CN1048291C - Preparation of reinforced ion beam-deposited hydroxyl apatite coating for medical implant - Google Patents
Preparation of reinforced ion beam-deposited hydroxyl apatite coating for medical implant Download PDFInfo
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- CN1048291C CN1048291C CN97120353A CN97120353A CN1048291C CN 1048291 C CN1048291 C CN 1048291C CN 97120353 A CN97120353 A CN 97120353A CN 97120353 A CN97120353 A CN 97120353A CN 1048291 C CN1048291 C CN 1048291C
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- ion beam
- energy
- torr
- electric current
- bombardment
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 25
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 25
- 239000011248 coating agent Substances 0.000 title claims abstract description 11
- 238000000576 coating method Methods 0.000 title claims abstract description 11
- 150000002500 ions Chemical class 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000007943 implant Substances 0.000 title claims description 8
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010884 ion-beam technique Methods 0.000 claims abstract description 14
- 238000004544 sputter deposition Methods 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 4
- 238000000151 deposition Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000010849 ion bombardment Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000005477 sputtering target Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 7
- 238000005507 spraying Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 3
- 238000001659 ion-beam spectroscopy Methods 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The present invention relates to a method for preparing reinforced ion beam-deposited hydroxyl apatite coating for medical implanting objects. The method takes 50 % of sinter ceramic of hydroxyl apatite as a sputtering target. Firstly, samples are bombarded by Ar ions to be cleaned, the sputtering target is bombarded by an ion beam under the condition of keeping steam partial pressure, and films are formed by sputtering on the surfaces of substrate samples; simultaneously, the substrate samples are bombarded by an auxiliary high-energy Ar ion beam, and film samples are taken out from a vacuum chamber and are annealed in wet air after the film samples are heated to 380 to 420 DEG C. The coating prepared by the present invention has the advantages of strong binding force of films and basal pieces, high density of the films, good biocompatibility, etc.
Description
The present invention relates to a kind of preparation method who restraints the reinforced ion beam-deposited hydroxyl apatite coating of medical implant, use ion beam enhanced depositing (IBAD) technology to be coated with hydroxyapatite (Hydroxyapatite on metal, pottery, high molecular polymer surface, HA) film belongs to materials science field.
The method for preparing hydroxyapatite (HA) film mainly contains plasma spray coating, ion plating, ion beam sputtering, magnetron sputtering, radio-frequency sputtering and ion implantation combining, pulsed laser deposition, electrophoretic deposition, HIP sintering and gluing plating.At present most popular is the plasma spray coating technology.Plasma spray coating technology ionic medium flame is the Ar by the arc method plasma, N
2Or H
2Gas composition.Flame temperature can reach about 20000 ℃, and the outgoing speed of flame surpasses mach one (Mach).Hydroapatite particles is ejected into the substrate sample surface filming by flame fusing back with the speed that surpasses mach one.Afterwards, film just can obtain the hydroxyapatite film of certain degree of crystallinity through washing, thermal treatment.
Use the plasma spray coating technology,, medically obtaining application widely at the surface deposition hydroxyl apatite coating of artificial medical science organ.But secular medical science follow-up study shows that this artificial bone is implanted the work-ing life of organ and lacked (about 7～8 years), and in the more teenager of activity, its work-ing life is just shorter.This is because the HA that makes with this technology has two great weakness:
1) bonding force of film and substrate sample is good inadequately.
2) density of film own is not high enough, makes film/substrate sample be subjected to the erosion of body fluid at the interface easily, causes under the human body environment, and the bonding force of film and substrate sample descends significantly, causes coming off of film, harm patient's body health.
The objective of the invention is to study a kind of preparation method of reinforced ion beam-deposited hydroxyl apatite coating of medical implant, to improve film and the bonding force of substrate sample, the density of raising film itself, the work-ing life of finally improving the artificial bone implanting prosthetic.
The preparation method of the reinforced ion beam-deposited hydroxyl apatite coating of medical implant of the present invention comprises following each step:
(1) clean: with electric current is 30～60mA, and energy is the Ar ion beam bombardment substrate sample surface of 0.8～1.2KeV, and bombardment time is 10～15 minutes, and background pressure is 5 * 10
-6Torr, in the working process, keeping steam partial pressure is 0～2 * 10
-4Torr, operating pressure are 0.5～2.5 * 10
-4Torr;
(2) make the interface: the hydroxyapatite sintered ceramic with 50% is as sputtering target, with electric current is 20～60mA, energy is the ion beam bombardment of 0.3～3.5KeV, in substrate sample surface sputtering film forming, be 1～3mA with electric current simultaneously, energy is the high energy Ar ion beam bombardment substrate sample surface of 24～30KeV, and sputtering time is 10～30 minutes;
(3) deposited film growth: the sputter procedure in above-mentioned second step is proceeded, with electric current is that 40～100mA, energy are the ion beam bombardment of 3～3.5KeV, continues spatter film forming, is 5～20mA with electric current simultaneously, energy is the energy Ar ion bombardment of 0.5～400eV, and sputtering time is 1～5 hour;
(4) behind the plated film 1 hour, the sample in above-mentioned the 3rd step is taken out from vacuum, be heated to 380 ℃～420 ℃, annealed 0～4 hour in humidity greater than 70% damp atmosphere, can obtain possessing the medical implant of hydroxyl apatite coating.
In above-mentioned preparation method, when the steam partial pressure in the first step was 0, the last handling process in the 4th step was just essential.If keep certain steam partial pressure in the first step, the aftertreatment in the 4th step is decided by the degree of crystallinity of required rete, when degree of crystallinity is not determined to require, can exempt last handling process.
Among the above-mentioned preparation method, used substrate sample can be any in metal, pottery or the high molecular polymer.
Utilize the membrane sample of method preparation of the present invention, it is made the scratch experiment result shows, the film that obtains in this way, in loading rate is under the condition of 2000gf/min, ion beam enhanced depositing (IBAD) film is respectively 1050gf and 660gf with the critical load that is used for correlated ion beam sputtering (IBSD) film, the former is the latter's a twice nearly, the raising that this explanation ion beam enhanced depositing (IBAD) method is bigger the bonding force of film and substrate sample.Relevant result of study is verified, the bonding force of ion beam sputtering film and plasma spray plated film quite, therefore can infer that the bonding force of ion beam enhanced depositing (IBAD) film also is improved largely than the bonding force of plasma spray plated film.And the bonding force problem of film and substrate sample perplexs the problem that the plasma spray coating technology prepares the hydroxyapatite film just for a long time always.Like this, utilize the IBAD technology, successfully solved this subject matter.
SEM result shows the very densification of film that the IBAD method obtains, and its density is far longer than the hydroxyapatite film that other method obtains.This shows that the IBAD method can improve the density of film itself greatly.
Cytologic experiment shows that the IBAD film has good biocompatibility, and IBAD is in the mechanical property that improves film itself in this explanation, has kept the biology advantage of hydroxyapatite film at least.
Description of drawings:
Fig. 1 is an equipment used synoptic diagram of the present invention.
Among Fig. 1,1 is and the vacuum pump interface, and 2 is rotatable water-cooled sample table, and 3 is substrate sample, and 4 and 5 is the plasma sputter source, and 6 is rotatable hydroxyapatite sintered ceramic water cooled target, and 7 is high energy bombarding ion source, and 8 is low energy bombarding ion source.
Introduce embodiments of the invention below:
Embodiment 1 adopts the listed parameter plated film of following table, and at 400 ± 20 ℃, humidity was not less than in 70% the air annealing 2 hours, just can obtain degree of crystallinity near 100% hydroxyapatite film.
| Substrate sample | The Ti-6Al-4V alloy | |
| Background pressure | 5×10 -6Torr (torr) | |
| Steam partial pressure | 5×10 -6Torr (torr) | |
| Operating pressure | 5×10 -6Torr (torr) | |
| Ionic fluid cleans | (1.0keV kiloelectron volt), 50mA (milliampere), 12min (minute) | |
| Make the interface | The high energy bombardment | 28keV (kiloelectron volt), 2mA (milliampere), |
| Make the interface | Sputter | (3.5keV kiloelectron volt), 45mA (milliampere), |
| Make the interface | Time | 30min (minute) |
| Deposition growing | The low energy bombardment | Do not have |
| Deposition growing | Sputter | (3.25keV kiloelectron volt), 60mA (milliampere), |
| Deposition growing | Time | 3hr (hour) |
| Aftertreatment | 400 ± 20 ℃, 2hr (hour) | |
Embodiment 2
| Substrate sample | Al 2O 3Pottery | |
| Background pressure | 5×10 -6Torr (torr) | |
| Steam partial pressure | Do not have | |
| Operating pressure | 2.2×10 -4Torr (torr) | |
| Ionic fluid cleans | (1.0keV kiloelectron volt), 50mA (milliampere), 12min (minute) | |
| Make the interface | The high energy bombardment | 30keV (kiloelectron volt), 2mA (milliampere), |
| Make the interface | Sputter | (3.25keV kiloelectron volt), 45mA (milliampere), |
| Make the interface | Time | 15min (minute) |
| Deposition growing | The low energy bombardment | 150eV (electron-volt), 10mA (milliampere) |
| Deposition growing | Sputter | (3.25keV kiloelectron volt), 90mA (milliampere), |
| Deposition growing | Time | 2.5hr (hour) |
| Aftertreatment | 400 ± 20 ℃, 2hr (hour) | |
Embodiment 3
| Substrate sample | Ultra high molecular polyethylene | |
| Background pressure | 5×10 -6Torr (torr) | |
| Steam partial pressure | 1.2×10 -4Torr (torr) | |
| Operating pressure | 2.2×10 -4Torr (torr) | |
| Ionic fluid cleans | (1.0keV kiloelectron volt), 30mA (milliampere), 5min (minute) | |
| Make the interface | The high energy bombardment | 25keV (kiloelectron volt), 1mA (milliampere), |
| Make the interface | Sputter | (3.25keV kiloelectron volt), 30mA (milliampere), |
| Make the interface | Time | 10min (minute) |
| Deposition growing | The low energy bombardment | 150eV (electron-volt), 10mA (milliampere) |
| Deposition growing | Sputter | (3.25keV kiloelectron volt), 50mA (milliampere), |
| Deposition growing | Time | 3hr (hour) |
| Aftertreatment | Do not have | |
Claims (2)
1, a kind of preparation method of reinforced ion beam-deposited hydroxyl apatite coating of medical implant is characterized in that this method comprises following each step:
(1) clean: electric current is 30～60mA, is the Ar ion beam bombardment substrate sample surface of 0.8～1.2KeV with energy, and bombardment time is 10～15 minutes, and background pressure is 5 * 10
-6Torr, in the working process, keeping steam partial pressure is 0～2 * 10
-4Torr, operating pressure are 0.5～2.5 * 10
-4Torr;
(2) make the interface: the hydroxyapatite sintered ceramic target with 50% is sputter, with electric current is 20～60mA, energy is the ion beam bombardment of 0.3～3.5KeV, in substrate sample surface sputtering film forming, be 1～3mA with electric current simultaneously, energy is the high energy Ar ion beam bombardment substrate sample surface of 24～30KeV, and sputtering time is 10～30 minutes;
(3) deposition growing: the sputter procedure in above-mentioned second step is proceeded, with electric current is that 40～100mA, energy are the ion beam bombardment of 3～3.5KeV, continues spatter film forming, is 5～20mA with electric current simultaneously, energy is the energy Ar ion bombardment of 0.5～400eV, and sputtering time is 1～5 hour;
(4) behind the plated film 1 hour, the membrane sample in above-mentioned the 3rd step is taken out from vacuum, be heated to 380 ℃～420 ℃, annealed 0～4 hour in humidity greater than 70% damp atmosphere, can obtain possessing the medical implant of hydroxyl apatite coating.
2, preparation method as claimed in claim 1 is characterized in that wherein said substrate sample is any in metal, pottery or the high molecular polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97120353A CN1048291C (en) | 1997-12-12 | 1997-12-12 | Preparation of reinforced ion beam-deposited hydroxyl apatite coating for medical implant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97120353A CN1048291C (en) | 1997-12-12 | 1997-12-12 | Preparation of reinforced ion beam-deposited hydroxyl apatite coating for medical implant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1190136A CN1190136A (en) | 1998-08-12 |
| CN1048291C true CN1048291C (en) | 2000-01-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97120353A Expired - Fee Related CN1048291C (en) | 1997-12-12 | 1997-12-12 | Preparation of reinforced ion beam-deposited hydroxyl apatite coating for medical implant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1048291C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100751505B1 (en) * | 2006-09-28 | 2007-08-23 | 한국기계연구원 | Hydroxyapatite coatings with excellent bio-compatibility and preparation method thereof |
| CN101584881B (en) * | 2009-06-26 | 2012-11-21 | 北京工业大学 | Composite hydroxylapatite coating layer and preparing method thereof |
| CN104164644A (en) * | 2014-05-07 | 2014-11-26 | 北京百慕航材高科技股份有限公司 | Crystallization treatment method of plasma-sprayed hydroxyapatite coating |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58110465A (en) * | 1981-12-23 | 1983-07-01 | 旭光学工業株式会社 | Hydroxy apatite target |
| EP0285826A2 (en) * | 1987-04-04 | 1988-10-12 | BK LADENBURG GmbH, Gesellschaft für chemische Erzeugnisse | Implant with a bioactive coating |
| JPS63279835A (en) * | 1987-05-11 | 1988-11-16 | Nippon Kentetsu Co Ltd | Artificial dental root |
| CN1047627A (en) * | 1989-06-01 | 1990-12-12 | 河北轻化工学院 | Hydroox apatite artificial bone material preparation method |
| JPH04146762A (en) * | 1990-10-11 | 1992-05-20 | Terumo Corp | Hard tissue prosthetic material and manufacture thereof |
-
1997
- 1997-12-12 CN CN97120353A patent/CN1048291C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58110465A (en) * | 1981-12-23 | 1983-07-01 | 旭光学工業株式会社 | Hydroxy apatite target |
| EP0285826A2 (en) * | 1987-04-04 | 1988-10-12 | BK LADENBURG GmbH, Gesellschaft für chemische Erzeugnisse | Implant with a bioactive coating |
| JPS63279835A (en) * | 1987-05-11 | 1988-11-16 | Nippon Kentetsu Co Ltd | Artificial dental root |
| CN1047627A (en) * | 1989-06-01 | 1990-12-12 | 河北轻化工学院 | Hydroox apatite artificial bone material preparation method |
| JPH04146762A (en) * | 1990-10-11 | 1992-05-20 | Terumo Corp | Hard tissue prosthetic material and manufacture thereof |
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| Publication number | Publication date |
|---|---|
| CN1190136A (en) | 1998-08-12 |
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