CN104018020A - Preparation method for porous titanium matrix/hydroxyapatite coating composite material - Google Patents
Preparation method for porous titanium matrix/hydroxyapatite coating composite material Download PDFInfo
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- CN104018020A CN104018020A CN201410213144.5A CN201410213144A CN104018020A CN 104018020 A CN104018020 A CN 104018020A CN 201410213144 A CN201410213144 A CN 201410213144A CN 104018020 A CN104018020 A CN 104018020A
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Abstract
The invention relates to a preparation method for a porous titanium matrix/hydroxyapatite coating composite material. The preparation method comprises the steps of weighing TiH2 powder and a pore-forming agent-sodium chloride particles according to a certain mass ratio; mixing for use; putting the mixture into a mold; preparing into a blank; putting the blank into a vacuum sintering furnace; heating to decompose titanium hydride powder; heating continuously to finish sintering; cooling; dissolving the pore-forming agent-sodium chloride in hot water; washing for use; dissolving a certain amount of a Ca(NO)3.4H2O reagent and a P2O5 reagent in ethanol respectively to form precursors; mixing with stirring to form a hydroxyapatite gel; dissolving a certain amount of AgNO3 and KNO3 reagents in ethanol; mixing with the gel under stirring; immersing/extracting porous titanium from the gel for a plurality of times to obtain a silver- and potassium-containing hydroxyapatite coating on the surface of porous titanium, and thus the porous titanium matrix/hydroxyapatite coating composite material is obtained. The preparation method is simple in process and is energy conservation. The porous titanium matrix/hydroxyapatite coating composite material has wide porosity and size ranges.
Description
Technical field
The present invention relates to biomedical materials field, particularly relate to a kind of preparation method of POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material.
Background technology
Some people need to adopt medical material to carry out sclerous tissues as replacement and the reparation of bone, root of the tooth etc.Some bone of human body has vesicular structure feature.Medical porous titanium because have that good biocompatibility, vesicular structure are conducive to that tissue is grown into and the conveying of body fluid and nutrient, mechanical property especially Young's modulus the feature such as mate with sclerous tissues and be expected to become hard tissue implanting material.But the biologically inert of metallic substance itself need to improve by approach such as surface modifications, as at porous metal surface deposition hydroxyl apatite biological painting, and improve its biocompatibility.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material.Present method can sinter POROUS TITANIUM into, and on POROUS TITANIUM surface, prepares the hydroxyapatite coating layer of argentiferous and potassium by sol-gel method.The pore texture of this matrix material is conducive to tissue and grows into and body fluid and nutrient conveying; Hydroxyapatite coating layer has biological activity, can induce growing into of osseous tissue, and silver has anti-microbial effect, and potassium is the essential element that bone forms.
The technical scheme adopting is:
A preparation method for POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material, comprises the following steps:
(1) be averaged the titanium hydride (TiH of granularity≤150 micron
2) powder is standby, then it is standby as pore-forming material to get the near cubical sodium-chlor chemical reagent particle of 100-400 micron.
(2) by the TiH of corresponding mass
2powder and pore-forming material mix 8-12 hour resulting mixture in blender, standby.The massfraction of its pore-forming material in mixture is 5-50%.
(3) said mixture is put into mould, the blank that is pressed into setting shape under the pressure of 50-100MPa is standby.
(4) above-mentioned blank is put into the vacuum sintering furnace of 0.01Pa≤vacuum tightness≤1Pa, its sintering standard is:
blank is heated to 800 ℃ of insulations 1 hour with the speed of≤20 ℃/min, so that titanium hydride powders is decomposed into titanium and hydrogen, gas is discharged blank and furnace chamber, is protective atmosphere.
blank is continued to the speed of≤20 ℃/min, be heated to 1160-1250 ℃ of insulations to be cooled to room temperature for 4-8 hours with the furnace and completes POROUS TITANIUM sintering.
after cooling, POROUS TITANIUM is put into the beaker that distilled water is housed and be heated to 90 ℃, every 1 hour, change time water, pore-forming material NaCl can be dissolved after 10-15 time.
(5) by the POROUS TITANIUM HF:HNO after cleaning
3: H
2o=1:4:10(volume ratio) reagent pickling is after 5-10 minute, then with acetone and distilled water ultrasonic cleaning 50-60 minute respectively, standby.
(6) Ca (NO that is 10:3 by mol ratio
3)
24H
2o reagent and P
2o
5reagent is dissolved into precursor respectively in the ethanol reagent of equivalent, through mixing and stirring and within 6-8 hour, make hydroxyapatite colloidal sols.Then be heated to 65 ℃ and keep 1 hour, treat that hydroxyapatite colloidal sols becomes opaque shape, be cooled to room temperature, standing 48 hours, standby.Ca (the NO of every mole wherein
3)
24H
2the ethanol reagent of the corresponding 600-750ml of O reagent.
(7) by a certain amount of AgNO
3and KNO
3reagent dissolves in ethanol, and with hydroxyapatite colloidal sols mix and blend.Then be heated to 85 ℃ and keep 1 hour, make ethanol volatilization.Ca (NO wherein
3)
24H
2o:AgNO
3: KNO
3=10:(1-3): (1-3) (mol ratio); The AgNO of every mole
3and KNO
3the ethanol of the respectively corresponding 500-600ml of reagent.
(8) POROUS TITANIUM of cleaning being dried speed with 2-5mm/ minute in above-mentioned colloidal sol immerses/extract out, is then heated to 300 ℃ and keeps forming gel and being cooled to room temperature for 15-20 minute, completes one-period.Repeatedly after 6-12 times, be heated to 600 ℃ keep 10 minutes and be cooled to room temperature after can obtain on POROUS TITANIUM surface the hydroxyapatite coating layer of argentiferous and potassium.Thereby obtain POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material.
The porosity scope of above-mentioned step (4) gained POROUS TITANIUM is about 10-70%, and average pore size scope is 130-430 microns, has nearly cubical pore texture.Large 30 microns than the mean particle size of pore-forming material of the average pore size of the POROUS TITANIUM of sintering.
Rule-of-thumb relation between the porosity (P) of the POROUS TITANIUM of above-mentioned institute's sintering and the pore-forming material mass percent (D) in the mixture of metal-powder and pore-forming material is P ≈ 0.034+1.316D+0.038D
2, D=20% for example, 0.2 o'clock, P ≈ 0.299,29.9%.
POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material of the present invention has the Young's modulus mating with human body hard tissue, and vesicular structure is similar to the microtexture of human body spongy bone.In hydroxyapatite coating layer, containing Ag and K element, wherein Ag has antibacterial feature, and K is the skeletogenous essential element of shape.This matrix material can be used for replacement and the reparation of bone, root of the tooth etc., is desirable hard tissue substituting material.Technique of the present invention is easier, energy-conservation, environmental protection, and porosity wide ranges, average pore size wide ranges, the thickness of hydroxyapatite coating layer is controlled, and coating is containing Ag and K element.
Embodiment
Embodiment mono-
(1) be averaged the commercial TiH of granularity≤50 micron
2powder, standby.The size range of screening of the learning from else's experience pore-forming material sodium chloride particle that is 100-150 microns, standby.
(2) get the TiH of 90g
2powder mixes 8 hours with the sodium chloride particle of 10g in blender, makes the mixture of metal-powder and pore-forming material.Put into mould, under 50MPa pressure, be pressed into
fthe blank of 40mm * 60mm.
(3) subsequently blank is put into vacuum sintering furnace and be heated to 800 ℃ of insulations 1 hour with the speed of 20 ℃/min, then be heated to 1250 ℃ of insulations 4 hours, the cooling POROUS TITANIUM that obtains with the speed of 20 ℃/min.Vacuum sintering furnace (vacuum tightness 0.1Pa).After cooling, POROUS TITANIUM is put into distilled water and be heated to 90 ℃, every 1 hour, change time water, pore-forming material NaCl can be dissolved after 10 times.
(4) by the POROUS TITANIUM HF:HNO after cleaning
3: H
2the reagent pickling of O=1:4:10 is after 5 minutes, then with the ultrasonic cleaning 50 minutes respectively of acetone and distilled water, standby.
(5) by the Ca (NO of 0.2 mol
3)
24H
2the P of O reagent and 0.06 mol
2o
5reagent dissolves respectively in the ethanol reagent of 130ml, then mixes and stirs and within 6 hours, make hydroxyapatite colloidal sols.Then be heated to 65 ℃ and keep 1 hour, treat that colloidal sol color becomes opaque shape, be cooled to room temperature, standing 48 hours, standby.By the AgNO of 0.02 mol
3with 0.02mol KNO
3reagent dissolves respectively in the ethanol of 10ml, and with colloidal sol mix and blend.Then be heated to 85 ℃ and keep 1 hour, make ethanol volatilization.
(6) POROUS TITANIUM of cleaning being dried speed with 2 mm/ minutes in above-mentioned colloidal sol immerses/extract out, is heated to 300 ℃ and keeps forming gel and being cooled to room temperature for 15 minutes, completes one-period.Repeatedly after 6 times, be heated to 600 ℃ keep 10 minutes and be cooled to room temperature after can obtain on POROUS TITANIUM surface the hydroxyapatite coating layer that contains silver and potassium.Thereby obtain POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material.
Average pore size scope is 130-180 micron, is subsphaeroidal and near cubical pore texture.Porosity is 16.6%.
Embodiment bis-
(1) be averaged the commercial TiH of granularity≤90 micron
2powder, standby.The size range of sieving of learning from else's experience is the pore-forming material sodium chloride particle of 150-200 micron, standby.
(2) get the TiH of 80g
2powder mixes 12 hours with the sodium chloride particle of 20g in blender.Put into mould, under 90MPa pressure, be pressed into
fthe blank of 40mm * 70mm.
(3) subsequently blank is put into vacuum sintering furnace and be heated to 800 ℃ of insulations 1 hour with the speed of 20 ℃/min, then be heated to 1200 ℃ of insulations 6 hours, the cooling POROUS TITANIUM that obtains with the speed of 15 ℃/min.Vacuum sintering furnace (vacuum tightness 0.01Pa).POROUS TITANIUM is put into distilled water and be heated to 90 ℃, every 1 hour, change time water, NaCl can be dissolved after 15 times.
(4) by the POROUS TITANIUM HF:HNO after cleaning
3: H
2the reagent pickling of O=1:4:10 is after 10 minutes, then with the ultrasonic cleaning 50 minutes respectively of acetone and distilled water, standby.
(5) by the Ca (NO of 0.3mol
3)
24H
2the P of O reagent and 0.09 mol
2o
5reagent dissolves respectively in the ethanol reagent of 200ml, then mixes and stirs and within 6 hours, make hydroxyapatite colloidal sols.Then be heated to 65 ℃ and keep 1 hour, treat that colloidal sol color becomes opaque shape, be cooled to room temperature, standing 48 hours, standby.By the AgNO of 0.06mol
3with 0.06 mol KNO
3reagent dissolves respectively in the ethanol of 35ml, and with colloidal sol mix and blend.Then be heated to 85 ℃ and keep 1 hour, make ethanol volatilization.
(6) POROUS TITANIUM of cleaning being dried speed with 5 mm/ minutes in above-mentioned colloidal sol immerses/extract out, reheats to 300 ℃ and keeps forming gel and being cooled to room temperature for 20 minutes, completes one-period.Repeatedly after 8 times, be heated to 600 ℃ keep 10 minutes and be cooled to room temperature after can obtain on POROUS TITANIUM surface the hydroxyapatite coating layer that contains silver and potassium.Thereby obtain POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material.
Average pore size scope is 180-230 micron, is subsphaeroidal and near cubical pore texture.Porosity is 29.9%.
Embodiment tri-
(1) be averaged the commercial TiH of granularity≤150 micron
2powder, standby.The setting size range of sieving of learning from else's experience is the pore-forming material sodium chloride particle of 300-350 micron, standby.
(2) get the TiH of 60g
2powder mixes 10 hours with the sodium chloride particle of 40g in blender, makes the mixture of metal-powder and pore-forming material.Put into mould, under 100MPa pressure, be pressed into
fthe blank of 50mm * 80mm.
(3) subsequently blank is put into vacuum sintering furnace and be heated to 800 ℃ of insulations 1 hour with the speed of 20 ℃/min, then be heated to 1160 ℃ of insulations 8 hours, the cooling POROUS TITANIUM that obtains with the speed of 20 ℃/min.Vacuum sintering furnace (vacuum tightness 1Pa).POROUS TITANIUM is put into distilled water and be heated to 90 ℃, every 1 hour, change time water, NaCl can be dissolved after 15 times.
(4) by the POROUS TITANIUM HF:HNO after cleaning
3: H
2the reagent pickling of O=1:4:10 is after 8 minutes, then with the ultrasonic cleaning 55 minutes respectively of acetone and distilled water, standby.
(5) by the Ca (NO of 0.4mol
3)
24H
2the P of O reagent and 0.12 mol
2o
5reagent dissolves respectively in the ethanol reagent of 230ml, then mixes and stirs and within 6 hours, make hydroxyapatite colloidal sols.Then be heated to 65 ℃ and keep 1 hour, treat that colloidal sol color becomes opaque shape, be cooled to room temperature, standing 48 hours, standby.By the AgNO of 0.04 mol
3with 0.04mol KNO
3reagent dissolves respectively in the ethanol of 20ml, and with colloidal sol mix and blend.Then be heated to 85 ℃ and keep 1 hour, make ethanol volatilization.
(6) POROUS TITANIUM of cleaning being dried speed with 3 mm/ minutes in above-mentioned colloidal sol immerses/extract out, reheats to 300 ℃ and keeps forming gel and being cooled to room temperature for 20 minutes, completes one-period.Repeatedly after 10 times, be heated to 600 ℃ keep 10 minutes and be cooled to room temperature after can obtain on POROUS TITANIUM surface the hydroxyapatite coating layer that contains silver and potassium.Thereby obtain POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material.
Average pore size scope is 330-380 micron, is nearly cubical pore texture.Porosity is 56.6%.
Claims (3)
1. a preparation method for POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material, is characterized in that comprising the following steps:
(1) be averaged the titanium hydride powders of granularity≤150 micron standby, then it is standby as pore-forming material to get the near cubical sodium-chlor chemical reagent particle of 100-400 micron;
(2) by the TiH of corresponding mass
2it is standby that powder and pore-forming material mix 8-12 hour resulting mixture in blender, and the massfraction of its pore-forming material in mixture is 5-50%;
(3) said mixture is put into mould, the blank that is pressed into setting shape under the pressure of 50-100MPa is standby;
(4) above-mentioned blank is put into the vacuum sintering furnace of 0.01Pa≤vacuum tightness≤1Pa, its sintering standard is:
blank is heated to 800 ℃ of insulations 1 hour with the speed of≤20 ℃/min, so that titanium hydride powders is decomposed into titanium and hydrogen, gas is discharged blank and furnace chamber, is protective atmosphere;
blank is continued to the speed of≤20 ℃/min, be heated to 1160-1250 ℃ of insulations to be cooled to room temperature for 4-8 hours with the furnace and completes POROUS TITANIUM sintering;
after cooling, POROUS TITANIUM is put into the beaker that distilled water is housed and be heated to 90 ℃, every 1 hour, change time water, pore-forming material sodium-chlor can be dissolved after 10-15 time;
(5) by the POROUS TITANIUM volume ratio after cleaning, be HF:HNO
3: H
2the reagent pickling 5-10 minute of O=1:4:10, then with acetone and distilled water difference ultrasonic cleaning 50-60 minute, standby;
(6) Ca (NO that is 10:3 by mol ratio
3)
24H
2o reagent and P
2o
5reagent is dissolved into precursor respectively in the ethanol reagent of equivalent, through mixing and stirring and within 6-8 hour, make hydroxyapatite colloidal sols, is then heated to 65 ℃ and keep 1 hour, treat that hydroxyapatite colloidal sols becomes opaque shape, be cooled to room temperature, standing 48 hours standby, wherein Ca (the NO of every mole
3)
24H
2the ethanol reagent of the corresponding 600-750ml of O reagent;
(7) by a certain amount of AgNO
3and KNO
3reagent dissolves in ethanol, and with hydroxyapatite colloidal sols mix and blend, be then heated to 85 ℃ and keep 1 hour, make ethanol volatilization, wherein Ca (NO
3)
24H
2o:AgNO
3: KNO
3=10:(1-3): (1-3), its ratio is mol ratio; The AgNO of every mole
3and KNO
3the ethanol of the respectively corresponding 500-600ml of reagent;
(8) POROUS TITANIUM of cleaning being dried speed with 2-5mm/ minute in above-mentioned colloidal sol immerses/extract out, then being heated to 300 ℃ keeps forming gel and being cooled to room temperature for 15-20 minute, complete one-period, repeatedly after 6-12 times, after being heated to 600 ℃ of maintenances 10 minutes and being cooled to room temperature, can obtain on POROUS TITANIUM surface the hydroxyapatite coating layer of argentiferous and potassium, thereby obtain POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material.
2. the preparation method of a kind of POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material according to claim 1, the porosity scope that it is characterized in that described step (4) gained POROUS TITANIUM is 10-70%, average pore size scope is 130-430 microns, there is nearly cubical pore texture, large 30 microns than the mean particle size of pore-forming material of the average pore size of the POROUS TITANIUM of sintering.
3. the preparation method of a kind of POROUS TITANIUM matrix/hydroxyapatite coating layer matrix material according to claim 1, is characterized in that the porosity P of POROUS TITANIUM of described institute's sintering and the rule-of-thumb relation between the mass percent D of pore-forming material in the mixture of metal-powder and pore-forming material are P ≈ 0.034+1.316D+0.038D
2, D=20% for example, 0.2 o'clock, P ≈ 0.299,29.9%.
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| CN108611528A (en) * | 2018-05-09 | 2018-10-02 | 西南交通大学 | A kind of graphene enhancing titanium-based/nano HA composite material and preparation method |
| CN109111343A (en) * | 2018-09-10 | 2019-01-01 | 大连理工大学 | A kind of low-carbon alcohols catalyzed conversion prepares the method and used catalyst of benzylalcohol and homologue |
| CN111230128A (en) * | 2020-03-11 | 2020-06-05 | 昆明理工大学 | Based on TiH2Method for preparing porous titanium and titanium alloy by adding CaO |
| CN113737055A (en) * | 2021-09-07 | 2021-12-03 | 淮阴工学院 | Titanium alloy surface co-doped antibacterial/osteoinductive material and preparation method thereof |
| CN114377196A (en) * | 2021-12-28 | 2022-04-22 | 天衍医疗器材有限公司 | Coating with biological activity and antibacterial function and application thereof |
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| CN103290248A (en) * | 2013-05-31 | 2013-09-11 | 西华大学 | Preparation method of particle-reinforced wearable porous titanium |
| CN103540784A (en) * | 2013-10-29 | 2014-01-29 | 昆明理工大学 | Preparation method of biomedical porous titanium alloy |
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Patent Citations (3)
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| US20110281127A1 (en) * | 2010-05-13 | 2011-11-17 | Korea Institute Of Machinery And Materials | Preparation method of hydroxyapatite coating layer using aerosol deposition and hydrothermal treatment, and nanostructured hydroxyapatite coating layer prepared by the method |
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| CN108611528A (en) * | 2018-05-09 | 2018-10-02 | 西南交通大学 | A kind of graphene enhancing titanium-based/nano HA composite material and preparation method |
| CN109111343A (en) * | 2018-09-10 | 2019-01-01 | 大连理工大学 | A kind of low-carbon alcohols catalyzed conversion prepares the method and used catalyst of benzylalcohol and homologue |
| CN109111343B (en) * | 2018-09-10 | 2021-05-07 | 大连理工大学 | Method for preparing benzyl alcohol and homologues through catalytic conversion of low-carbon alcohol and used catalyst |
| CN111230128A (en) * | 2020-03-11 | 2020-06-05 | 昆明理工大学 | Based on TiH2Method for preparing porous titanium and titanium alloy by adding CaO |
| CN111230128B (en) * | 2020-03-11 | 2022-12-20 | 昆明理工大学 | Based on TiH 2 Method for preparing porous titanium and titanium alloy by adding CaO |
| CN113737055A (en) * | 2021-09-07 | 2021-12-03 | 淮阴工学院 | Titanium alloy surface co-doped antibacterial/osteoinductive material and preparation method thereof |
| CN113737055B (en) * | 2021-09-07 | 2022-06-03 | 淮阴工学院 | Titanium alloy surface co-doped antibacterial/osteoinductive material and preparation method thereof |
| CN114377196A (en) * | 2021-12-28 | 2022-04-22 | 天衍医疗器材有限公司 | Coating with biological activity and antibacterial function and application thereof |
| CN114892164A (en) * | 2022-05-19 | 2022-08-12 | 湘潭大学 | Preparation method of porous membrane on inner wall of stainless steel heat pipe |
| CN114892164B (en) * | 2022-05-19 | 2023-10-27 | 湘潭大学 | Preparation method of porous membrane on inner wall of stainless steel heat pipe |
| US11896960B1 (en) * | 2022-07-20 | 2024-02-13 | Jiangsu Vocational College of Agriculture and Forestry | High-efficiency visible-light catalytic material and preparation method and application thereof |
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