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CN103740963A - Method for preparing porous tantalum medical implant material by selective laser sintering formation - Google Patents

Method for preparing porous tantalum medical implant material by selective laser sintering formation Download PDF

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CN103740963A
CN103740963A CN201310692704.5A CN201310692704A CN103740963A CN 103740963 A CN103740963 A CN 103740963A CN 201310692704 A CN201310692704 A CN 201310692704A CN 103740963 A CN103740963 A CN 103740963A
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CN103740963B (en
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叶雷
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Chongqing Runze Pharmaceutical Co Ltd
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Abstract

The invention relates to a preparation method of a porous tantalum medical implant material. The preparation method comprises the following steps: by adopting pure tantalum powder with the particle size of not more than 10mu m as a raw material, directly performing selective laser sintering formation to form a human bone metal biomimetic material, wherein the thickness of powder spread in each layer during selective laser sintering is 60-80mu m; further sintering and cooling the formed human bone metal biomimetic material to obtain the porous tantalum medical implant material. The porous tantalum medical implant material with complete three-dimensional communication is obtained by sintering and cooling treatment of a formed blank prepared by selective laser sintering, and has a consistent microstructure with a bone tissue of a human body, so that the porous metal implant material has good biocompatibility and biological safety. The method provided by the invention further has the advantages of simple process equipment, low operation cost, no pollution in the whole preparation process, no side effect on a human body, capacity of ensuring the biological safety of the implant material and high forming speed, and is very conductive to industrial production and application.

Description

Adopt selective laser sintering moulding to prepare the method for porous tantalum medical embedded material
The present patent application is application number 201210022123.6, the applying date on 01 31st, 2012, the dividing an application of denomination of invention " a kind of method that adopts selective laser sintering moulding to prepare porous tantalum medical embedded material ".
Technical field
The present invention relates to the preparation field of porous medical metal implanted material, particularly a kind of method that adopts selective laser sintering technology to prepare porous medical metal implanted material.
Background technology
Porous medical metal implanted material has the important and special purposes such as treatment osseous tissue wound and bone formation necrosis, and existing this common class material has metal stainless steel, porous metal titanium etc.Porous embedded material as osseous tissue wound and the use of bone formation necrosis therapeutic, its porosity should reach 30~80%, and hole is preferably all communicated with and is uniformly distributed, or hole is partly communicated with and is uniformly distributed as required, make it both consistent with the bone growth of human body, alleviate again the weight of material itself, to be applicable to human body, implanted use.
And refractory metals tantalum, because it has outstanding biocompatibility and mechanical property, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative, becomes the biomaterial mainly as bone necrosis's treatment.Due to metal tantalum to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, tantalum is goed deep into as the further of body implanting material cognition, and people become more and more urgent to human body by the demand of porous metal tantalum material, also more and more higher to its requirement., as porous medical metal tantalum, if can there is the very high physical and mechanical properties that is uniformly distributed open pore and adapts with human body, be wherein the heavy connection constituent material that guarantees freshman bone tissue's normal growth.
The preparation method of porous tantalum biomaterial mainly contains powder loose sintering method, foam impregnation sintering process at present, slurry foaming etc., and these methods all need to apply mould.And the maximum feature of biomaterial is complex-shaped, high to small details requirement, therefore, forming technique has been proposed to very high requirement, yet traditional forming technique cannot meet the demands owing to being subject to the restriction of mould.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of simple and efficient, porous tantalum medical embedded material that cost is low, the porous tantalum medical embedded material good biocompatibility making.
The object of the invention is achieved by the following scheme:
A kind of preparation method of porous tantalum medical embedded material, it is characterized in that: adopting the pure tantalum powder of particle diameter≤10 μ m (preferably adopting the pure tantalum powder of 5~10 μ m) is raw material, directly carry out selective laser sintering moulding people bone metal biomimetic material, during selective laser sintering, the paving powder thickness of every layer is at 60~80 μ m; Again people's bone metal biomimetic material of moulding is comprised to sintering, the cooling porous tantalum medical embedded material that obtains.
Adopt forming blank that above-mentioned selective laser sintering makes through sintering, cooling process, to obtain the porous tantalum medical embedded material, consistent with body bone tissue microtexture of the complete three-dimensional communication of hole, make this porous metal embedded material biocompatibility, biological safety good.According to the needs of corresponding implantation, the present invention also can be by regulate the processing parameter of selective laser sintering moulding and sintering to control the porosity of final porous tantalum, make the corresponding osseous tissue of its mechanical property and human body consistent simultaneously, thereby the stress concentration of avoiding porous tantalum not mate with body mechanics's performance and causing affects the long-term effect of implant, with this, meets different requirements; As regulate and control corresponding process parameters and can prepare and substitute human bearing position osseous tissue as porous tantalum embedded materials such as femur, face thighs, also can prepare the porous tantalum embedded material that substitutes human body non-bearing osseous tissue.The laser sintered device adopting in selective laser sintering method of the present invention is known, selective laser sintering technology (SLS) is a kind of technology of the rapid shaping based on laser sintered, adopt laser layering sintering solid powder selectively, and the cured layer that makes sinter molding is layering and generates the sample of desired shape, its whole technological process comprises the foundation of three-dimensional model and data processing, paving powder, thermal sintering etc., the material that at present, can successfully carry out SLS forming process has paraffin, polymer, metal, ceramic powder and their composite powder material.Can adjust as required the shape of moulding sample, the use of selective laser sintering device is that the three-dimensional model file designing is input in molding device software kit and carries out selective laser sintering, and this is this area routine techniques.The inventive method also has that processing unit is simple, running cost is low, whole preparation process is pollution-free, without any side effects to human body, be beneficial to the biological safety that guarantees embedded material, shaping speed is beneficial to suitability for industrialized production application soon, very much simultaneously.
Further; in order to make the porous tantalum medical embedded material that is suitable for substituting human bearing's osseous tissue; the preferred processing parameter of selective laser sintering moulding process of the present invention is: laser power is at 50~65W; sweep velocity is 15~25mm/s; sweep span is 0.05~0.15mm; every layer spreads bisque thick is 60~80 μ m, and whole moulding process is carried out in argon shield atmosphere, and purity of argon is greater than 99.999%.
More particularly, the preparation method of porous tantalum medical embedded material of the present invention is specific as follows:
1, selective laser sintering moulding: by particle diameter, be that the pure tantalum powder of 5~10 μ m is transported on shaped platform, roll extrusion laying, then the UG three-dimensional model file of the porous tantalum embedded material designing is input to molding device software kit, and carry out selective laser sintering; The processing parameter of selective laser sintering is: laser power is at 50~65W, sweep velocity is 15~25mm/s, and sweep span is 0.05~0.15mm, and every layer spreads bisque thick is 60~80 μ m, whole moulding process is carried out in argon shield atmosphere, and purity of argon is greater than 99.999%;
2, the vacuum sintering of above-mentioned gained shaping blank, cooling: first stage is the high-temperature vacuum sintering stage, rises to 1200~1250 ℃ with the speed of 10~15 ℃/min, insulation 30~60min, and vacuum tightness is 10 -4pa~10 -3pa; Speed with 10~20 ℃/min rises to 1500 ℃, insulation 30~60min, and vacuum tightness is 10 -4pa~10 -3pa, rises to 2000~2200 ℃ with the speed of 6~20 ℃/min, insulation 120~240min, and vacuum tightness is 10 -4pa~10 -3pa; Second stage is the Slow cooling stage, and vacuum tightness is 10 -4pa~10 -3pa; Speed with 10~20 ℃/min is cooled to 1500~1600 ℃, insulation 30~60min; Speed with 12~20 ℃/min is cooled to 1200~1250 ℃, insulation 60~90min; Speed with 10~20 ℃/min is cooled to 800 ℃, then furnace cooling.
For sintering obtains more even, thorough, make the porous tantalum embedded material obdurability that makes better, be suitable as and substitute human bearing position osseous tissue as porous tantalum embedded materials such as femur, face thighs, above-mentioned the sintering process of shaping blank is preferably carried out as follows: in vacuum tightness, be 10 -4pa~10 -3pa, with 10~20 ℃/min, be warming up to 1500~1800 ℃, be incubated 120~240min, with stove, be chilled to 200~300 ℃, with 10~20 ℃/min, be warming up to 1500~1800 ℃, insulation 180~240min again, with 5~10 ℃/min, be warming up to 2000~2200 ℃, insulation 120~360min.
For eliminate more fully porous tantalum embedded material internal stress, that it is organized is more even, further improves toughness, above-mentioned sintering, also carries out anneal after cooling, described anneal step is that vacuum tightness is 10 -4pa~10 -3pa, is warming up to 800~900 ℃, insulation 240~480min with 10~20 ℃/min, then is chilled to 400 ℃, insulation 120~300min with 2~5 ℃/min, then cools to room temperature with the furnace.
The selective laser sintering device that selective laser sintering moulding process of the present invention adopts is comprised of powder cylinder and moulding cylinder, during work, powder cylinder piston (powder feeding piston) rises, by powder-laying roller, powder is gone up to uniform spreading last layer at moulding cylinder piston (working piston), computer is controlled the two-dimensional scan track of laser beam according to the section model of prototype, the pure tantalum powder that sintering is carried is selectively to form an aspect of part.Powder completes after one deck, a bed thickness of working piston decline, paving powder system is spread new tantalum powder, controls laser beam and scans the new layer of sintering again, so moves in circles, be layering, until three-dimensional sample moulding, last, by unsintered Powder Recovery in powder cylinder, and take out profiled member and obtain shaping blank, whole selective laser sintering is in a vacuum environment.
Most preferably, a kind of method of preparing porous tantalum medical embedded material, carry out according to the following steps:
1, selective laser sintering moulding: by particle diameter, be that the pure tantalum powder of 5~10 μ m is transported on shaped platform, roll extrusion laying, then the UG three-dimensional model file of the porous tantalum embedded material designing is input to molding device software kit, and carry out selective laser sintering; The processing parameter of selective laser sintering is: laser power is at 55~60W, sweep velocity is 15~25mm/s, and sweep span is 0.05~0.15mm, and every layer spreads bisque thick is 70~75 μ m, whole moulding process is carried out in argon shield atmosphere, and purity of argon is greater than 99.999%;
2, the vacuum sintering of above-mentioned gained shaping blank, cooling, annealing: first stage is the high-temperature vacuum sintering stage, in vacuum tightness, is 10 -4pa~10 -3pa, with 10~20 ℃/min, be warming up to 1500~1800 ℃, be incubated 120~240min, with stove, be chilled to 200~300 ℃, with 10~20 ℃/min, be warming up to 1500~1800 ℃, insulation 180~240min again, with 5~10 ℃/min, be warming up to 2000~2200 ℃, insulation 120~360min; Second stage is the Slow cooling stage, and vacuum tightness is 10 -4pa~10 -3pa; Speed with 10~20 ℃/min is cooled to 1500~1600 ℃, insulation 30~60min; Speed with 12~20 ℃/min is cooled to 1200~1250 ℃, insulation 60~90min; Speed with 10~20 ℃/min is cooled to 800 ℃, then furnace cooling; Three phases is annealing, and vacuum tightness is 10 -4pa~10 -3pa, is warming up to 800~900 ℃, insulation 240~480min with 10~20 ℃/min, then is chilled to 400 ℃, insulation 120~300min with 2~5 ℃/min, then cools to room temperature with the furnace.
The present invention has following beneficial effect:
The porous tantalum medical embedded material that selective laser sintering moulding process of the present invention makes has been realized the complete three-dimensional communication of hole, it is consistent with body bone tissue microtexture, the biocompatibility of material, biological safety excellence, present method has also realized and has adjusted flexibly as required the shape of blank sample simultaneously.In conjunction with the techniques such as preferred sintering aftertreatment, porous tantalum medical embedded material density reachable 5.00~7.00g/cm that the present invention makes 3, the dispersity of hole is high, porosity can reach 60~80%, the complete three-dimensional communication of hole and be evenly distributed, good biocompatibility, aperture can be at 200 μ m~400 μ m; Young's modulus can reach that 5.0~6.5Gpa, flexural strength can reach 125~145Mpa, ultimate compression strength can reach 80~90Mpa, is suitable as very much the embedded material that substitutes human bearing's osseous tissue.Moreover, preparation method's technique of the present invention simply, easily control; Whole preparation process is harmless, pollution-free, toxicological harmless dust, without any side effects to human body.
Accompanying drawing explanation
Fig. 1 is the vertical microscope analysis chart of the preparation method of the present invention microtexture that makes porous tantalum; From accompanying drawing, can be observed: the complete three-dimensional communication of porous tantalum hole that the present invention makes, and be evenly distributed.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1
A kind of preparation method of porous tantalum medical embedded material, the pure tantalum powder that is 5 μ m by particle diameter is transported on the platform of 3 D-printing, roll extrusion laying, and the sample size that design will be prepared is φ 10 * 100mm, and by its UG file molding equipment, carry out selective laser sintering moulding.Computer is controlled the two-dimensional scan track of laser beam according to the section model of prototype, the pure tantalum powder that sintering is carried is selectively to form an aspect of part, powder completes after one deck, the working piston 50 μ m that decline, paving powder system is spread new tantalum powder, every layer and is spread bisque thick to be 80 μ m, to control laser beam and scan the new layer of sintering again, so move in circles, be layering, until three-dimensional sample moulding.Then take out moulding sample, put into vacuum oven and carry out high-temperature vacuum sintering, with the speed of 10~15 ℃/min, from room temperature, rise to 1200 ℃, insulation 1.0h, vacuum tightness is 1 * 10 -4pa; Speed with 10 ℃/min rises to 1500 ℃, insulation 1.0h, and vacuum tightness is 1 * 10 -4pa~1 * 10 -3pa; Speed with 6 ℃/min rises to 2100 ℃, insulation 3h, and vacuum tightness is 1 * 10 -3pa; Sintering is complete, and vacuum tightness is 1 * 10 -4pa~1 * 10 -3pa; Speed with 15 ℃/min is cooled to 1250 ℃, insulation 1h; Speed with 13 ℃/min is cooled to 800 ℃, insulation 1.5h, then furnace cooling; The complete three-dimensional communication of porous tantalum medical embedded material hole making, it is 5.31g/cm that contriver records its density by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 3, porosity is about 70%, ultimate compression strength 65.2MPa, flexural strength 73.8MPa, Young's modulus 2.6GPa.
Embodiment 2
A kind of preparation method of porous tantalum medical embedded material, the pure tantalum powder that is 10 μ m by particle diameter is transported on the platform of 3 D-printing, roll extrusion laying, and the sample size that design will be prepared is φ 10 * 100mm, and by its UG file molding equipment, carry out selective laser sintering moulding.Computer is controlled the two-dimensional scan track of laser beam according to the section model of prototype, the pure tantalum powder that sintering is carried is selectively to form an aspect of part, powder completes after one deck, the working piston 50 μ m that decline, paving powder system is spread new tantalum powder, controls laser beam and scans the new layer of sintering again, so moves in circles, be layering, until three-dimensional sample moulding; In selective laser sintering process, laser power is at 65W, and sweep velocity is 15mm/s, and sweep span is 0.1mm, and every layer spreads bisque thick is 70 μ m, and whole moulding process is carried out in argon shield atmosphere, and purity of argon is greater than 99.999%.Then take out moulding sample, put into vacuum oven and carry out high-temperature vacuum sintering, with the speed of 13 ℃/min, from room temperature, rise to 1250 ℃, insulation 0.5h, vacuum tightness is 1 * 10 -4pa; Speed with 20 ℃/min rises to 1500 ℃, insulation 0.5h, and vacuum tightness is 1 * 10 -4pa~1 * 10 -3pa; Speed with 20 ℃/min rises to 2200 ℃, insulation 240min, and vacuum tightness is 1 * 10 -3pa; Sintering is complete, and vacuum tightness is 1 * 10 -4pa~1 * 10 -3pa; Speed with 15 ℃/min is cooled to 1550 ℃, insulation 1h; Speed with 18 ℃/min is cooled to 1200 ℃, and insulation 1.5h, is cooled to 800 ℃ with the speed of 12 ℃/min, then furnace cooling; The complete three-dimensional communication of porous tantalum medical embedded material hole making, it is 5.82g/cm that contriver records its density by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 3, porosity is about 65%, ultimate compression strength 70.5MPa, flexural strength 82.3MPa, Young's modulus 3.3GPa.
Embodiment 3~7: according to the following steps and processing parameter carry out, all the other are with embodiment 1.
Figure BDA0000439432680000051
Figure BDA0000439432680000052
Figure BDA0000439432680000061
Figure BDA0000439432680000071
Gained porous tantalum finished product three-dimensional is communicated with completely, porous nickel distributes, and good biocompatibility is as follows by preceding method detected result:
Embodiment 3 4 5 6 7
Density (g/cm 3) 5.37 5.63 7.00 6.25 5.88
Porosity (%) 80 75 60 68 70
Young's modulus (GPa) 5.5 3.5 6.5 5.0 6.1
Flexural strength (MPa) 135 102 127 130 143
Ultimate compression strength (MPa) 85 72 80 90 83

Claims (1)

1. the preparation method of a porous tantalum medical embedded material, the pure tantalum powder that is 10 μ m by particle diameter is transported on the platform of 3 D-printing, roll extrusion laying, and the sample size that design will be prepared is φ 10 * 100mm, and by its UG file molding equipment, carry out selective laser sintering moulding; Computer is controlled the two-dimensional scan track of laser beam according to the section model of prototype, the pure tantalum powder that sintering is carried is selectively to form an aspect of part, powder completes after one deck, the working piston 50 μ m that decline, paving powder system is spread new tantalum powder, controls laser beam and scans the new layer of sintering again, so moves in circles, be layering, until three-dimensional sample moulding; In selective laser sintering process, laser power is at 58W, and sweep velocity is 19mm/s, and sweep span is 0.13mm, and every layer spreads bisque thick is 80 μ m, and whole moulding process is carried out in argon shield atmosphere, and purity of argon is greater than 99.999%; Then take out moulding sample, put into vacuum oven and carry out high-temperature vacuum sintering, the speed of 17 ℃/min rises to 1750 ℃ from room temperature, and insulation 135min, is chilled to 260 ℃ with stove, and vacuum tightness is 10 -4pa; Speed with 15 ℃/min rises to 1650 ℃, insulation 220min; Speed with 7.5 ℃/min rises to 2150 ℃, insulation 160min, and vacuum tightness is 10 -3pa; Vacuum tightness is 10 -4pa~10 -3pa; Speed with 15 ℃/min is cooled to 1520 ℃, insulation 45min; Speed with 16 ℃/min is cooled to 1220 ℃, insulation 60min; Speed with 13 ℃/min is cooled to 800 ℃, then furnace cooling; Sintering is complete, and vacuum tightness is 10 -4pa~10 -3pa, is warming up to 850 ℃, insulation 420min with 20 ℃/min, then is chilled to 400 ℃, insulation 270min with 4 ℃/min, then cools to room temperature with the furnace.
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CN106390198A (en) * 2016-09-19 2017-02-15 西安交通大学 Method for preparing individualized porous implant through selective laser formation and electrolytic reduction
CN107598166A (en) * 2017-09-13 2018-01-19 西北有色金属研究院 The method that porous tantalum medical embedded material is prepared based on electron beam selective melting technology
CN107901419A (en) * 2017-12-21 2018-04-13 北京工业大学 A kind of method for making annealing treatment regulation and control PA3200 3D printing surface of shaped parts wetabilitys
CN109261970A (en) * 2018-10-23 2019-01-25 武汉三迪创为科技有限公司 3D printing equipment and the method for preparing medical porous tantalum metal implant material using the equipment
CN109513050A (en) * 2018-12-17 2019-03-26 广东省新材料研究所 Depth-graded porous structure personalization tantalum implant and the preparation method and application thereof
CN110421172A (en) * 2019-08-27 2019-11-08 西安九洲生物材料有限公司 A method of medical porous tantalum part is prepared based on selective laser melting process
CN110614369A (en) * 2018-06-20 2019-12-27 韩国生产技术研究院 One-step method for producing a laminated porous member
CN111299584A (en) * 2019-12-17 2020-06-19 吉林大学 Preparation method of bionic impact-resistant multilayer composite gradient material based on amorphous alloy
CN113427022A (en) * 2021-07-02 2021-09-24 长沙理工大学 High-strength high-toughness post-treatment method for 3D printing of biomedical metal tantalum and metal tantalum

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CN106390198B (en) * 2016-09-19 2019-07-23 西安交通大学 A method for preparing personalized porous implants by selective laser forming and electrolytic reduction
CN106390198A (en) * 2016-09-19 2017-02-15 西安交通大学 Method for preparing individualized porous implant through selective laser formation and electrolytic reduction
CN107598166A (en) * 2017-09-13 2018-01-19 西北有色金属研究院 The method that porous tantalum medical embedded material is prepared based on electron beam selective melting technology
CN107598166B (en) * 2017-09-13 2020-01-24 西安赛隆金属材料有限责任公司 Method for preparing porous tantalum medical implant material based on electron beam selective melting technology
CN107901419B (en) * 2017-12-21 2019-09-27 北京工业大学 A method for regulating the surface wettability of PA3200 3D printing molded parts by annealing treatment
CN107901419A (en) * 2017-12-21 2018-04-13 北京工业大学 A kind of method for making annealing treatment regulation and control PA3200 3D printing surface of shaped parts wetabilitys
CN110614369A (en) * 2018-06-20 2019-12-27 韩国生产技术研究院 One-step method for producing a laminated porous member
CN109261970A (en) * 2018-10-23 2019-01-25 武汉三迪创为科技有限公司 3D printing equipment and the method for preparing medical porous tantalum metal implant material using the equipment
CN109513050A (en) * 2018-12-17 2019-03-26 广东省新材料研究所 Depth-graded porous structure personalization tantalum implant and the preparation method and application thereof
CN109513050B (en) * 2018-12-17 2021-08-17 广东省新材料研究所 Personalized tantalum implant with graded gradient porous structure and its preparation method and application
CN110421172A (en) * 2019-08-27 2019-11-08 西安九洲生物材料有限公司 A method of medical porous tantalum part is prepared based on selective laser melting process
CN111299584A (en) * 2019-12-17 2020-06-19 吉林大学 Preparation method of bionic impact-resistant multilayer composite gradient material based on amorphous alloy
CN111299584B (en) * 2019-12-17 2021-05-25 吉林大学 Preparation method of biomimetic impact-resistant multilayer composite gradient material based on amorphous alloy
CN113427022A (en) * 2021-07-02 2021-09-24 长沙理工大学 High-strength high-toughness post-treatment method for 3D printing of biomedical metal tantalum and metal tantalum
CN113427022B (en) * 2021-07-02 2023-09-22 长沙理工大学 High-strength high-toughness post-treatment method for 3D printing biomedical metal tantalum and metal tantalum

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