pro E, CAD or CT scan, MRI technology, the threedimensional model of structure implant can carry out to the implant (such as cantilever, hollow and insert structure etc.) of any complicated shape the design of Extraordinary threedimensional model;
(3) be under the protection of 99.0%~99.9% inert argon, with CO in purity
2Laser instrument is thermal source, according to pre-designed processing route mixed-powder is carried out selective laser sintering (SLS), obtains the green part of required implant.The SLS technological parameter is: laser power: 10~40W, and sweep speed is 1500~2500mm/s, and sweep span is 0.08~0.25mm, and slice thickness is 0.08~0.25mm, and powder bed preheat temperature is 45~160 ℃;
(4) under vacuum or inert gas shielding, the implant green part is put into debinding furnace, directly carry out hot degreasing; The degreasing main technologic parameters is: skimming temp is 20~750 ℃, and temperature retention time is 0.5~3h, and removing speed is 1~5 ℃/min;
(5) under vacuum or inert gas shielding, implant degreasing part is put into sintering furnace, carry out high temperature sintering, finally obtain the titanium maxter alloy implant.The sintering main technologic parameters is: 800~1500 ℃ of sintering temperatures, temperature retention time are 0.5~3h, and heating rate is 1~5 ℃/min.
The particle diameter of described raw material Ti powder, Mo powder and polymeric powder is respectively: 100~325 orders, 100~500 orders and 100~800 orders.
Described high-molecular organic material is thermoplastic resin and thermosetting resin; Thermoplastic resin comprises polyethylene, high density polyethylene (HDPE), polypropylene, polystyrene, polyamide, polymethyl methacrylate, Merlon or ethylene-vinyl acetate copolymer, and thermosetting resin comprises phenolic resins, melamine, amino resins or epoxy resin.
Advantage of the present invention is:
(1) in the face of different patients' demand, can personalized designs, and directly prepare the bio-medical implant of any complicated shape and high dimensional accuracy;
(2) be easy to regulate alloying component, stock utilization is high, additive level is few, little to material and environmental pollution;
(3) forming technology has digitlization and without the technical characterstic of modelling, step of preparation process is simple, and operability and repeatability are strong;
(4) by regulating Mo content, SLS forming technology and sintering process parameter, can realize the control of pore character, matrix microscopic structure and the mechanical property of porous Ti-Mo alloy material;
(5) prepared titanium maxter alloy material hole even tissue, porosity, percent opening and aperture adjustable extent is wide, mechanical property is excellent, its elastic modelling quantity and intensity and natural bone coupling can satisfy as the needed biomechanical compatibility requirement of bio-medical material.
The specific embodiment
Embodiment 1
Preparation raw material powder: at first adopt electronic balance to take by weighing respectively 300 order Ti powder 340g, 200 order Mo powder 60g, 160 purpose high density polyethylene (HDPE) (HDPE) powder 35g, then above-mentioned powder is packed into and mix in the ball mill, ratio of grinding media to material is 3:1, and Ball-milling Time is 10h, and rotating speed is 55r/min;
Make up threedimensional model: use Pro E software, the 3D shape of drawing implant, and adopt delamination software that threedimensional model is carried out slicing treatment, the two-dimentional lamella information that processing is obtained stores the forming machine of selective laser sintering into the STL form;
Selective laser sintering (SLS): take forming accuracy and green strength as standard, laser beam carries out selective laser sintering (SLS) according to two-dimentional lamella information, and all lamellas is successively coupled together under computer control, obtains implant.Choose the SLS technological parameter of optimization: laser power 34W, sweep speed 1650mm/s, sweep span 0.18mm, slice thickness 0.18mm, 100 ℃ of preheat temperatures;
Hot degreasing: be under 99.8% the argon shield, the implant that SLS is shaped to be put into debinding furnace in purity, to remove organic polymer, degreasing process was divided into for three steps: the first step, and 25~250 ℃, 5 ℃/min of programming rate does not need insulation; Second step, 250~420 ℃, 3 ℃/min of heating rate, insulation 1h; In the 3rd step, 420~600 ℃, 2 ℃/min of heating rate is incubated 1h, and cools off with stove;
High temperature sintering: the implant through degreasing is put into the sintering furnace that vacuum is 2Pa, sinter to 1200 ℃ from room temperature, 3 ℃/min of heating rate, and at 1200 ℃ of insulation 3h, with the stove cooling, obtain the porous implant of Ti-15Mo alloy.
By Measurement and analysis, the porosity of the Ti-15Mo alloy that this technique obtains is 52.8%, and percent opening is 48.6%, and pore size is 180 μ m; Elastic modelling quantity is 5.55GPa, and compressive yield strength is 113.56MPa, with the elastic modelling quantity of people's bone (3.21~30GPa) and compression strength (130~180MPa) is very approaching.
Embodiment 2
On the basis of embodiment 1, only change quality proportioning and the high temperature sintering temperature of Ti powder and Mo powder, i.e. Ti/Mo=9/1 is heated to 1500 ℃ from room temperature by the heating rate of 3 ℃/min, and be incubated 3 hours, with the stove cooling, obtain the Ti-10Mo alloy afterwards, its porosity is 18%, percent opening is 16.3%, the aperture mean size is 30 μ m, and elastic modelling quantity is 54.89MPa, and compressive yield strength is 486.38 MPa.
Embodiment 3
Preparation raw material powder: at first adopt electronic balance to take by weighing respectively 100 purpose Ti powder 460g, 325 purpose Mo powder 40g, 400 purpose polystyrene (PS) powder 30g, then above-mentioned powder is packed into and mix in the ball mill, ratio of grinding media to material is 2:1, and Ball-milling Time is 8h, and rotating speed is 70r/min;
Make up threedimensional model: the 3D shape of using CAD to draw implant, and adopt delamination software that threedimensional model is carried out slicing treatment, the two-dimentional lamella information that processing is obtained stores the forming machine of selective laser sintering into the STL form;
Selective laser sintering (SLS): take forming accuracy and green strength as standard, laser beam carries out selective laser sintering (SLS) according to two-dimentional lamella information, and all lamellas is successively coupled together under computer control, obtains implant.Choose the SLS technological parameter of optimization: laser power 23W, sweep speed 1800mm/s, sweep span 0.20mm, slice thickness 0.20mm, 130 ℃ of preheat temperatures;
Hot degreasing: be under 99.8% the argon shield, the implant that SLS is shaped to be put into debinding furnace in purity, to remove organic polymer, degreasing process was divided into for three steps: the first step, and 25~300 ℃, 5 ℃/min of programming rate does not need insulation; Second step, 300~550 ℃, 3 ℃/min of heating rate, insulation 2h; In the 3rd step, 550~700 ℃, 2 ℃/min of heating rate is incubated 1h, and cools off with stove;
High temperature sintering: the implant through degreasing is put into the sintering furnace that vacuum is 2Pa, sinter to 1250 ℃ from room temperature, 3 ℃/min of heating rate, and at 1250 ℃ of insulation 2h, with the stove cooling, obtain the porous implant of Ti-8Mo alloy.
By Measurement and analysis, the porosity of the Ti-8Mo alloy that this technique obtains is 37.35%, and percent opening is 35.72%, and the maximum diameter of hole reaches 120 μ m; Elastic modelling quantity is 17.76GPa, and compressive yield strength is 255.96MPa
Embodiment 4
On the basis of embodiment 3, only change the content of binding agent, polystyrene becomes 10g by 30g, namely accounts for the 2wt% of metal dust total amount, is shaped by identical SLS technological parameter, obtains the Ti-8Mo preform.
In SLS is shaped the follow-up clear powder process that finishes, preform causes intensity too little because binder content is excessively low, slightly careless or the big city of exerting oneself is damaged during operation, just seem more difficult for back carrying and transportation to carry out degreasing and sintering process, especially thin-wall part more easily damages.
This shows, in order to obtain enough green strengths, with convenient follow-up operational processes, the content of binding agent must be controlled at 3wt% and more than; For complicated shape and large-sized thin-wall part, the content of binding agent should increase relatively, and the upper limit can be controlled in the 15wt%.
Embodiment 5
Preparation raw material powder: at first adopt electronic balance weighing 200 purpose Ti powder 480g, 400 purpose molybdenum powder 20g, 300 purpose polyamide (PA) powder 20g, then above-mentioned powder is packed into and mix in the ball mill, ratio of grinding media to material is 1:1, and Ball-milling Time is 6h, and rotating speed is 40r/min;
Make up threedimensional model: the 3D shape of using CAD to draw implant, and adopt delamination software that threedimensional model is carried out slicing treatment, the two-dimentional lamella information that processing is obtained stores the forming machine of selective laser sintering into the STL form;
Selective laser sintering (SLS): take forming accuracy and green strength as standard, laser beam carries out selective laser sintering (SLS) according to two-dimentional lamella information, and all lamellas is successively coupled together under computer control, obtains implant.Choose the SLS technological parameter of optimization: laser power 18W, sweep speed 2000mm/s, sweep span 0.25mm, slice thickness 0.25mm, 155 ℃ of preheat temperatures;
Hot degreasing: be under 99.8% the argon shield, the implant that SLS is shaped to be put into debinding furnace in purity, to remove organic polymer, degreasing process was divided into for three steps: the first step, and 25~350 ℃, 5 ℃/min of programming rate does not need insulation; Second step, 350~500 ℃, 2 ℃/min of heating rate, insulation 2h; In the 3rd step, 500~600 ℃, 3 ℃/min of heating rate is incubated 1h, and cools off with stove;
High temperature sintering: the implant through degreasing is put into the sintering furnace that vacuum is 2Pa, be warming up to 1100 ℃ from room temperature, 3 ℃/min of heating rate, and at 1100 ℃ of insulation 2h, with the stove cooling, obtain the porous implant of Ti-4Mo alloy, its porosity is 48.79%, percent opening is 47%, and the maximum diameter of hole reaches 160 μ m; Elastic modelling quantity is 4.18GPa, and compressive yield strength is 103.74MPa.
Embodiment 6
This example preparation porous Ti-2Mo alloy is selected 200 order titanium valves, 325 order molybdenum powders, and 300 order phenolic resins are material powder, adopt ball mill to mix: ratio of grinding media to material 2:1, rotating speed 40r/min, ball milling 6h; Selective laser sintering (SLS), 20 ℃ of powder bed tempertaure stuck-at-1s, table one are SLS technological parameter corresponding to the phenolic resins of different content.
Table 1 mixed-powder SLS forming technology
By the preform that above SLS technological parameter obtains, degreasing in the argon gas atmosphere of purity 〉=99.5%, to be bonded dose decompose fully and volatilize after, put into vacuum drying oven and sinter to 800 ℃, and insulation 2h, with stove cooling, obtain porous Ti-2Mo alloy afterwards.By analysis, the porosity of Ti-2Mo alloy can reach 60%, pore size 50~200 μ m, and elastic modelling quantity is 3.25GPa, compressive yield strength is 78.84 MPa.