CN1331541C - Hydroxy apatite Ni3Al composite material and its preparing method - Google Patents

Hydroxy apatite Ni3Al composite material and its preparing method Download PDF

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CN1331541C
CN1331541C CNB2005101045797A CN200510104579A CN1331541C CN 1331541 C CN1331541 C CN 1331541C CN B2005101045797 A CNB2005101045797 A CN B2005101045797A CN 200510104579 A CN200510104579 A CN 200510104579A CN 1331541 C CN1331541 C CN 1331541C
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composite
hydroxy apatite
hours
powder
hydroxyapatite
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CN1775310A (en
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孙康宁
孙昌
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Shandong University
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Shandong University
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Abstract

The present invention discloses hydroxyapatite-Ni3 Al composite material. The present invention has the components of 92% to 98% of hydroxyapatite and 2% to 8% of Ni3Al by weight. The present invention also discloses a preparation method of the composite material. The preparation method has the technological process that firstly, a chemical precipitation method is used for synthesizing the hydroxyapatite; mechanical alloying is combined with a heat treatment process to prepare Ni3 Al intermetallic compounds; then, the hydroxyapatite and the Ni3 Al intermetallic compound powder are uniformly mixed to prepare hydroxyapatite Ni3 Al intermetallic compound composite material. The composite material has the advantages of favorable mechanical property, tissue biocompatibility, certain magnetic property and certain wave absorbing property; the present invention has application potential in the aspects of human body's weight bearing bones, magnetic material and wave absorbing material.

Description

A kind of hydroxy apatite Ni 3Al composite and preparation method thereof
Technical field
The present invention relates to composite of a kind of intermetallic compound and preparation method thereof, relate in particular to a kind of hydroxy apatite Ni 3Al composite and preparation method thereof belongs to the medical material field that learns a skill.
Background technology
Last century middle nineteen thirties, people such as Nims, Korber and Tromel at first synthetic hydroxyapatite, begun new era that hydroxyapatite is used.Find that by clinical practice this material has excellent biological activity, with the animal body tissue better biocompatibility is arranged, have no side effect, has bone conductibility, can provide the physiology support for the precipitation of new bone, can form direct synostosis with osseous tissue, it is a kind of artificial bone of biology performance excellence, therefore be widely used in clinical non-bearing bone and filling aspect, and repair and load-bearing artificial bone graft application facet at the large tracts of land bone, then be subjected to the restriction of the fragility height of material own, poor mechanical property.Therefore be restricted in the load-bearing material application facet, and it is functional not outstanding.Present many methods have been used for the enhancing of hydroxylapatite ceramic and have mended tough.For example, layer structure, nano-particle, metallic particles, whisker, fiber, CNT etc.Compound advantage is that the toughness of hydroxylapatite ceramic and intensity are improved.But owing to introduce second decline that tends to cause biocompatibility, and might quicken the decomposition of hydroxyapatite, in general, the biological activity of the enhanced hydroxyapatite material of the enhanced apatite material of bio-inert material can be lower than the pure ha.The enhanced hydroxyapatite composite material of whisker has toughening effect preferably, and still, being used for whisker can enter into human body from the hydroxyapatite matrix, causes serious health problem easily, and potential carcinogenecity is arranged.
Summary of the invention
At the deficiencies in the prior art, it is matrix, Ni with the hydroxylapatite ceramic material that the problem to be solved in the present invention provides a kind of 3The Al intermetallic compound is for strengthening the composite of body; Preliminary experiment shows that this composite has excellent biological compatibility, and the intensity height has no side effect, and can satisfy the requirement of human loaded bone.The present invention also provides this composite material and preparation method thereof simultaneously.
The hydroxy apatite Ni that the present invention relates to 3The Al composite, its component and percentage by weight thereof are: hydroxyapatite 92%～98%, Ni 3Al 2%～8%.
Wherein, described component and percentage by weight thereof are preferably: hydroxyapatite 96%, Ni 3Al 4%.
At above-mentioned hydroxy apatite Ni 3In the Al composite, the mol ratio of calcium P elements is 1.67 in the described hydroxyapatite.
Hydroxy apatite Ni of the present invention 3The preparation method of Al composite, realized by following steps:
(1) prepares Ca (NO respectively 3) 2Solution and (NH 4) 2HPO 4Solution; Earlier with Ca (NO 3) 2Solution adds there-necked flask, and regulates its pH value to 10～12 with ammonia, again with (NH 4) 2HPO 4Solution adds separatory funnel;
(2) be that 1.67 amount is with (NH by the mol ratio of calcium P elements 1) 2HPO 4Drips of solution adds above-mentioned Ca (NO 3) 2React in the solution, titration time is controlled in 1 hour and keeps stirring; After reaction is finished, the product water-bath is heated to 90 ℃, is incubated 3 hours;
(3) naturally cool to room temperature, the precipitation that reaction produces is carried out sucking filtration, be washed with distilled water to neutrality earlier, reuse absolute ethanol washing 3 times; Then precipitation is sent in the electric heating bellows, 120 ℃～140 ℃ dryings 20～30 hours, again in 900 ℃ of calcinings 0.5～2 hour, cooling is then ground powder body, sieve, and promptly gets hydroxy apatite powder;
(4) analytical pure nikel powder and analytical pure aluminium powder are pressed 3: 1 uniform mixing of atomic ratio, with 450～500 rev/mins of high-energy ball millings 9～11 hours, make solid solution with planetary ball mill;
(5) with above-mentioned solid solution 600 ℃, vacuum 6.65 * 10 -2Carry out vacuum heat under the Pa condition, promptly obtain Ni 3The Al intermetallic compound;
(6) in the amount of percentage by weight, hydroxy apatite powder with 92%～98% and 2%～8% Ni 3The Al intermetallic compound mixes, and by 450～500 rev/mins mechanical ball millings 3～5 hours, promptly obtains hydroxy apatite Ni 3The composite powder of Al mix homogeneously;
(7) pour above-mentioned composite powder into the mould cold-press moulding, promptly make hydroxy apatite Ni 3The idiosome of Al composite, idiosome carry out pressureless sintering with 1100 ℃～1200 ℃ temperature conditions in vacuum sintering furnace, temperature retention time 2～3 hours promptly gets hydroxy apatite Ni 3The Al composite.
Wherein, preferably 0.5～1 hour described 900 ℃ of incinerating times of step (3).
Wherein, the time of the described high-energy ball milling of step (4) is preferably 10 hours.
Wherein, the described mechanical ball milling condition optimization of step (6) is: 450 rev/mins, and ball milling 4 hours.
Wherein, the described sintering temperature of step (7) is preferably 1150 ℃.
Hydroxy apatite Ni of the present invention 3The preparation method of Al composite is based on hydroxyapatite and Ni 3The premium properties of Al intermetallic compound utilizes Ni 3Toughness reinforcing and the toughness reinforcing cooperative effect of plastic deformation of Al intermetallic compound, and nano effect make composite have higher bending strength and fracture toughness, and have excellent biological compatibility, have certain magnetic and microwave absorbability simultaneously.Realized wild phase and preparation condition are optimized selection, improved the combination property of hydroxyapatite.
The hydroxy apatite Ni of the present invention's preparation 3The Al composite, utilize intermetallic compound to have the superstructure of long-range order, make it to have many special physicochemical and mechanical property, for example Du Te electrical properties, magnetic property, acoustic properties, electron emission character, catalytic property, chemical stability and heat stability etc., being important new function material and structural material, still is a kind of ceramic toughening material of excellence simultaneously.
The hydroxy apatite Ni that utilizes the present invention to prepare 3The Al composite is measured through performance test: its leading indicator is bending strength 80-180MPa, fracture toughness 1.0-2.6MPam 1/2
The hydroxy apatite Ni of the present invention's preparation 3The Al composite has application potential aspect human loaded bone and magnetic and the absorbing material.
The specific embodiment
Embodiment 1:
(1) prepares Ca (NO respectively 3) 2Solution and (NH 4) 2HPO 4Solution; Earlier with Ca (NO 3) 2Solution adds there-necked flask, and regulates its pH value to 10 with ammonia, again with (NH 4) 2HPO 4Solution adds separatory funnel;
(2) be that 1.67 amount is with (NH by the mol ratio of calcium P elements 4) 2HPO 4Drips of solution adds above-mentioned Ca (NO 3) 2React in the solution, titration time is controlled in 1 hour and keeps stirring; After reaction is finished, the product water-bath is heated to 90 ℃, is incubated 3 hours;
(3) naturally cool to room temperature, the precipitation that reaction produces is carried out sucking filtration, be washed with distilled water to neutrality earlier, reuse absolute ethanol washing 3 times; Then precipitation is sent in the electric heating bellows, 120 ℃ of dryings 30 hours, again in 900 ℃ of calcinings 0.6 hour, cooling is then ground powder body, sieve, and promptly gets hydroxy apatite powder;
(4) analytical pure nikel powder and analytical pure aluminium powder are pressed 3: 1 uniform mixing (analytical pure nikel powder 19.24 grams are with analytical pure aluminium powder 2.95 grams) of atomic ratio, with 450 rev/mins of high-energy ball millings 11 hours, made solid solution with planetary ball mill;
(5) with above-mentioned solid solution 600 ℃, vacuum 6.65 * 10 -3Carry out vacuum heat under the Pa condition, promptly obtain Ni 3The Al intermetallic compound;
(6) in the amount of percentage by weight, hydroxy apatite powder with 98% and 2% Ni 3The Al intermetallic compound mixes, and by 500 rev/mins mechanical ball millings 3 hours, promptly obtains hydroxy apatite Ni 3The composite powder of Al mix homogeneously;
(7) pour above-mentioned composite powder into the mould cold-press moulding, promptly make hydroxy apatite Ni 3The idiosome of Al composite, idiosome carry out pressureless sintering with 1200 ℃ of temperature conditions in vacuum sintering furnace, temperature retention time 2 hours promptly gets hydroxy apatite Ni 3The Al composite.
After measured, the hydroxy apatite Ni that makes 3The main performance of Al intermetallic compound composite biological material: bending strength 90MPa, fracture toughness 1.2MPam 1/2, biocompatibility is better.
Embodiment 2:
(1) prepares Ca (NO respectively 3) 2Solution and (NH 4) 2HPO 4Solution; Earlier with Ca (NO 3) 2Solution adds there-necked flask, and regulates its pH value to 11 with ammonia, again with (NH 4) 2HPO 4Solution adds separatory funnel;
(2) be that 1.67 amount is with (NH by the mol ratio of calcium P elements 4) 2HPO 4Drips of solution adds above-mentioned Ca (NO 3) 2React in the solution, titration time is controlled in 1 hour and keeps stirring; After reaction is finished, the product water-bath is heated to 90 ℃, is incubated 3 hours;
(3) naturally cool to room temperature, the precipitation that reaction produces is carried out sucking filtration, be washed with distilled water to neutrality earlier, reuse absolute ethanol washing 3 times; Then precipitation is sent in the electric heating bellows, 130 ℃ of dryings 25 hours, again in 900 ℃ of calcinings 1 hour, cooling is then ground powder body, sieve, and promptly gets hydroxy apatite powder;
(4) analytical pure nikel powder and analytical pure aluminium powder are pressed 3: 1 uniform mixing of atomic ratio, with 450 rev/mins of high-energy ball millings 10 hours, make solid solution with planetary ball mill;
(5) with above-mentioned solid solution 600 ℃, vacuum 6.65 * 10 -3Carry out vacuum heat under the Pa condition, promptly obtain Ni 3The Al intermetallic compound;
(6) in the amount of percentage by weight, hydroxy apatite powder with 96% and 4% Ni 3The Al intermetallic compound mixes, and by 450 rev/mins mechanical ball millings 4 hours, promptly obtains hydroxy apatite Ni 3The composite powder of Al mix homogeneously;
(7) pour above-mentioned composite powder into the mould cold-press moulding, promptly make hydroxy apatite Ni 3The idiosome of Al composite, idiosome carry out pressureless sintering with 1150 ℃ of temperature conditions in vacuum sintering furnace, temperature retention time 2.5 hours promptly gets hydroxy apatite Ni 3The Al composite.
After measured, the hydroxy apatite Ni that makes 3The main performance of Al intermetallic compound composite biological material: bending strength 131MPa, fracture toughness 1.6MPam 1/2, good biocompatibility.
Embodiment 3:
(1) prepares Ca (NO respectively 3) 2Solution and (NH 4) 2HPO 4Solution; Earlier with Ca (NO 3) 2Solution adds there-necked flask, and regulates its pH value to 12 with ammonia, again with (NH 4) 2HPO 4Solution adds separatory funnel;
(2) be that 1.67 amount is with (NH by the mol ratio of calcium P elements 4) 2HPO 4Drips of solution adds above-mentioned Ca (NO 3) 2React in the solution, titration time is controlled in 1 hour and keeps stirring; After reaction is finished, the product water-bath is heated to 90 ℃, is incubated 3 hours;
(3) naturally cool to room temperature, the precipitation that reaction produces is carried out sucking filtration, be washed with distilled water to neutrality earlier, reuse absolute ethanol washing 3 times; Then precipitation is sent in the electric heating bellows, 140 ℃ of dryings 20 hours, again in 900 ℃ of calcinings 2 hours, cooling is then ground powder body, sieve, and promptly gets hydroxy apatite powder;
(4) analytical pure nikel powder and analytical pure aluminium powder are pressed 3: 1 uniform mixing of atomic ratio, with 500 rev/mins of high-energy ball millings 9 hours, make solid solution with planetary ball mill;
(5) with above-mentioned solid solution 600 ℃, vacuum 6.65 * 10 -3Carry out vacuum heat under the pa condition, promptly obtain Ni 3The Al intermetallic compound;
(6) in the amount of percentage by weight, hydroxy apatite powder with 92% and 8% Ni 3The Al intermetallic compound mixes, and by 480 rev/mins mechanical ball millings 3.5 hours, promptly obtains hydroxy apatite Ni 3The composite powder of Al mix homogeneously;
(7) pour above-mentioned composite powder into the mould cold-press moulding, promptly make hydroxy apatite Ni 3The idiosome of Al composite, idiosome carry out pressureless sintering with 1100 ℃ of temperature conditions in vacuum sintering furnace, temperature retention time 3 hours promptly gets hydroxy apatite Ni 3The Al composite.
The hydroxy apatite Ni that makes after measured 3The main performance of Al intermetallic compound composite biological material: bending strength 152MPa, fracture toughness 1.8MPam 1/2, biocompatibility is better.

Claims (8)

1. hydroxy apatite Ni 3The Al composite, its component and percentage by weight thereof are: hydroxyapatite 92%～98%, Ni 3Al2%～8%.
2. hydroxy apatite Ni as claimed in claim 1 3The Al composite is characterized in that, described component and percentage by weight thereof are: hydroxyapatite 96%, Ni 3Al4%.
3. hydroxy apatite Ni as claimed in claim 1 or 2 3The Al composite is characterized in that, the mol ratio of calcium P elements is 1.67 in the described hydroxyapatite.
4. the described hydroxy apatite Ni of claim 1 3The preparation method of Al composite, realized by following steps:
(1) prepares Ca (NO respectively 3) 2Solution and (NH 4) 2HPO 4Solution; Earlier with Ca (NO 3) 2Solution adds there-necked flask, and regulates its pH value to 10～12 with ammonia, again with (NH 4) 2HPO 4Solution adds separatory funnel;
(2) be that 1.67 amount is with (NH by the mol ratio of calcium P elements 4) 2HPO 4Drips of solution adds above-mentioned Ca (NO 3) 2React in the solution, titration time is controlled in 1 hour and keeps stirring; After reaction is finished, the product water-bath is heated to 90 ℃, is incubated 3 hours;
(3) naturally cool to room temperature, the precipitation that reaction produces is carried out sucking filtration, be washed with distilled water to neutrality earlier, reuse absolute ethanol washing 3 times; Then precipitation is sent in the electric heating bellows, 120 ℃～140 ℃ dryings 20～30 hours, again in 900 ℃ of calcinings 0.5～2 hour, cooling is then ground powder body, sieve, and promptly gets hydroxy apatite powder;
(4) analytical pure nikel powder and analytical pure aluminium powder are pressed 3: 1 uniform mixing of atomic ratio, with 450～500 rev/mins of high-energy ball millings 9～11 hours, make solid solution with planetary ball mill;
(5) with above-mentioned solid solution 600 ℃, vacuum 6.65 * 10 -3Carry out vacuum heat under the Pa condition, promptly obtain Ni 3The Al intermetallic compound;
(6) in the amount of percentage by weight, hydroxy apatite powder with 92%～98% and 2%～8% Ni 3The Al intermetallic compound mixes, and by 450～500 rev/mins mechanical ball millings 3～5 hours, promptly obtains hydroxy apatite Ni 3The composite powder of Al mix homogeneously;
(7) pour above-mentioned composite powder into the mould cold-press moulding, promptly make hydroxy apatite Ni 3The idiosome of Al composite, idiosome carry out pressureless sintering with 1100 ℃～1200 ℃ temperature conditions in vacuum sintering furnace, temperature retention time 2～3 hours promptly gets hydroxy apatite Ni 3The Al composite.
5, hydroxy apatite Ni as claimed in claim 4 3The preparation method of Al composite is characterized in that, described 900 ℃ of incinerating times of step (3) are 0.5～1 hour.
6, hydroxy apatite Ni as claimed in claim 4 3The preparation method of Al composite is characterized in that, the time of the described high-energy ball milling of step (4) is 10 hours.
7, hydroxy apatite Ni as claimed in claim 4 3The preparation method of Al composite is characterized in that, the described mechanical ball milling condition of step (6) is: 450 rev/mins, and ball milling 4 hours.
8, hydroxy apatite Ni as claimed in claim 4 3The preparation method of Al composite is characterized in that, the described sintering temperature of step (7) is 1150 ℃.
CNB2005101045797A 2005-11-18 2005-11-18 Hydroxy apatite Ni3Al composite material and its preparing method Expired - Fee Related CN1331541C (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4146936A (en) * 1975-12-30 1979-04-03 Sumitomo Chemical Company Limited Implants for bones, joints and tooth roots
JPH0413605A (en) * 1990-05-01 1992-01-17 Sangi Co Ltd Inorganic antimicrobial agent and production thereof
CN1060531C (en) * 1998-04-21 2001-01-10 冶金工业部钢铁研究总院 Method for preparation of composite ceramic-Ni-Al intermetallic material
CN1172873C (en) * 2003-04-02 2004-10-27 山东大学 Composite hydroxyapatite/carbon nanotube material and its prepn process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4146936A (en) * 1975-12-30 1979-04-03 Sumitomo Chemical Company Limited Implants for bones, joints and tooth roots
JPH0413605A (en) * 1990-05-01 1992-01-17 Sangi Co Ltd Inorganic antimicrobial agent and production thereof
CN1060531C (en) * 1998-04-21 2001-01-10 冶金工业部钢铁研究总院 Method for preparation of composite ceramic-Ni-Al intermetallic material
CN1172873C (en) * 2003-04-02 2004-10-27 山东大学 Composite hydroxyapatite/carbon nanotube material and its prepn process

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