CN101279106A - Preparation of gel injection molding of porous titanium-cobalt alloy medical implant article - Google Patents
Preparation of gel injection molding of porous titanium-cobalt alloy medical implant article Download PDFInfo
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- CN101279106A CN101279106A CNA2008101122138A CN200810112213A CN101279106A CN 101279106 A CN101279106 A CN 101279106A CN A2008101122138 A CNA2008101122138 A CN A2008101122138A CN 200810112213 A CN200810112213 A CN 200810112213A CN 101279106 A CN101279106 A CN 101279106A
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Abstract
The invention relates to a gel casting preparation method for a medical multi-hole titanium-cobalt alloy implant. The gel casting preparation method pertains to the technical field of the medical material preparation. Acrylamide monomer, a crosslinking agent N, N'-methylene-bisacrylamide and deionized water are prepared into a premixed solution with a certain concentration; a dispersing agent oleic acid is added to the premixed solution to lead titanium-cobalt alloy powders to suspend in the premixed solution so as to prepare a slurry body; the pH value is adjusted to 9.0 to 10.0, then a proper amount of catalyst N, N, N', N'-TMEDA (tetramethylethylenediamine) and an evocating agent ammonium persulfate are added to the slurry body and are evenly stirred, then the slurry body is injected to a mold after being degassed; monomers in the mold undergo polymerization, therefore, a meshy structure is formed to cover the titanium-cobalt powders, then a blank body meshy-shaped by large molecules is formed. A product is obtained after the blank body is dried, batched out and sintered. In addition, the porosity and the mechanical property of the multi-hole titanium-cobalt alloy can be changed through adjusting the solid content, so as to meet the performance requirements of various medical implants. The gel casting preparation method for the multi-hole titanium-cobalt alloy medical implant requires no complicate devices and special degreasing techniques, has simple process, can greatly reduce production costs, and is particularly applicable to the medical implants with the characteristics of various specifications and mass production.
Description
Technical field
The invention belongs to the medical material preparing technical field, particularly provide a kind of gel injection-moulding to prepare the method for good, the complex-shaped porous medical implant of biocompatibility.
Background technology
The good biocompatibility of titanium-base alloy, density is low, approaches body bone tissue, and elastic modelling quantity is lower, and intensity is apparently higher than other metal, and corrosion resisting property is good, and its each side characteristic more near cortical bone, is suitable for use as biological and medicinal implant material than other metal.Porous titanium-cobalt alloy has the structural advantage of porous three-dimensional support, and the hole of three-dimensional perforation and suitable surface micropore structure make tissue and implant obtain firm physiological and fix for growing into of surrounding tissue provides support; Have both simultaneously titanium excellent in chemical, mechanical property and biocompatibility again.Porous titanium-cobalt alloy has boundless prospect aspect medical implant.
Usually, the manufacturing process of porous metal material mainly comprises powder metallurgy pressing method, slurry foaming etc.Wherein, the production technology that the powder metallurgy pressing legal system is equipped with porous metal material is simple, cost is low and can access the uniform porous metal material of organizational structure, but porosity is lower, also be difficult to satisfy the requirement of medical implant complicated shape, and die cost is higher, small-scale production cost height; The slurry foaming can obtain Higher porosity, and shortcoming is restive bubble size, thus be difficult to obtain the porous material of even aperture distribution, and be difficult to obtain complicated shape.
The preparation of the porous titanium-cobalt alloy medical implant article of in the present invention, adopt that water base acrylamide system gel casting technology realizes that biocompatibility is good, complex-shaped, space and mechanical property are adjustable; Adopt the gel casting technology to solve the problem of complicated shape shaping difficulty on the one hand, reached the porous requirement of medical implant again, this has just simplified production process greatly, gel casting forming technology die cost is very low in addition, has solved the high problem of medical implant small-scale production cost; The more important thing is and introduced the metallic cobalt that has no side effect, improved the intensity of its implant, strengthened the safety of medical implant as alloying element.
Summary of the invention
The object of the present invention is to provide the method for a kind of low-cost preparation biocompatibility and the porous titanium-cobalt alloy medical implant article that tissue bond is good, complex-shaped, mechanical property is adjustable, improve performance and reduce cost.
The principle of the invention is as follows: adopt water base acrylamide system gel casting.Acrylamide solution can polymerization becomes the gel of the polymer-solvent of high-intensity, horizontal connection.With monomer acrylamide, cross-linking agent N, N '-methylene-bisacrylamide and deionized water are mixed with certain density premixed liquid, adding dispersant oleic acid is suspended in the titanium cobalt dust and makes slurry in the premixed liquid, regulate pH value to 9.0～10.0, add proper catalyst N then, N, N ', N '-tetramethylethylenediamine and initiator ammonium persulfate stir, after aerofluxus, inject mould, monomer polymerization reaction take place in the mould forms network structure with titanium cobalt powder body parcel, becomes the base substrate by the macromolecular network typing.Base substrate drying, binder removal, sintering obtain product, as Fig. 1.Can change the porosity and the mechanical property of porous titanium-cobalt alloy in addition by the adjusting solid content, to satisfy the performance requirement of various medical implants.
A kind of gel injection moulding preparation of porous titanium-cobalt alloy medical implant article, concrete technology is as follows:
1, take by weighing the titanium cobalt powder respectively, wherein cobalt powder is 2%～40% of a titanium cobalt mixture, and ball milling made its mix homogeneously in 1～4 hour.
2, with monomer acrylamide and monomer crosslinked dose of N, N '-methylene-bisacrylamide is with mass ratio (1～250): 1 mixes, and the mixture of acrylamide and cross-linking agent is dissolved in deionized water, and to make mass fraction be 1～55% uniform and stable solution;
3, the dispersant oleic acid of measuring titanium cobalt powder volume 0.01%～3% adds in 2 solution, regulates pH value to 9.0～10.0, stirs, and makes slurry;
4, slurry is put into high vacuum environment aerofluxus 5～40 minutes;
5, be coated with very thin one deck releasing agent isooctanol at mould inner wall; Measure the catalyst n of monomer mass 0.01%～1%, N, N ', N '-tetramethylethylenediamine and monomer mass 0.01%～2% initiator ammonium persulfate in the slurry after the adding aerofluxus, stir;
6, the slurry that will contain catalyst and initiator slowly injects mould, in the injection process, moves up and down to avoid the slurry injection process not produce bubble with thin Glass rod;
7, after slip casting finishes, the slip casting mould put into 20 ℃～65 ℃ vacuum drying oven inner drying;
8, after dry 20～60 minutes, the demoulding, repaired biscuit is put into 20 ℃～65 ℃ vacuum drying oven inner drying 30～60 hours again;
9, the base substrate that drying is crossed sintering under fine vacuum can obtain POROUS TITANIUM cobalt medical implant.
Mold Making:
1, takes by weighing an amount of silicone rubber, add 0.8%～2% curing initiator, stir;
2, on parts surface, be coated with the very thin silicone rubber of last layer equably, will avoid producing bubble in the process, left standstill 1～2 hour; Every 1～2 hour repaste one deck silicone rubber, need three layers altogether, left standstill then 12 hours.
3, take by weighing an amount of Gypsum Fibrosum powder, add 5%～35% water, stir, pour in the carton of size greater than parts, half of parts that will wrap up silicone rubber then immerses in carton calcium plaster, after 10～30 minutes, three layers of soft paper in Gypsum Fibrosum section shop in carton, pour calcium plaster again into to not having 1～4 centimetre of parts, left standstill 6～12 hours, make the Gypsum Fibrosum pattern;
4, take out the parts of parcel silicone rubber, select a simple side, cut off, outer silicone rubber sleeve is taken out, put into the Gypsum Fibrosum pattern, so far make silicon rubber mould with shears.
The invention has the advantages that:
1, provide a kind of and prepare biocompatibility and the new technique of the porous titanium-cobalt alloy medical implant article that tissue bond is good, complex-shaped, hole and mechanical property are adjustable from producing, the intensity of this material is significantly improved with respect to pure titanium;
2, this technology does not need complex device, does not need special degreasing process, and technology is simple, and production cost is significantly reduced, and is particularly suitable for that the medical implant specification is various, the characteristics of large-scale production.
Description of drawings
Fig. 1 is a gel casting cemented carbide parts process chart
The specific embodiment
The shaping sintering:
Embodiment 1:
1, takes by weighing titanium valve, the 80g cobalt powder of 1920g, in planetary ball mill, mixed powder 2 hours;
2, the 159.7g monomer acrylamide that takes by weighing, 0.13g cross-linking agent N, N '-methylene-bisacrylamide is dissolved in the 807ml deionized water, and adds mixed powder in 1, stirs;
3, the dispersant oleic acid of measuring 4.35ml adds in 2 solution, stirs, and makes slurry;
4,3 slurries were put into the high vacuum environment aerofluxus 15 minutes;
5, be coated with very thin one deck releasing agent isooctanol at mould inner wall; Measure the 4ml catalyst n, N, N ', N '-tetramethylethylenediamine and 4ml initiator ammonium persulfate (assurance has the enough injection molding time) add in 4 slurries, stir;
6, after slip casting finishes, put it into 60 ℃ of homothermic vacuum drying oven inner dryings;
7, after dry 30 minutes, the demoulding, repaired biscuit was put into 60 ℃ of homothermic vacuum drying oven inner dryings 48 hours again;
8, the base substrate that drying is crossed sintering under fine vacuum can obtain artificial POROUS TITANIUM cobalt hipbone alternative.
Embodiment 2:
1, takes by weighing titanium valve, the 50g cobalt powder of 1600g, in planetary ball mill, mixed powder 2 hours;
2, the 135g monomer acrylamide that takes by weighing, 0.1g cross-linking agent N, N '-methylene-bisacrylamide is dissolved in the 750ml deionized water, and adds mixed powder in 1, stirs;
3, the dispersant oleic acid of measuring 3.5ml adds in 2 solution, stirs, and makes slurry;
4,3 slurries were put into the high vacuum environment aerofluxus 15 minutes;
5, be coated with very thin one deck releasing agent isooctanol at mould inner wall; Measure the 3.5ml catalyst n, N, N ', N '-tetramethylethylenediamine and 3.5ml initiator ammonium persulfate (assurance has the enough injection molding time) add in 4 slurries, stir;
6, after slip casting finishes, put it into 60 ℃ of homothermic vacuum drying oven inner dryings;
7, after dry 30 minutes, the demoulding, repaired biscuit was put into 60 ℃ of homothermic vacuum drying oven inner dryings 48 hours again;
8, the base substrate that drying is crossed sintering under fine vacuum can obtain artificial POROUS TITANIUM cobalt hipbone alternative.
Mold Making:
1, takes by weighing the silicone rubber of 200g, add the curing initiator of 2.6g, stir;
2, on the hipbone model surface, be coated with the very thin silicone rubber of last layer equably, will avoid producing bubble in the process, left standstill 1 hour; Take by weighing the silicone rubber of 300g again, add the curing initiator of 3.9g, stir, be coated on the last layer silicone rubber, left standstill 1 hour, repeat previous step again, need three layers of silicone rubber altogether, left standstill then 12 hours.
3, take by weighing the Gypsum Fibrosum powder of 2000g, add 200ml water, stir, pour in the carton of size greater than the hipbone model, half of hipbone model that will wrap up silicone rubber then immerses in carton calcium plaster, after 20 minutes, three layers of soft paper in Gypsum Fibrosum section shop in carton, pour calcium plaster again into to not having hipbone model 2cm, left standstill 10 hours, make the Gypsum Fibrosum pattern;
4, take out the hipbone model of parcel silicone rubber, select a simple side, cut off, outer silicone rubber sleeve is taken out, put into the Gypsum Fibrosum pattern, so far make the silicon rubber mould of hipbone with shears.
Claims (2)
1. the gel injection moulding preparation of a porous titanium-cobalt alloy medical implant article, the sintering step that it is characterized in that specifically being shaped is:
(1), respectively take by weighing the titanium cobalt powder, wherein cobalt powder is 2%～40% of a titanium cobalt mixture, and ball milling made its mix homogeneously in 1～4 hour;
(2), with monomer acrylamide and monomer crosslinked dose of N, N '-methylene-bisacrylamide is with mass ratio (1～250): 1 mixes, and the mixture of acrylamide and cross-linking agent is dissolved in deionized water, and to make mass fraction be 1～55% uniform and stable solution;
(3), the dispersant oleic acid of measuring titanium cobalt powder volume 0.01%～3% adds in (2) solution, regulates pH value to 9.0～10.0, stirs, and makes slurry;
(4), slurry is put into high vacuum environment aerofluxus 5～40 minutes;
(5), be coated with very thin one deck releasing agent isooctanol at mould inner wall; Measure the catalyst n of monomer mass 0.01%～1%, N, N ', N '-tetramethylethylenediamine and monomer mass 0.01%～2% initiator ammonium persulfate in the slurry after the adding aerofluxus, stir;
(6), the slurry that will contain catalyst and initiator slowly injects mould, in the injection process, move up and down to avoid the slurry injection process not produce bubble with thin Glass rod;
(7), after slip casting finishes, the slip casting mould put into 20 ℃～65 ℃ vacuum drying oven inner drying;
(8), after dry 20～60 minutes, the demoulding, repaired biscuit is put into 20 ℃～65 ℃ vacuum drying oven inner drying 30～60 hours again;
(9), with base substrate sintering under fine vacuum that drying is crossed, can obtain POROUS TITANIUM cobalt medical implant.
2. the gel injection moulding preparation of a kind of porous titanium-cobalt alloy medical implant article as claimed in claim 1 is characterized in that the Mold Making step is:
(1), take by weighing an amount of silicone rubber, add 0.8%～2% curing initiator, stir;
(2), on parts surface, be coated with the very thin silicone rubber of last layer equably, to avoid producing bubble in the process, left standstill 1～2 hour; Every 1～2 hour repaste one deck silicone rubber, need three layers altogether, left standstill then 12 hours;
(3), take by weighing Gypsum Fibrosum powder, add 5%～35% water, stir, pour in the carton of size greater than parts, half of parts that will wrap up silicone rubber then immerses in carton calcium plaster, after 10～30 minutes, three layers of soft paper in Gypsum Fibrosum section shop in carton, pour calcium plaster again into to not having 1～4 centimetre of parts, left standstill 6～12 hours, make the Gypsum Fibrosum pattern;
(4), take out the parts of parcel silicone rubber, select a simple side, cut off with shears, with outer silicone rubber sleeve taking-up, put into the Gypsum Fibrosum pattern, so far make silicon rubber mould.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101518820B (en) * | 2009-03-31 | 2010-07-28 | 北京科技大学 | Method for extruding and molding metal powder gelatin |
| CN102242288A (en) * | 2011-06-20 | 2011-11-16 | 烟台工程职业技术学院 | Preparation method of porous titanium |
| CN102407332A (en) * | 2011-12-05 | 2012-04-11 | 烟台工程职业技术学院 | Preparation method for porous titanium |
| CN102554228A (en) * | 2012-01-13 | 2012-07-11 | 北京科技大学 | Method for forming ultrathin-wall porous metal pipe fitting |
| CN104212993A (en) * | 2014-07-24 | 2014-12-17 | 昆明理工大学 | Preparation method of porous titanium alloy material |
| WO2015154872A1 (en) * | 2014-04-11 | 2015-10-15 | Heinrich Steger | Method for the production of a molded blank from metal powder |
| CN105543526A (en) * | 2015-12-31 | 2016-05-04 | 中国钢研科技集团有限公司 | Method for preparing high-compactness titanium or titanium alloy by using gel casting formation |
| US9610174B2 (en) | 2013-11-29 | 2017-04-04 | Metal Industries Research & Development Centre | Intervertebral implant |
| CN108372293A (en) * | 2018-03-05 | 2018-08-07 | 北京科技大学 | A kind of method of metal powder gel injection molding catalysis degumming |
| CN110978500A (en) * | 2019-12-25 | 2020-04-10 | 深圳光韵达光电科技股份有限公司 | 3D printing method and device based on thermal initiator addition |
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2008
- 2008-05-21 CN CNA2008101122138A patent/CN101279106A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101518820B (en) * | 2009-03-31 | 2010-07-28 | 北京科技大学 | Method for extruding and molding metal powder gelatin |
| CN102242288A (en) * | 2011-06-20 | 2011-11-16 | 烟台工程职业技术学院 | Preparation method of porous titanium |
| CN102242288B (en) * | 2011-06-20 | 2012-09-26 | 烟台工程职业技术学院 | Preparation method of porous titanium |
| CN102407332A (en) * | 2011-12-05 | 2012-04-11 | 烟台工程职业技术学院 | Preparation method for porous titanium |
| CN102554228A (en) * | 2012-01-13 | 2012-07-11 | 北京科技大学 | Method for forming ultrathin-wall porous metal pipe fitting |
| CN102554228B (en) * | 2012-01-13 | 2013-11-06 | 北京科技大学 | Method for forming ultrathin-wall porous metal pipe fitting |
| US9610174B2 (en) | 2013-11-29 | 2017-04-04 | Metal Industries Research & Development Centre | Intervertebral implant |
| WO2015154872A1 (en) * | 2014-04-11 | 2015-10-15 | Heinrich Steger | Method for the production of a molded blank from metal powder |
| CN104212993A (en) * | 2014-07-24 | 2014-12-17 | 昆明理工大学 | Preparation method of porous titanium alloy material |
| CN105543526A (en) * | 2015-12-31 | 2016-05-04 | 中国钢研科技集团有限公司 | Method for preparing high-compactness titanium or titanium alloy by using gel casting formation |
| CN108372293A (en) * | 2018-03-05 | 2018-08-07 | 北京科技大学 | A kind of method of metal powder gel injection molding catalysis degumming |
| CN110978500A (en) * | 2019-12-25 | 2020-04-10 | 深圳光韵达光电科技股份有限公司 | 3D printing method and device based on thermal initiator addition |
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