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

Abstract

The invention discloses a hydroxyapatite-Ni ₃ Al composite material. The components and weight percentage thereof are: 92%-98% of hydroxyapatite and 2%-8% of Ni ₃ Al. The invention also discloses a preparation method of the composite material, the process of which is to firstly synthesize hydroxyapatite by chemical precipitation method, then prepare Ni ₃ Al intermetallic compound by mechanical alloying combined with heat treatment, and then combine hydroxyapatite with Ni ₃ The Al intermetallic compound powders are evenly mixed to prepare the hydroxyapatite Ni ₃ Al intermetallic compound composite material. The composite material has good mechanical properties and tissue biocompatibility, and has certain magnetism and wave-absorbing properties, and has application potential in human body load-bearing bones and magnetic and wave-absorbing materials.

Description

A kind of hydroxyapatite-Ni3Al composite material and its preparation method

technical field

The invention relates to a composite material of an intermetallic compound and a preparation method thereof, in particular to a hydroxyapatite-Ni ₃ Al composite material and a preparation method thereof, belonging to the technical field of medical materials science.

Background technique

In the mid-1930s, Nims, Korber and Tromel first synthesized hydroxyapatite, which started a new era of hydroxyapatite application. Through clinical application, it is found that the material has excellent biological activity, has good biocompatibility with animal tissues, has no toxic side effects, has osteoconductivity, can provide a physiological scaffold for the precipitation of new bone, and can form direct contact with bone tissue. Osseointegration is an artificial bone material with excellent biological properties, so it is widely used in clinical non-load-bearing bone and filling, while in the application of large-area bone repair and load-bearing artificial bone graft, the material itself is subject to high brittleness. , The limitation of poor mechanical properties. Therefore, it is limited in the application of load-bearing materials, and its functionality is not outstanding. At present, many methods have been used to strengthen and toughen hydroxyapatite ceramics. For example, layered structures, nanoparticles, metal particles, whiskers, fibers, carbon nanotubes, etc. The advantage of compounding is to improve the toughness and strength of hydroxyapatite ceramics. However, since the introduction of the second term often leads to a decrease in biocompatibility and may accelerate the decomposition of hydroxyapatite, generally speaking, the biological activity of hydroxyapatite materials enhanced by biologically inert materials will be lower than that of pure hydroxyapatite. Whisker-reinforced hydroxyapatite composites have a good toughening effect, but the whiskers can enter the human body from the hydroxyapatite matrix, which is likely to cause serious health problems and has potential carcinogenicity. .

Contents of the invention

In view of the deficiencies in the prior art, the problem to be solved in the present invention is to provide a composite material with hydroxyapatite ceramic material as matrix and Ni ₃ Al intermetallic compound as reinforcement; preliminary experiments show that the composite material has good biological Compatibility, high strength, no toxic side effects, can meet the requirements of human body load-bearing bones. The invention also provides the preparation method of the composite material.

The composition and weight percentage of the hydroxyapatite-Ni ₃ Al composite material involved in the present invention are: hydroxyapatite 92%-98%, Ni ₃ Al 2%-8%.

Wherein, the components and their weight percentages are preferably: hydroxyapatite 96%, Ni ₃ Al 4%.

In the above-mentioned hydroxyapatite-Ni ₃ Al composite material, the molar ratio of calcium and phosphorus in the hydroxyapatite is 1.67.

The preparation method of the hydroxyapatite- _Ni3Al composite material of the present invention is realized by the following steps:

(1) Prepare Ca(NO ₃ ) ₂ solution and (NH ₄ ) ₂ HPO ₄ solution respectively; first add Ca(NO ₃ ) ₂ solution into a three-necked flask, adjust its pH value to 10-12 with ammonia water, and then add ( NH ₄ ) ₂ HPO ₄ solution was added to the separatory funnel;

(2) Add the (NH ₁ ) ₂ HPO ₄ solution dropwise into the above-mentioned Ca(NO ₃ ) ₂ solution in such a way that the molar ratio of calcium and phosphorus elements is 1.67, and the titration time is controlled within 1 hour and kept in a stirring state; the reaction After completion, heat the product in a water bath to 90°C and keep it warm for 3 hours;

(3) Naturally cool to room temperature, suction filter the precipitate produced by the reaction, wash it with distilled water until it is neutral, and then wash it 3 times with absolute ethanol; then send the precipitate into an electric blower box and dry it at 120°C to 140°C 20 to 30 hours, then calcined at 900°C for 0.5 to 2 hours, then cooled, ground and sieved the powder to obtain hydroxyapatite powder;

(4) uniformly mix the analytically pure nickel powder and the analytically pure aluminum powder in an atomic ratio of 3: 1, and use a planetary ball mill to mill for 9 to 11 hours at 450 to 500 rpm high-energy balls to obtain a solid solution;

(5) Vacuum heat treatment of the above solid solution at 600°C and vacuum degree of 6.65×10 ^-2 Pa to obtain Ni ₃ Al intermetallic compound;

(6) In terms of weight percent, mix 92% to 98% of hydroxyapatite powder with 2% to 8% of Ni ₃ Al intermetallic compound, and pass through mechanical ball milling at 450 to 500 rpm for 3 to Within 5 hours, a composite powder with hydroxyapatite-Ni ₃ Al mixed uniformly was obtained;

(7) Pour the above-mentioned composite powder into a mold for cold pressing to form the embryo body of the hydroxyapatite-Ni ₃ Al composite material. Pressing and sintering, the holding time is 2-3 hours, and the hydroxyapatite-Ni ₃ Al composite material is obtained.

Wherein, the time for calcination at 900° C. in step (3) is preferably 0.5 to 1 hour.

Wherein, the time of the high-energy ball milling described in step (4) is preferably 10 hours.

Wherein, the mechanical ball milling condition in step (6) is preferably: 450 rpm, ball milling for 4 hours.

Wherein, the sintering temperature in step (7) is preferably 1150°C.

The preparation method of the hydroxyapatite-Ni ₃ Al composite material of the present invention is based on the excellent properties of hydroxyapatite and Ni ₃ Al intermetallic compounds, and utilizes the synergistic effect of Ni ₃ Al intermetallic compound toughening and plastic deformation toughening , and the nano effect, so that the composite material has high flexural strength and fracture toughness, and has good biocompatibility, and has certain magnetic properties and microwave absorption. The optimized selection of the reinforcing phase and preparation conditions is realized, and the comprehensive performance of hydroxyapatite is improved.

The hydroxyapatite-Ni ₃ Al composite material prepared by the present invention utilizes the intermetallic compound to have a long-range ordered superlattice structure, so that it has many special physical, chemical and mechanical properties, such as unique electrical properties and magnetic properties , acoustic properties, electron emission properties, catalytic properties, chemical stability and thermal stability, etc. It is an important new functional material and structural material, and it is also an excellent ceramic toughening material.

The performance test of the hydroxyapatite-Ni ₃ Al composite material prepared by the invention shows that its main indicators are: bending strength 80-180MPa, fracture toughness 1.0-2.6MPa·m ^1/2 .

The hydroxyapatite-Ni ₃ Al composite material prepared by the invention has application potential in the aspects of human body's load-bearing bone and magnetic and wave-absorbing materials.

Detailed ways

Example 1:

(1) Prepare Ca(NO ₃ ) ₂ solution and (NH ₄ ) ₂ HPO ₄ solution respectively; first put the Ca(NO ₃ ) ₂ solution into the three-necked flask, adjust its pH value to 10 with ammonia water, and then add (NH ₄ ) ₂ HPO ₄ solution was added to the separatory funnel;

(2) Add the (NH ₄ ) ₂ HPO ₄ solution dropwise into the above-mentioned Ca(NO ₃ ) ₂ solution in such a way that the molar ratio of calcium and phosphorus elements is 1.67 to react, and the titration time is controlled within 1 hour and kept in a stirring state; the reaction After completion, heat the product in a water bath to 90°C and keep it warm for 3 hours;

(3) Naturally cool to room temperature, suction filter the precipitate produced by the reaction, wash it with distilled water to neutrality, and then wash it 3 times with absolute ethanol; then send the precipitate into an electric blower box, and dry it at 120°C for 30 hours. Then calcined at 900°C for 0.6 hours, then cooled, ground and sieved the powder to obtain hydroxyapatite powder;

(4) Evenly mix the analytically pure nickel powder and the analytically pure aluminum powder at an atomic ratio of 3:1 (19.24 grams of analytically pure nickel powder, 2.95 grams of analytically pure aluminum powder), and use a planetary ball mill to mill for 11 hours with 450 rpm high-energy ball mill , to obtain a solid solution;

(5) Vacuum heat treatment of the above solid solution at 600°C and vacuum degree of 6.65×10 ^-3 Pa to obtain Ni ₃ Al intermetallic compound;

(6) In terms of weight percent, mix 98% hydroxyapatite powder with 2% Ni ₃ Al intermetallic compound, and pass through mechanical ball milling at 500 rpm for 3 hours to obtain hydroxyapatite- Composite powder with Ni ₃ Al mixed evenly;

(7) Pour the above composite powder into a mold for cold pressing to form an embryo body of the hydroxyapatite-Ni ₃ Al composite material. The embryo body is sintered without pressure in a vacuum sintering furnace at a temperature of 1200 ° C. The holding time is 2 hours, and the hydroxyapatite-Ni ₃ Al composite material is obtained.

The main properties of the prepared hydroxyapatite-Ni ₃ Al intermetallic compound biomaterial are as follows: flexural strength 90MPa, fracture toughness 1.2MPa·m ^1/2 , good biocompatibility.

Example 2:

(1) Prepare Ca(NO ₃ ) ₂ solution and (NH ₄ ) ₂ HPO ₄ solution respectively; first add Ca(NO ₃ ) ₂ solution into a three-necked flask, adjust its pH value to 11 with ammonia water, and then add (NH ₄ ) ₂ HPO ₄ solution was added to the separatory funnel;

(2) Add the (NH ₄ ) ₂ HPO ₄ solution dropwise into the above-mentioned Ca(NO ₃ ) ₂ solution in such a way that the molar ratio of calcium and phosphorus elements is 1.67 to react, and the titration time is controlled within 1 hour and kept in a stirring state; the reaction After completion, heat the product in a water bath to 90°C and keep it warm for 3 hours;

(3) Naturally cool to room temperature, suction filter the precipitate produced by the reaction, wash it with distilled water to neutrality, and then wash it 3 times with absolute ethanol; then send the precipitate into an electric blower box, and dry it at 130°C for 25 hours. Then calcined at 900°C for 1 hour, then cooled, ground and sieved the powder to obtain hydroxyapatite powder;

(4) uniformly mix the analytically pure nickel powder and the analytically pure aluminum powder in an atomic ratio of 3: 1, and use a planetary ball mill to mill for 10 hours at 450 rev/min high-energy balls to obtain a solid solution;

(5) Vacuum heat treatment of the above solid solution at 600°C and vacuum degree of 6.65×10 ^-3 Pa to obtain Ni ₃ Al intermetallic compound;

(6) In terms of weight percent, 96% of hydroxyapatite powder is mixed with 4% of Ni ₃ Al intermetallic compound, and passed through mechanical ball milling at 450 rpm for 4 hours to obtain hydroxyapatite- Composite powder with Ni ₃ Al mixed evenly;

(7) Pour the above composite powder into a mold for cold pressing to form a hydroxyapatite-Ni ₃ Al composite material embryo. The embryo is sintered in a vacuum sintering furnace at a temperature of 1150°C without pressure. The holding time is 2.5 hours, and the hydroxyapatite-Ni ₃ Al composite material is obtained.

The main properties of the prepared hydroxyapatite-Ni ₃ Al intermetallic compound biomaterial are as follows: flexural strength 131MPa, fracture toughness 1.6MPa·m ^1/2 , good biocompatibility.

Example 3:

(1) Prepare Ca(NO ₃ ) ₂ solution and (NH ₄ ) ₂ HPO ₄ solution respectively; first add Ca(NO ₃ ) ₂ solution into a three-necked flask, adjust its pH value to 12 with ammonia water, and then add (NH ₄ ) ₂ HPO ₄ solution was added to the separatory funnel;

(2) Add the (NH ₄ ) ₂ HPO ₄ solution dropwise into the above-mentioned Ca(NO ₃ ) ₂ solution in such a way that the molar ratio of calcium and phosphorus elements is 1.67 to react, and the titration time is controlled within 1 hour and kept in a stirring state; the reaction After completion, heat the product in a water bath to 90°C and keep it warm for 3 hours;

(3) Naturally cool to room temperature, suction filter the precipitate produced by the reaction, wash it with distilled water until it is neutral, and then wash it 3 times with absolute ethanol; then send the precipitate into an electric blower box, and dry it at 140°C for 20 hours. Then calcined at 900°C for 2 hours, then cooled, ground and sieved the powder to obtain hydroxyapatite powder;

(4) uniformly mix the analytically pure nickel powder and the analytically pure aluminum powder in an atomic ratio of 3:1, and use a planetary ball mill for 9 hours to obtain a solid solution with 500 rpm high-energy ball milling;

(5) Vacuum heat treatment of the above solid solution at 600°C and vacuum degree of 6.65×10 ^-3 Pa to obtain Ni ₃ Al intermetallic compound;

(6) In terms of weight percent, mix 92% hydroxyapatite powder with 8% Ni ₃ Al intermetallic compound, and pass through mechanical ball milling at 480 rpm for 3.5 hours to obtain hydroxyapatite- Composite powder with Ni ₃ Al mixed evenly;

(7) Pour the above composite powder into a mold for cold pressing to form a hydroxyapatite-Ni ₃ Al composite material embryo. The embryo is sintered in a vacuum sintering furnace at a temperature of 1100°C without pressure. The holding time is 3 hours, and the hydroxyapatite-Ni ₃ Al composite material is obtained.

The main properties of the prepared hydroxyapatite-Ni ₃ Al intermetallic compound biomaterials were determined: the bending strength was 152MPa, the fracture toughness was 1.8MPa·m ^1/2 , and the biocompatibility was good.

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 ℃.