CN104623734A - Rapid preparation method of magnesium/hydroxyapatite degradable composite material - Google Patents
Rapid preparation method of magnesium/hydroxyapatite degradable composite material Download PDFInfo
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- CN104623734A CN104623734A CN201510049748.5A CN201510049748A CN104623734A CN 104623734 A CN104623734 A CN 104623734A CN 201510049748 A CN201510049748 A CN 201510049748A CN 104623734 A CN104623734 A CN 104623734A
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Abstract
The invention relates to a rapid preparation method of a magnesium/hydroxyapatite degradable composite material. Aiming at the special requirements of bone tissue engineering materials in the clinical medicine, magnesium and hydroxyapatite are used as raw materials and are subjected to ball-milling, mixing, die filling and spark plasma sintering to quickly prepare the magnesium/hydroxyapatite degradable composite material. The preparation method is advanced in process, accurate and detailed in data, high in preparation speed, and high in technological parameter index; according to the prepared magnesium/hydroxyapatite degradable composite material, the block microhardness reaches 60HV, the compactness reaches 98.47%; the bending strength reaches 180MPa; the breaking tenacity reaches 5.2MPa.m<1/2>; the prepared magnesium/hydroxyapatite degradable composite material can be used as a bone implantation material in the clinical medicine, and the preparation method is an ideal rapid preparation method of the magnesium/hydroxyapatite degradable composite material.
Description
Technical field
The present invention relates to the fast preparation method of a kind of magnesium/hydroxyapatite degradable composite material, belong to the technical field of the preparations and applicatio of biomaterial.
Background technology
In clinical medicine application, biomedical metal material can make the passive sclerous tissues of sclerotin usually, can be made into cardiac valve, meninges, peritoneum soft tissue, conventional biomedical metal material has rustless steel, cobalt-base alloys, titanium-base alloy, nickel billon, these materials have intensity when being applied to bone tissue engineer high, good toughness and good counter-bending fatigue strength, but the stress-shielding effect caused because intensity is higher can affect therapeutic effect, these materials all can not be absorbed by the body, the ion of degrading in-service also may damage human body, so under arms the phase terminate after need to carry out second operation and remove, both misery was brought to patient, also have impact on therapeutic effect, return patient and bring financial burden, the degradable biological medical metal material of therefore researching and developing function admirable is very important.
Magnesium metal aboundresources, with the Compact bone similar density of people's bone, magnesium has higher specific strength and specific stiffness, and processing characteristics is excellent, effectively can reduce stress-shielding effect, the trace release of magnesium ion to human body is useful, biocompatibility is good, but the corrosion-resistant of magnesium, what can become in corrosive medium is loose porous, mechanical properties decrease, pure magnesium is difficult to be applied to clinical, if add nonmetallic materials in magnesium matrix, improve its mechanical property, magnesium being expanded property application in biomedicine will be made.
At present, the preparation for magnesio biodegradable composite material is also in conceptual phase, there is preparation process complexity, and the shortcoming that material performance index is low does not reach the requirement of clinical practice.
Summary of the invention
Goal of the invention
The object of the invention is the present situation for background technology, be raw material with magnesium, hydroxyapatite, through ball milling, batch mixing, die-filling, discharge plasma sintering, prepare magnesium/hydroxyapatite degradable composite material fast, the index making composite closer to nature bone is added, to improve the decay resistance of material by hydroxyapatite.
Technical scheme
The chemical substance material that the present invention uses is: magnesium, hydroxyapatite, dehydrated alcohol, argon, graphite block, graphite cushion block, graphite briquetting, graphite paper, and it is as follows that it prepares consumption: with gram, milliliter, centimetre
3for measurement unit
Magnesium: Mg 30g ± 0.01g
Hydroxyapatite: Ca
10(PO
4)
6(OH)
23g ± 0.01g
Dehydrated alcohol: C
2h
6o 1000mL ± 10mL
Argon: Ar 10000cm
3± 100cm
3
Graphite block: C 200mm × 100mm × 100mm
Graphite cushion block: C Φ 20mm × 10mm
Graphite briquetting: C Φ 20mm × 10mm
Graphite paper: C 100mm × 1mm × 50mm
Sand paper: 400 order 300mm × 0.5mm × 200mm
Preparation method is as follows:
(1) selected chemical substance material
To carry out selected to the chemical substance material used, and carry out precision, control of purity:
Magnesium: solid powder 99.99%
Hydroxyapatite: solid powder 99%
Graphite block: C solid slug 98.5%
Graphite cushion block: C solid slug 98.5%
Graphite briquetting: C solid slug 98.5%
Graphite paper: C solid slug 98.5%
Dehydrated alcohol: liquid liquid 99.7%
Argon: gaseous atmospheres 99.99%
(2) graphite jig is made
Graphite jig graphite block makes, and mold cavity is cylindrical cavity, and die cavity diameter is Φ 20mm, mold cavity surface roughness Ra≤0.08 ~ 0.16 μm;
(3) prepare burden
In vacuum glove box, take magnesium powder 30g ± 0.01g, hydroxylapatite powder 3g ± 0.01g, put into ball grinder, mix with agate ball abrading-ball;
(4) ball milling mixes powder
Ball grinder is arranged in ball mill;
Start ball mill, carry out ball milling, rotational speed of ball-mill is 532r/min, and Ball-milling Time is 180min, becomes mixing fine powders after ball milling;
(5) feed
Graphite cylindrical mould is vertically placed on steel flat board, uses washes of absolute alcohol mold cavity;
Put graphite cushion block at graphite jig cavity bottom, put graphite paper on graphite cushion block top, put mixing fine powders on graphite paper top, put graphite paper on mixing fine powders top, put graphite briquetting on graphite paper top;
(6) discharge plasma sintering prepares magnesium/hydroxyapatite degradable composite material
The sintering of magnesium/hydroxyapatite degradable composite material carries out in discharge plasma sintering stove, heating, exerts pressure, completes under argon shield;
1. open the water cycle cooling tube of discharge plasma sintering stove outside, carry out outer water cycle cooling;
2. open discharge plasma sintering stove, by the workbench in the graphite jig straight immigration discharge plasma sintering stove of charging, close fire door, airtight;
3. open the vacuum pump of discharge plasma sintering stove, extract furnace air, make pressure in furnace chamber reach 2Pa;
4. open argon bottle, in furnace chamber, input argon, argon input speed 100cm
3/ min, makes pressure≤10 in furnace chamber
5pa;
5. the heater of star t-up discharge plasma agglomeration stove, heat-agglomerating temperature is 480 DEG C ± 2 DEG C, sintering time 5min;
6., after terminating, stop heating, make graphite jig and interior magnesium/hydroxyapatite mixing fine powders thereof cool to 25 DEG C with the furnace, after cooling, become magnesium/hydroxyapatite block;
(7) blow-on, delivery, taking-up block materials
Open discharge plasma sintering stove, take out graphite jig;
Graphite jig is placed on forcing press, extrudes the magnesium/hydroxyapatite block in mold cavity, that is: magnesium/hydroxyapatite degradable composite material;
(8) shaping
Magnesium/hydroxyapatite degradable composite material block is placed on steel flat board, with sand papering periphery and positive and negative surface, removes graphite paper, make any surface finish;
(9) clean
By magnesium/hydroxyapatite degradable composite material block is placed on laboratory bench, with washes of absolute alcohol periphery and positive and negative surface, make it clean;
Dry after cleaning;
(10) detect, analyze, characterize
Magnesium/the pattern of hydroxyapatite degradable composite material block prepared, color and luster, microhardness, thing phase, decay resistance are analyzed, characterized;
With metallurgical microscope, scanning electron microscope, observation analysis is carried out to composite block surface pattern;
With nano-hardness tester, Resarch on A New Type is carried out to composite;
With XRD analysis instrument, material phase analysis is carried out to composite;
Conclusion: magnesium/hydroxyapatite degradable composite material is silvery white cylindrical block, and microhardness reaches 60HV, and density reaches 98.74%, and bending strength reaches 180MPa, and fracture toughness reaches 5.2MPam
1/2;
(11) packing and storing
Magnesium/hydroxyapatite degradable composite material block soft material the vacuum packaging of preparation, stores shady and cool clean environment, moistureproof, sun-proof, anti-acid-alkali salt to corrode, storage temperature 20 DEG C, relative humidity≤10%.
Beneficial effect
The present invention has obvious advance compared with background technology, it is the particular/special requirement for clinical medicine engineering material of bone tissue, adopt magnesium, hydroxyapatite is raw material, through ball milling, batch mixing, die-filling, discharge plasma sintering, prepare magnesium/hydroxyapatite degradable composite material block fast, this preparation method technique is advanced, data are accurately full and accurate, preparation speed is fast, technological parameter index is high, magnesium/hydroxyapatite degradable composite material block the microhardness of preparation reaches 60HV, density reaches 98.74%, bending strength reaches 180MPa, fracture toughness reaches 5.2MPam
1/2, can meet clinical medical orthopedic implanting material and use, be the fast preparation method of very good magnesium/hydroxyapatite degradable composite material.
Accompanying drawing explanation
Fig. 1, magnesium/hydroxyapatite degradable composite material discharge plasma sintering state diagram
Fig. 2, magnesium/hydroxyapatite degradable composite material cross section shape appearance figure
Fig. 3, magnesium/hydroxyapatite degradable composite material XRD diffracted intensity collection of illustrative plates
Shown in figure, list of numerals is as follows:
1, discharge plasma sintering stove, 2, footstock, 3, base, 4, bearing, 5, outer water cycle cooling tube, 6, vacuum pump, 7, vacuum tube, 8, cooling water tank, 9, water pump, 10, water inlet pipe, 11 return pipes, 12, workbench, 13, pressure block, 14, graphite jig, 15, lower cushion block, 16, first graphite paper, 17, magnesium/hydroxyapatite mixed powder, 18, second graphite paper, 19, upper holder block, 20, to give vent to anger pipe valve, 21, pressure motor, 22, argon bottle, 23, argon valve, 24, tunger tube, 25, argon, 26, electric cabinet, 27, display screen, 28, display lamp, 29, heating temperature control, 30, controller for vacuum pump, 31, water pump controller, 32, pressure electric machine controller, 33, first wire, 34, second wire, 35, privates, 36, furnace chamber.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention will be further described:
Shown in Fig. 1, be magnesium/hydroxylapatite biology degradable composite material discharge plasma sintering state diagram, each position, annexation wants correct, and proportioning according to quantity, operates according to the order of sequence.
The value of the chemical substance material that preparation uses determines by the scope pre-set, with gram, milliliter, millimeter, centimetre
3for measurement unit.
The preparation of magnesium/hydroxyapatite degradable composite material is carried out in discharge plasma sintering stove, heating, exerts pressure, completes under argon shield;
Discharge plasma sintering stove is vertical, is footstock 2, bottom is base 3, bearing 4 on the top of discharge plasma sintering stove 1; Top, top 2 is provided with pressure motor 21; Vacuum pump 6, cooling water tank 8 is provided with in base 3, bearing 4; In the outside of discharge plasma sintering stove 1 by outer water cycle cooling tube 5 around; Be furnace chamber 36 in discharge plasma sintering stove 1, be provided with workbench 12 at the inner bottom part of furnace chamber 36, on table 12 vertically graphite jig 14; Be lower cushion block 15 at graphite jig 14 inner bottom part, be the first graphite paper 16 on lower cushion block 15 top, be magnesium/hydroxyapatite mixed powder 17 on the first graphite paper 16 top, be the second graphite paper 18 on magnesium/hydroxyapatite mixed powder 17 top, second graphite paper 18 top is upper holder block 19, upper holder block 19 top Bonding pressure block 13, pressure block 13 is connected with the pressure motor 21 on footstock 2 top; Vacuum pump 6 is communicated with furnace chamber 36 by vacuum tube 7; Be provided with water pump 9 on cooling water tank 8 top, water pump 9 connects the outer water cycle cooling tube 5 of right part by water inlet pipe 10, and outer water cycle cooling tube 5 connects cooling water tank 8 by the return pipe 11 of left part, forms water-flow circuit; Be provided with argon bottle 22 at the left part of discharge plasma sintering stove 1, argon bottle 22 top is communicated with furnace chamber 36 by argon valve 23, tunger tube 24, and inputs argon 25 in furnace chamber 36; Be provided with electric cabinet 26 at the right part of discharge plasma sintering stove 1, electric cabinet 26 is provided with display screen 27, display lamp 28, heating temperature control 29, controller for vacuum pump 30, water pump controller 31, pressure electric machine controller 32; Electric cabinet 26 is connected with vacuum pump 6 by the first wire 33, and electric cabinet 26 is connected with water pump by the second wire 34, and electric cabinet 26 is connected with pressure motor 21 by privates 35.
Shown in Fig. 2; for magnesium/hydroxyapatite degradable composite material cross section shape appearance figure; shown in figure, hydroxyapatite is evenly distributed in magnesium granules surface, protects magnesium granules; the membership that adds of hydroxyapatite causes the mechanical strength of material to reduce; but the elasticity due to magnesium is greater than the elastic modelling quantity of people's bone, its intensity still can meet the demands, on the other hand; low elastic modelling quantity, can alleviate stress-shielding effect.
Shown in Fig. 3, for magnesium/hydroxyapatite degradable composite material XRD diffracted intensity collection of illustrative plates, as shown in the figure, main phase after magnesium/hydroxyapatite degradable composite material discharge plasma sintering has Mg, hydroxyapatite, still the existence of hydroxyapatite is had in composite, illustrate that the magnesium in matrix does not have and hydroxyapatite generation chemical reaction, this is conducive to the biological activity keeping the original composition of composite.
Claims (2)
1. the fast preparation method of magnesium/hydroxyapatite degradable composite material, it is characterized in that: the chemical substance material of use is: magnesium, hydroxyapatite, dehydrated alcohol, argon, graphite block, graphite cushion block, graphite briquetting, graphite paper, it is as follows that it prepares consumption: with gram, milliliter, centimetre
3for measurement unit
Magnesium: Mg 30g ± 0.01g
Hydroxyapatite: Ca
10(PO
4)
6(OH)
23g ± 0.01g
Dehydrated alcohol: C
2h
6o 1000mL ± 10mL
Argon: Ar 10000cm
3± 100cm
3
Graphite block: C 200mm × 100mm × 100mm
Graphite cushion block: C Φ 20mm × 10mm
Graphite briquetting: C Φ 20mm × 10mm
Graphite paper: C 100mm × 1mm × 50mm
Sand paper: 400 order 300mm × 0.5mm × 200mm
Preparation method is as follows:
(1) selected chemical substance material
To carry out selected to the chemical substance material used, and carry out precision, control of purity:
Magnesium: solid powder 99.99%
Hydroxyapatite: solid powder 99%
Graphite block: C solid slug 98.5%
Graphite cushion block: C solid slug 98.5%
Graphite briquetting: C solid slug 98.5%
Graphite paper: C solid slug 98.5%
Dehydrated alcohol: liquid liquid 99.7%
Argon: gaseous atmospheres 99.99%
(2) graphite jig is made
Graphite jig graphite block makes, and mold cavity is cylindrical cavity, and die cavity diameter is Φ 20mm, mold cavity surface roughness Ra≤0.08 ~ 0.16 μm;
(3) prepare burden
In vacuum glove box, take magnesium powder 30g ± 0.01g, hydroxylapatite powder 3g ± 0.01g, put into ball grinder, mix with agate ball abrading-ball;
(4) ball milling mixes powder
Ball grinder is arranged in ball mill;
Start ball mill, carry out ball milling, rotational speed of ball-mill is 532r/min, and Ball-milling Time is 180min, becomes mixing fine powders after ball milling;
(5) feed
Graphite cylindrical mould is vertically placed on steel flat board, uses washes of absolute alcohol mold cavity;
Put graphite cushion block at graphite jig cavity bottom, put graphite paper on graphite cushion block top, put mixing fine powders on graphite paper top, put graphite paper on mixing fine powders top, put graphite briquetting on graphite paper top;
(6) discharge plasma sintering prepares magnesium/hydroxyapatite degradable composite material
The sintering of magnesium/hydroxyapatite degradable composite material carries out in discharge plasma sintering stove, heating, exerts pressure, completes under argon shield;
1. open the water cycle cooling tube of discharge plasma sintering stove outside, carry out outer water cycle cooling;
2. open discharge plasma sintering stove, by the workbench in the graphite jig straight immigration discharge plasma sintering stove of charging, close fire door, airtight;
3. open the vacuum pump of discharge plasma sintering stove, extract furnace air, make pressure in furnace chamber reach 2Pa;
4. open argon bottle, in furnace chamber, input argon, argon input speed 100cm
3/ min, makes pressure≤10 in furnace chamber
5pa;
5. the heater of star t-up discharge plasma agglomeration stove, heat-agglomerating temperature is 480 DEG C ± 2 DEG C, sintering time 5min;
6., after terminating, stop heating, make graphite jig and interior magnesium/hydroxyapatite mixing fine powders thereof cool to 25 DEG C with the furnace, after cooling, become magnesium/hydroxyapatite block;
(7) blow-on, delivery, taking-up block materials
Open discharge plasma sintering stove, take out graphite jig;
Graphite jig is placed on forcing press, extrudes the magnesium/hydroxyapatite block in mold cavity, that is: magnesium/hydroxyapatite degradable composite material;
(8) shaping
Magnesium/hydroxyapatite degradable composite material block is placed on steel flat board, with sand papering periphery and positive and negative surface, removes graphite paper, make any surface finish;
(9) clean
By magnesium/hydroxyapatite degradable composite material block is placed on laboratory bench, with washes of absolute alcohol periphery and positive and negative surface, make it clean;
Dry after cleaning;
(10) detect, analyze, characterize
Magnesium/the pattern of hydroxyapatite degradable composite material block prepared, color and luster, microhardness, thing phase, decay resistance are analyzed, characterized;
With metallurgical microscope, scanning electron microscope, observation analysis is carried out to composite block surface pattern;
With nano-hardness tester, Resarch on A New Type is carried out to composite;
With XRD analysis instrument, material phase analysis is carried out to composite;
Conclusion: magnesium/hydroxyapatite degradable composite material is silvery white cylindrical block, and microhardness reaches 60HV, and density reaches 98.74%, and bending strength reaches 180MPa, and fracture toughness reaches 5.2MPam
1/2;
(11) packing and storing
Magnesium/hydroxyapatite degradable composite material block soft material the vacuum packaging of preparation, stores shady and cool clean environment, moistureproof, sun-proof, anti-acid-alkali salt to corrode, storage temperature 20 DEG C, relative humidity≤10%.
2. the fast preparation method of a kind of magnesium/hydroxyapatite degradable composite material according to claim 1, it is characterized in that: the preparation of magnesium/hydroxyapatite degradable composite material is carried out in discharge plasma sintering stove, heating, exert pressure, complete under argon shield;
Discharge plasma sintering stove is vertical, is footstock (2), bottom is base (3), bearing (4) on the top of discharge plasma sintering stove (1); Top (2) top is provided with pressure motor (21); Vacuum pump (6), cooling water tank (8) is provided with in base (3), bearing (4); In the outside of discharge plasma sintering stove (1) by outer water cycle cooling tube (5) around; Be furnace chamber (36) in discharge plasma sintering stove (1), be provided with workbench (12) at the inner bottom part of furnace chamber (36), vertically graphite jig (14) on workbench (12); Be lower cushion block (15) at graphite jig (14) inner bottom part, be the first graphite paper (16) on lower cushion block (15) top, it is magnesium/hydroxyapatite mixed powder (17) on the first graphite paper (16) top, be the second graphite paper (18) on magnesium/hydroxyapatite mixed powder (17) top, second graphite paper (18) top is upper holder block (19), upper holder block (19) top Bonding pressure block (13), pressure block (13) is connected with the pressure motor (21) on footstock (2) top; Vacuum pump (6) is communicated with furnace chamber (36) by vacuum tube (7); Water pump (9) is provided with on cooling water tank (8) top, water pump (9) connects the outer water cycle cooling tube (5) of right part by water inlet pipe (10), outer water cycle cooling tube (5) connects cooling water tank (8) by the return pipe (11) of left part, forms water-flow circuit; Argon bottle (22) is provided with at the left part of discharge plasma sintering stove (1), argon bottle (22) top is communicated with furnace chamber (36) by argon valve (23), tunger tube (24), and input argon (25) in furnace chamber (36); Be provided with electric cabinet (26) at the right part of discharge plasma sintering stove (1), electric cabinet (26) is provided with display screen (27), display lamp (28), heating temperature control (29), controller for vacuum pump (30), water pump controller (31), pressure electric machine controller (32); Electric cabinet (26) is connected with vacuum pump (6) by the first wire (33), electric cabinet (26) is connected with water pump by the second wire (34), and electric cabinet (26) is connected with pressure motor (21) by privates (35).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105397090A (en) * | 2015-10-30 | 2016-03-16 | 昆明理工大学 | Preparation method for porous nickel titanium/hydroxyapatite composite material |
| CN105869922A (en) * | 2016-04-11 | 2016-08-17 | 太原理工大学 | Rapid preparation method of manganese oxide/carbon sphere composite material for three-dimensional (3D) printing |
| CN106583740A (en) * | 2016-11-29 | 2017-04-26 | 太原理工大学 | Preparing method for nanocrystalline magnesium alloy block |
| CN109631567A (en) * | 2018-11-30 | 2019-04-16 | 太原理工大学 | A kind of ultrasonic auxiliary electric stream activated sintering furnace |
| CN112620630A (en) * | 2020-12-15 | 2021-04-09 | 昆明理工大学 | Preparation method of zinc-magnesium/hydroxyapatite porous composite material |
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| CN101099873A (en) * | 2006-07-03 | 2008-01-09 | 佳木斯大学 | Technology method for producing porous magnesium/hydroxyl apatite |
| CN101603160A (en) * | 2009-07-07 | 2009-12-16 | 重庆大学 | Hydroxyapatite crystal whisker/magnesium metal base composite material and preparation method thereof |
| KR101101711B1 (en) * | 2009-12-22 | 2012-01-05 | 한국세라믹기술원 | Thermoelectric device and manufacturing method of the same |
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| CN101099873A (en) * | 2006-07-03 | 2008-01-09 | 佳木斯大学 | Technology method for producing porous magnesium/hydroxyl apatite |
| CN101603160A (en) * | 2009-07-07 | 2009-12-16 | 重庆大学 | Hydroxyapatite crystal whisker/magnesium metal base composite material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105397090A (en) * | 2015-10-30 | 2016-03-16 | 昆明理工大学 | Preparation method for porous nickel titanium/hydroxyapatite composite material |
| CN105869922A (en) * | 2016-04-11 | 2016-08-17 | 太原理工大学 | Rapid preparation method of manganese oxide/carbon sphere composite material for three-dimensional (3D) printing |
| CN106583740A (en) * | 2016-11-29 | 2017-04-26 | 太原理工大学 | Preparing method for nanocrystalline magnesium alloy block |
| CN109631567A (en) * | 2018-11-30 | 2019-04-16 | 太原理工大学 | A kind of ultrasonic auxiliary electric stream activated sintering furnace |
| CN112620630A (en) * | 2020-12-15 | 2021-04-09 | 昆明理工大学 | Preparation method of zinc-magnesium/hydroxyapatite porous composite material |
| CN112620630B (en) * | 2020-12-15 | 2023-09-26 | 昆明理工大学 | Preparation method of zinc-magnesium/hydroxyapatite porous composite material |
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