CN101899599B - Preparation method of magnesium and porous beta-calcium phosphate composite material and vacuum suction casting instrument - Google Patents
Preparation method of magnesium and porous beta-calcium phosphate composite material and vacuum suction casting instrument Download PDFInfo
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- CN101899599B CN101899599B CN2010102353391A CN201010235339A CN101899599B CN 101899599 B CN101899599 B CN 101899599B CN 2010102353391 A CN2010102353391 A CN 2010102353391A CN 201010235339 A CN201010235339 A CN 201010235339A CN 101899599 B CN101899599 B CN 101899599B
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Abstract
The invention provides a preparation method of a magnesium and porous beta-calcium phosphate composite material and a vacuum suction casting instrument. The first stage is as follows: taking polyurethane foam as a framework, using beta-TCP slurry generated by the reaction to carry out impregnation-extrusion multiple treatment on the framework, uniformly coating the beta-TCP on the surface of the framework, and further sintering for obtaining a porous beta-TCP preform. The second stage is as follows: preheating the porous beta-TCP preform to 150 DEG C, adopting the homemade vacuum suction casting instrument to suck Mg or Mg alloy liquid at the temperature of 680 DEG C-720 DEG C into the preheated porous beta-TCP preform, keeping the temperature for 2min, then carrying out vacuum breaking and taking out a Mg or Mg alloy and porous beta-TCP composite material. The preparation method can save preparation time and have simple process and convenient operation. The prepared Mg or Mg alloy and porous beta-TCP composite material has dense structure and can also maintain the respective connectivity of the beta-TCP and the Mg or Mg alloy. The composite material has broad application prospects in the field of medical bone tissue substitutes.
Description
Technical field
What the present invention relates to is a kind of composite, the composite of particularly a kind of degradable Mg or Mg alloy and porous bio-ceramic.
Background technology
Bone tissue engineer is the focus in the Tissue Engineering Study, and the research of bone tissue engineering stent material is also being deepened continuously.The more material of research mainly contains degradable polymer and calcium orthophosphate base biological active ceramic material at present.Degradable polymer mainly contains PLA (PLA) and polyglycolic acid (PGA) etc., its stable in properties, and plasticity and repeatability are good, but strength and stiffness are low, and histocompatbility is poor, and catabolite can cause serious inflammatory reaction.Can absorb calcium phosphate biological ceramic to human non-toxic, no immune response; Have excellent biological compatibility, biologically active, osteoacusis even bone inductive effect; Be beneficial to the growth of bone tissue behind the implanting to human body, so calcium phosphate biological ceramic is widely used in bone tissue engineer research.Wherein beta-calcium phosphate (β-TCP) have favorable biological degradability, its calcium phosphorus mass ratio is 1.5, and is approaching with normal bone tissues; And porous beta-TCP can also provide big specific area; Help propagation, differentiation and the metabolism of cell, in its implantable bioartificial body, the Ca that degrades; P gets into the live body circulatory system, to forming area of new bone certain facilitation is arranged.Therefore, generally believe that β-TCP is the inorganic timbering material of a kind of comparatively ideal bone tissue engineer, has tempting application prospect.But because the intensity of porous beta-TCP is lower, toughness is too low, makes it receive certain restriction in the application aspect the bone defect repair.Numerous scholars are in order to improve the mechanical property of porous beta-TCP, and portion's doping metals, ceramic phase, macromolecular material perhaps in porous beta-TCP surface preparation coating, so form various composites within it, but the amplitude of improving is all smaller.Fine and close β-TCP can improve mechanical strength, but the biologically active performance slowly, is unfavorable for the formation of area of new bone.
Mg has lower elastic modelling quantity, suitable intensity, and good characteristics such as excellent biocompatibility and degradability are a kind of new metallic materials with potential applicability in clinical practice.Mg is the important activator of various enzyme systems in the cell metabolism, can activate many important enzymes.Mg can promote the growth of new bone tissue, can not produce harmful effect to human body when Mg degrades with given pace.Therefore Mg is for the growth of regulating cell with keep membrane structure and play an important role.Simultaneously, Mg is prone to generate the Mg ion and excretes by injected organism tissue absorption on every side or through body fluid in containing the solution of chlorion (like human body fluid), so Mg can be degraded by human body fluid fully.The Mg alloy is one of the lightest structural material, and its density is at 1.74g/cm
3About, with people's bone density (1.75g/cm
3) quite, and have high specific strength and specific stiffness.Yet because Mg degradation in vivo can change pericellular microenvironment, may cause the toxic action of pair cell, simultaneously, the problem of Mg alloy degradation in vivo excessive velocities also waits to solve.
Summary of the invention
The object of the present invention is to provide and a kind ofly can save preparation time greatly, technology is simple, does not need complex apparatus; The composite that makes has good mechanical stability and mechanical strength, helps magnesium and the preparation method of porous beta-calcium phosphate composite material of the reparation of bone behind the implanting to human body.The present invention also aims to provide a kind of vacuum suction casting instrument that is used to prepare magnesium and porous beta-calcium phosphate composite material.
The objective of the invention is to realize like this:
(1) preparation of beta-calcium phosphate slurry: 60 ℃ of water-baths, set Ca/P=1.48, under the pH=8 stirring condition with the diammonium hydrogen phosphate ((NH of 0.3mol/L
4)
2HPO
4) solution splashes into the calcium nitrate (Ca (NO of 0.4mol/L with the speed of 2～3ml/min
3)
24H
2O) in the solution, treat that titration finishes the back at 60 ℃ of insulation 1h, be heated to 95 ℃～98 ℃ insulation 2h continued again and be stirred to the nature cooling; Leave standstill, natural subsidence is outwelled supernatant liquor and is obtained beta-calcium phosphate solution; Adding 2% polyethylene glycol again stirs until there not being bubble to produce; Continue to stir and be warmed up to the polyvinyl alcohol of adding 8% after 95 ℃, naturally cool to room temperature after waiting to stir, form the beta-calcium phosphate slurry;
(2) preliminary treatment of polyurethane foam: with polyurethane foam clean up with absolute ethyl alcohol and ultrasonic Treatment 20min after dry, then polyurethane foam is put into the hydrochloric acid solution soaking and stirring 48h of 2mol/L, washing, drying earlier; Put into 5% sodium hydroxide solution soaking and stirring 48h again, washing, drying;
(3) preparation of porous beta-calcium phosphate precast body: will pass through pretreated polyurethane foam and put into the beta-calcium phosphate slurry; Obtain uniform coat through after the repeatedly processing of dipping-extruding; Behind 60 ℃ of drying box inner drying 24h in heat-treatment furnace sintering; Sintering condition is: the heating rate with 0.8 ℃/min is warmed up to 600 ℃ of insulation 60min with precast body, and the speed with 5 ℃/min is warmed up to 1150 ℃ then, and the cooling rate with 5 ℃/min is chilled to room temperature behind the insulation 5h;
(4) preparation of Mg or Mg alloy and porous beta-calcium phosphate composite material is carried out on the vacuum suction casting instrument, and detailed process is:
1. the melting of Mg or Mg alloy: with Mg or Mg alloy melting, the coverture protection, 680 ℃～720 ℃ insulations down, for use;
2. vacuum system is bled in advance: the open vacuum pump, open the vacuum system extraction valve, and vacuum system is evacuated in advance-close vavuum pump and vacuum system extraction valve behind 0.08～0.07MPa;
3. precast body preheating: be installed in the vacuum suction casting instrument after the porous beta-calcium phosphate precast body is preheating to 150 ℃;
4. suction pouring: the open vacuum pump, open the vacuum system extraction valve, open precast body air chamber extraction control valve, Mg or Mg alloy liquid are under the effect of vacuum, and the porous beta-calcium phosphate precast body is advanced in filling, and the time relay picks up counting simultaneously;
5. after being incubated 2min, vavuum pump and vacuum system extraction valve and extraction control valve are closed automatically, and open vacuum system decompression valve after the vacuum breaking, takes out simultaneously, obtains Mg or Mg alloy and porous beta-calcium phosphate composite material.
The composition that is used to prepare the vacuum suction casting instrument of magnesium and porous beta-calcium phosphate composite material of the present invention comprises that two ends pass through the mould cavity of cover closure up and down; The porous beta-calcium phosphate precast body is installed in the mould cavity; Have stalk on the lower cover, stalk is deep in the container of Mg that fusing is housed or Mg alloy, and the outside of container is provided with holding furnace; Upper cover plate connects exhaust tube; Exhaust tube links to each other with vavuum pump through surge tank, and the exhaust tube at surge tank two ends is provided with control valve, also is provided with relief valve on the exhaust tube.
With present compared with techniques, utilize the method for the invention to prepare composite, have that technology is simple, simple operation, do not need complex apparatus, timesaving advantage.The composite that makes both can have been alleviated the weakness of porous beta-TCP as the embedded material bad mechanical property; Also can solve the problem of magnesium alloy degradation speed and cell compatibility, and can reach the purpose of controlling composite degradation speed and performance through porosity and the pore size of regulating porous beta-TCP.
Existing report adopts the melt infiltration method that magnesium or magnesium alloy are penetrated in the porous tricalcium phosphate base substrate, makes magnesium or magnesium alloy and tricalcium phosphate composite material.Use the melt infiltration method in the preparation composite material, need be incubated infiltrations 1～8 hour, fully penetrate in the hole of porous tricalcium phosphate to guarantee magnesium or magnesium alloy at 700 ℃～800 ℃, more time-consuming like this.The vacuum suction casting technique that the present invention adopts is compared with the melt infiltration method, and porous beta-TCP contacts back 5 minutes with Mg or Mg alloy liquid just can accomplish the preparation process with interior, saved preparation time greatly, and technology is simple, does not need complex apparatus.The gained material structure both can have been alleviated the weakness of porous beta-TCP as the embedded material bad mechanical property; Also can solve the problem of Mg or Mg alloy degradation speed and cell compatibility, and can reach the purpose of controlling composite degradation speed and performance through porosity and the pore size of regulating porous beta-TCP.The composite of preparation be at first atresia with have good mechanical stability and mechanical strength, help the bone reparation like this, behind the certain hour, the degraded of Mg or Mg alloy just can form the inner porous beta-TCP structure of perforation each other, can support bone to grow into like this.Thereby the biodegradable of composite and osteoinductive are better coordinated.
Description of drawings
Fig. 1 is the structural representation of vacuum suction casting instrument.
Fig. 2 is the porous beta-TCP precursor structure.
Fig. 3 sucks the microstructure of composite that Mg-1%Ca alloy liquid forms in porous beta-TCP.
Fig. 4 sucks the microstructure of composite that Mg-1%Zn alloy liquid forms in porous beta-TCP.
The specific embodiment
For example the present invention is done in more detail below and describes:
Embodiment 1:
60 ℃ of water-baths, set Ca/P=1.48, under the pH=8 stirring condition with the diammonium hydrogen phosphate ((NH of 0.3mol/L
4)
2HPO
4) solution splashes into the calcium nitrate (Ca (NO of 0.4mol/L with the speed of (2～3) ml/min
3)
24H
2O) in the solution, treat that titration finishes the back at 60 ℃ of insulation 1h, be heated to 95 ℃～98 ℃ insulation 2h continued again and be stirred to the nature cooling; Leave standstill, natural subsidence is outwelled supernatant liquor and is obtained β-TCP solution; Adding 2% polyethylene glycol again stirs until there not being bubble to produce; Continue to stir and be warmed up to the polyvinyl alcohol of adding 8% after 95 ℃, naturally cool to room temperature after waiting to stir, form β-TCP slurry.With polyurethane foam clean up with absolute ethyl alcohol and ultrasonic Treatment 20min after dry, then polyurethane foam is put into the hydrochloric acid solution soaking and stirring 48h of 2mol/L, washing, drying earlier; Put into 5% sodium hydroxide solution soaking and stirring 48h again, washing, drying is so that foam has hydrophily preferably.To pass through pretreated polyurethane foam and put into β-TCP slurry, through obtaining uniform coat after the repeatedly processing of dipping-extruding, behind 60 ℃ of drying box inner drying 24h in heat-treatment furnace sintering.Sintering condition is: the heating rate with 0.8 ℃/min is warmed up to 600 ℃ of insulation 60min with precast body, and the speed with 5 ℃/min is warmed up to 1150 ℃ then, and the cooling rate with 5 ℃/min is chilled to room temperature behind the insulation 5h.Fig. 2 is the structure of the porous beta-TCP precast body of preparation.
In conjunction with Fig. 1, the composition that is used to prepare the vacuum suction casting instrument of magnesium and porous beta-calcium phosphate composite material comprises that two ends pass through the mould cavity 6 of cover plate 5 sealings up and down, and porous beta-calcium phosphate precast body 7 is installed in the mould cavity; Have stalk 4 on the lower cover; Stalk is deep in the container 3 of Mg that fusing is housed or Mg alloy, and the outside of container is provided with holding furnace 1, and upper cover plate connects exhaust tube; Exhaust tube links to each other with vavuum pump through surge tank; The exhaust tube at surge tank two ends is provided with control valve, also is provided with relief valve 8 on the exhaust tube, and control valve comprises precast body extraction valve 9 and vacuum system extraction valve 10.
Embodiment 2:
Method according to embodiment 1 prepares mesh structural porous structure β-TCP precast body.The Mg-1%Ca alloy is melted in electrical crucible by the atom proportioning, the coverture protection, 680 ℃～720 ℃ insulations down, for use; Vacuum system is bled in advance: the open vacuum pump, open the vacuum system extraction valve, vacuum system is evacuated in advance-close vavuum pump and vacuum system extraction valve behind 0.08～0.07MPa; Preheating precast body: the porous beta-TCP precast body is preheating to 150 ℃; Carry out suction pouring: the open vacuum pump, open the vacuum system extraction valve, open precast body air chamber extraction control valve, liquid magnesium alloy is under the effect of vacuum, and the porous beta-TCP precast body is advanced in filling, and the time relay picks up counting simultaneously.Behind the insulation 2min, vavuum pump and vacuum system extraction valve and extraction control valve are closed automatically, and open vacuum system decompression valve after the vacuum breaking, takes out sample simultaneously, obtains Mg or Mg alloy and porous beta-TCP composite.Fig. 3 injects the microstructure of composite that Mg-1%Ca alloy liquid forms in porous beta-TCP.As can be seen from the figure, β-TCP combines well with the Mg-1%Ca alloy, and microstructure of composite is fine and close, has also kept β-TCP and Mg connectedness separately simultaneously.
Embodiment 3:
Method according to embodiment 1 prepares mesh structural porous structure β-TCP precast body.The Mg-1%Zn alloy is melted in electrical crucible by the atom proportioning, the coverture protection, 680 ℃～720 ℃ insulations down, for use; Vacuum system is bled in advance: the open vacuum pump, open the vacuum system extraction valve, vacuum system is evacuated in advance-close vavuum pump and vacuum system extraction valve behind 0.08～0.07MPa; Preheating precast body: the porous beta-TCP precast body is preheating to 150 ℃; Carry out suction pouring: the open vacuum pump, open the vacuum system extraction valve, open precast body air chamber extraction control valve, liquid magnesium alloy is under the effect of vacuum, and the porous beta-TCP precast body is advanced in filling, and the time relay picks up counting simultaneously.Behind the insulation 2min, vavuum pump and vacuum system extraction valve and extraction control valve are closed automatically, and open vacuum system decompression valve after the vacuum breaking, takes out sample simultaneously, obtains Mg or Mg alloy and porous beta-TCP composite.Fig. 4 injects the microstructure of composite that Mg-1%Zn alloy liquid forms in porous beta-TCP.As can be seen from the figure, β-TCP combines well with the Mg-1%Zn alloy, and microstructure of composite is fine and close, has also kept β-TCP and Mg-1%Zn alloy connectedness separately simultaneously.
Can draw advantage of the present invention from above-mentioned experiment is: utilize the method for the invention to prepare composite, having technology simply, does not need complex apparatus, simple operation, timesaving advantage.The composite of preparation be at first atresia with have good mechanical stability and mechanical strength, help the bone reparation like this, implant certain hour after, the magnesium alloy degraded just can form the inner porous beta-TCP structure of perforation each other, can support bone to grow into like this.The composite of preparation both can have been alleviated the weakness of porous beta-TCP as the embedded material bad mechanical property; Also can solve the too fast problem with cell compatibility of magnesium alloy degradation speed, and can reach the purpose of controlling composite degradation speed and performance with pore size through the porosity of regulating porous beta-TCP.
Claims (2)
1. the preparation method of a magnesium or magnesium alloy and porous beta-calcium phosphate composite material is characterized in that:
(1) preparation of beta-calcium phosphate slurry: 60 ℃ of water-baths, set Ca/P=1.48, under the pH=8 stirring condition ammonium dibasic phosphate solution of the 0.3mol/L speed with 2～3ml/min is splashed in the calcium nitrate solution of 0.4mol/L; Treat that titration finishes the back at 60 ℃ of insulation 1h, be heated to 95 ℃～98 ℃ insulation 2h continued again and be stirred to the nature cooling, leave standstill; Natural subsidence; Outwell supernatant liquor and obtain beta-calcium phosphate solution, add 2% polyethylene glycol again and stir, continue to stir and be warmed up to and add 8% polyvinyl alcohol after 95 ℃ until there not being bubble to produce; Naturally cool to room temperature after waiting to stir, form the beta-calcium phosphate slurry;
(2) preliminary treatment of polyurethane foam: with polyurethane foam clean up with absolute ethyl alcohol and ultrasonic Treatment 20min after dry, then polyurethane foam is put into the hydrochloric acid solution soaking and stirring 48h of 2mol/L, washing, drying earlier; Put into 5% sodium hydroxide solution soaking and stirring 48h again, washing, drying;
(3) preparation of porous beta-calcium phosphate precast body: will pass through pretreated polyurethane foam and put into the beta-calcium phosphate slurry, through obtaining uniform coat after the repeatedly processing of dipping-extruding, behind 60 ℃ of drying box inner drying 24h in heat-treatment furnace sintering;
(4) preparation of Mg or Mg alloy and porous beta-calcium phosphate composite material is carried out on the vacuum suction casting instrument, and detailed process is:
1. the melting of Mg or Mg alloy: with Mg or Mg alloy melting, the coverture protection, 680 ℃～720 ℃ insulations down, for use;
2. vacuum system is bled in advance: the open vacuum pump, open the vacuum system extraction valve, and vacuum system is evacuated in advance-close vavuum pump and vacuum system extraction valve behind 0.08～0.07MPa;
3. precast body preheating: be installed in the vacuum suction casting instrument after the porous beta-calcium phosphate precast body is preheating to 150 ℃;
4. suction pouring: the open vacuum pump, open the vacuum system extraction valve, open precast body air chamber extraction control valve, Mg or Mg alloy liquid are under the effect of vacuum, and the porous beta-calcium phosphate precast body is advanced in filling, and the time relay picks up counting simultaneously;
5. after being incubated 2min, vavuum pump and vacuum system extraction valve and extraction control valve are closed automatically, and open vacuum system decompression valve after the vacuum breaking, takes out simultaneously, obtains Mg or Mg alloy and porous beta-calcium phosphate composite material.
2. the preparation method of magnesium according to claim 1 or magnesium alloy and porous beta-calcium phosphate composite material; It is characterized in that: the condition of said sintering is: the heating rate with 0.8 ℃/min is warmed up to 600 ℃ of insulation 60min with precast body; Speed with 5 ℃/min is warmed up to 1150 ℃ then, and the cooling rate with 5 ℃/min is chilled to room temperature behind the insulation 5h.
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| CN102727937B (en) * | 2012-06-28 | 2014-03-26 | 哈尔滨工程大学 | Biodegradable zinc (or zinc alloy) and porous biphase calcium phosphate composite material and preparation method thereof |
| CN102847916B (en) * | 2012-09-14 | 2015-08-05 | 西安航空动力股份有限公司 | A kind of suction pouring foundry goods removing from mould method |
| CN106166607A (en) * | 2016-08-29 | 2016-11-30 | 上海交通大学 | The suction pouring device of cast magnesium alloy |
| CN109807309A (en) * | 2017-11-20 | 2019-05-28 | 科华控股股份有限公司 | A kind of suction pouring room nitrogen charging explosion-protection equipment |
| CN108772555B (en) * | 2018-06-25 | 2020-01-03 | 溧阳市联华机械制造有限公司 | Explosion-proof device of vacuum suction casting chamber and control method thereof |
| CN111230044A (en) * | 2020-03-02 | 2020-06-05 | 青田保俐铸造有限公司 | Magnesium alloy investment casting equipment and method for carrying out investment casting by adopting same |
| CN111921011B (en) * | 2020-09-08 | 2022-07-19 | 西安点云生物科技有限公司 | Artificial bone coated with coating and preparation method thereof |
| CN113909456B (en) * | 2021-09-14 | 2023-04-25 | 昆明理工大学 | Preparation method of rare earth doped particle reinforced steel-based composite material |
| CN116832219B (en) * | 2023-08-29 | 2023-12-22 | 常州邦莱医疗科技有限公司 | Artificial bone repair material and preparation method thereof |
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| CN1792504A (en) * | 2005-12-26 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing composite material of high magnesium aluminium alloy-expanding ore |
| CN101559483A (en) * | 2008-04-15 | 2009-10-21 | 叶瑞文 | Vacuum updraught casting technology and equipment thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1792504A (en) * | 2005-12-26 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing composite material of high magnesium aluminium alloy-expanding ore |
| CN101559483A (en) * | 2008-04-15 | 2009-10-21 | 叶瑞文 | Vacuum updraught casting technology and equipment thereof |
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