CN101185773B - Method for preparing bioactivity gradient hard tissue alternate material - Google Patents
Method for preparing bioactivity gradient hard tissue alternate material Download PDFInfo
- Publication number
- CN101185773B CN101185773B CN2007101906600A CN200710190660A CN101185773B CN 101185773 B CN101185773 B CN 101185773B CN 2007101906600 A CN2007101906600 A CN 2007101906600A CN 200710190660 A CN200710190660 A CN 200710190660A CN 101185773 B CN101185773 B CN 101185773B
- Authority
- CN
- China
- Prior art keywords
- fha
- target
- ysz
- gradient
- sputter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a preparation method of bioactive gradient hard tissue replacement material. Firstly, the pure FHA target material and the FHA plus YSZ compound target materials are prepared by vacuum hot-pressing sintering; the medical metal substrate test sample which is obtained by wire cutting is polished by a metallographical sand paper and then washed, and the substrate after washing is firstly processed by acid etching and then the alkali-heat treatment, so as to obtain the substrate which is processed by activation; the FHA target material, the self-made various groups of compound target materials with different components (FHA plus YSZ) and the medical metal substrate are respectively arranged in a main sputtering chamber and a sample introduction chamber to carry out magnetron sputtering, and post-treatment is carried out in a heat treatment furnace after the completion of magnetron sputtering, then the artificial bone implant which is based on the medical metal surface (FHA plus YSZ) gradient biological coating is obtained. The adhesive strength of the gradient biological coating of the gradient hard tissue replacement material (FHA plus YSZ) which is prepared by the invention and the substrate is high, the temperature increase of the medical metal substrate is low, the components of the coating are even and stable, and the cost is lower; the gradient coating is thinner, the in vivo degradation speed of the FHA gradient coating is lower, the retention time is longer, and the invention is more conductive to the repair and reconstruction of the bone tissues with defects.
Description
Technical field
The present invention relates to sclerous tissues and replace and repair, refer in particular to based on preparing the bio-active gradient coating composite in medical metal (titanium alloy, magnesium alloy) surface magnetic control sputtering technology with bioactive composite material bone implantation body.
Background technology
Prepare hydroxyapatite (HA) bioactivity coatings or coating implantation body at medical metal Ti, Ti6Al4V, Mg and Mg alloy surface, because it combines metal good mechanical performance and HA excellent biological compatibility and biological activity, can make the artificial bone bigger, position easy to wear that bears a heavy burden such as hip joint, knee joint, tooth root, and can be after implant giving birth to body in the short period rapidly with give birth to biological closely combination of body sclerous tissues formation, non-loosening, indeformable, thus hard tissue repair and one of new focus of replacing area research become.Compare with pure HA, adopt the biological activity of the existing hydroxyapatite of fluoridated hydroxyapatite (FHA) of fluorine part substituted hydroxy formation, lower dissolubility is arranged simultaneously, degradation speed in vivo is low, longer retention time is arranged, so FHA more helps the long-lasting of coating.FHA is coated on the high medical metal matrix of intensity, both can have made coating surface have good biological activity, guaranteed the long-term good bonding of implant and area of new bone again.Yet the difference of the thermophysical property between metallic matrix and ceramic coating easily causes the deleterious thermal stress of the inner generation of coating, thereby reduces coating and high base strength, even causes disbonding, has restricted the reparation damaged to bone to a great extent.If with FHA and other material (as ZrO
2, TiO
2, bio-vitric (BG) etc.) cooperate, make the complex gradient coating material, then can dwindle the difference of the thermal coefficient of expansion between coating and the matrix, slow down the thermal stress of coating inside, improve Bond Strength of Coating.
Magnetron sputtering preparation (FHA+YSZ) biological activity complex gradient hard tissue alternate material is domestic on medical metal (Ti, Ti6Al4V, Mg and magnesium alloy) matrix does not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of FHA based on magnetically controlled sputter method preparation (+YSZ)/the novel sclerous tissues of medical metal (titanium, titanium alloy, magnesium and magnesium alloy) replaces and use the biological gradient composite.
1. magnetic control spattering target preparation
Adopt nanoscale FHA powder body, vacuum heating-press sintering prepares pure FHA target;
In the FHA powder body, add Y
2O
3Stable ZrO
2Powder body (YSZ), the FHA+YSZ composite granule of configuration heterogeneity, YSZ powder quality percentage composition accounts for 10%～90% of composite granule gross mass, and hot pressed sintering prepares the FHA+YSZ composite target material;
2. medical metal matrix surface activation processing
The medical metal matrix sample that the line cutting is obtained polishes and cleans with abrasive paper for metallograph, and the substrate after cleaning carries out acid etching earlier, carries out the alkali heat treatment again, thereby obtains the substrate of activation processing;
3. magnetron sputtering technique process
With pure FHA target, homemadely respectively organize heterogeneity (FHA+YSZ) composite target material and the medical metal matrix is inserted main sputtering chamber and Sample Room respectively, and main sputtering chamber and Sample Room are evacuated to 5 * 10
-5～8 * 10
-5Pa; At Sample Room the medical metal matrix was carried out pre-sputter clean after 20～40 minutes, it is sent into main sputtering chamber, in main sputtering chamber vacuum to 5 * 10
-1～9 * 10
-1Regulate the sputter of power build-up of luminance during Pa, sputter was taken out sample from main sputtering chamber after 2～5 hours, in heat-treatment furnace, carry out post processing, 300～500 ℃ of post-processing temperatures, what obtain after the temperature retention time 2～4 hours, post processing is based on medical metal surface (FHA+YSZ) gradient biological coating artificial bone implantation body.
Utilize (FHA+YSZ) composite target material of pure FHA target, heterogeneity to make up sputter on the medical metal matrix, wherein one deck of the corresponding sputter gradient coating of each piece target is according to 4～6 layers of target composition combination cosputterings, each layer sputter 0.5～1 hour.
The present invention compares with existing HA and FHA biofilm bone implantation body, and following advantage is arranged:
1, (FHA+YSZ) gradient biological coating and matrix adhesive strength height are greater than 50MPa.
2, medical metal-based body temperature liter is low, and coating composition is uniform and stable.
3, cost is lower.Gradient coating is thinner, and thickness is 19～36um, and used FHA powder body is less relatively.
4, FHA gradient coating degradation in vivo speed is lower, and longer retention time is arranged, and helps the repair and reconstruction of defective bone tissue.
The specific embodiment
The magnetically controlled sputter method preparation is based on medical metal (Ti, Ti6Al4V, Mg and magnesium alloy) surface (FHA+YSZ) gradient biological coating artificial bone implantation body, and the invention will be further described in conjunction with example now.
(1) magnetron sputtering FHA target and (FHA+YSZ) composite target material preparation
Take by weighing FHA nano-powder 60g, place air dry oven to dry, grinding is sieved.Prepare the FHA target with ZRY55 type multifunctional vacuum hot-pressed sintering furnace, hot pressing pressure 5t, 1150 ℃ of hot pressing temperatures, hot pressing atmosphere N
2, furnace cooling behind the pressurize 4h obtains specification and is
The magnetron sputtering FHA target of 60mm * 5mm.
In the FHA powder body, add YSZ powder body configuration (FHA+YSZ) composite granule respectively, add the YSZ powder quality and account for 90%, 80%, 75%, 70%, 60%, 50%, 40%, 30%, 25%, 20%, 10% of composite granule gross mass successively, obtain (FHA+YSZ) composite granule of 9 kinds of heterogeneities, place air dry oven to dry, grinding is sieved.These 9 kinds of composite granules are adopted and the same technological parameter hot pressed sintering of FHA powder body, specifically see Table 1, prepare specification and be
The magnetron sputtering of 60mm * 5mm (FHA+YSZ) composite target material.
More than prepared target be divided into five groups, be respectively:
First group: target I:FHA-90wt%YSZ (corresponding sputter gradient coating bottom); Target II:FHA-70wt%YSZ (the corresponding sputter gradient coating second layer); Target III:FHA-50wt%YSZ (the 3rd layer of corresponding sputter gradient coating); Target IV:FHA-30wt%YSZ (the 4th layer of corresponding sputter gradient coating); Target V:FHA-10wt%YSZ (corresponding sputter gradient coating layer 5); Target VI100%FHA (corresponding sputter gradient coating outermost layer).(first group of target as sputter is followed successively by in proper order: I, II, III, IV, V, VI)
Second group: target I:FHA-80wt%YSZ (corresponding sputter gradient coating bottom); Target II:FHA-60wt%YSZ (the corresponding sputter gradient coating second layer); Target III:FHA-40wt%YSZ (the 3rd layer of corresponding sputter gradient coating); Target IV:FHA-20wt%YSZ (the 4th layer of corresponding sputter gradient coating); Target V:100%FHA (corresponding sputter gradient coating outermost layer).(second group of target as sputter is followed successively by in proper order: I, II, III, IV, V)
The 3rd group: target I:FHA-75wt%YSZ (corresponding sputter gradient coating bottom); Target II:FHA-50wt%YSZ (the corresponding sputter gradient coating second layer); Target III:FHA-25wt%YSZ (the 3rd layer of corresponding sputter gradient coating); Target IV:100%FHA (corresponding sputter gradient coating outermost layer).(the 3rd group of target as sputter is followed successively by in proper order: I, II, III, IV)
The 4th group: target I:FHA-90wt%YSZ (corresponding sputter gradient coating bottom); Target II:FHA-60wt%YSZ (the corresponding sputter gradient coating second layer); Target III:FHA-30wt%YSZ (the 3rd layer of corresponding sputter gradient coating); Target IV:100%FHA (corresponding sputter gradient coating outermost layer).(the 4th group of target as sputter is followed successively by in proper order: I, II, III, IV)
The 5th group: target I:FHA-70wt%YSZ (corresponding sputter gradient coating bottom); Target II:FHA-40wt%YSZ (the corresponding sputter gradient coating second layer); Target III:FHA-10wt%YSZ (the 3rd layer of corresponding sputter gradient coating); Target IV:100%FHA (corresponding sputter gradient coating outermost layer).(the 5th group of target as sputter is followed successively by in proper order: I, II, III, IV)
(2) medical metal matrix surface activation processing
Medical metal matrix Ti, Ti6Al4V, Mg and the magnesium alloy sample that line cutting is obtained is polished down to 600 orders step by step with abrasive paper for metallograph and cleans up with acetone, substrate is earlier with oxalic acid solution acid etching 30～60min, place in the NaOH aqueous solution of 5mol/L, 80 ℃ of water bath heat preservation 10h take out substrate again, clean with deionized water, oven dry is placed in the vacuum furnace, is warming up to 600 ℃, insulation 1h, furnace cooling obtains the substrate of activation processing.
(3) magnetron sputtering technique process
Each group target and the medical metal matrix corresponding with it are inserted main sputtering chamber and Sample Room respectively, and main sputtering chamber and Sample Room are evacuated to 8 * 10
-5Pa carries out pre-sputter clean after 30 minutes at Sample Room to the medical metal matrix, and it is sent into main sputtering chamber, when main sputtering chamber vacuum reaches 9 * 10
-1Regulate the sputter of sputtering power build-up of luminance during Pa, each target as sputter 0.8 hour, sputter finishes the back and takes out sample from main sputtering chamber, carries out post processing in heat-treatment furnace, and post-processing temperature is 300 ℃～500 ℃, and temperature retention time is 3 hours.What obtain after the post processing is based on medical metal surface FHA gradient biological coating artificial bone implantation body.
Table 1 has provided five groups of examples of the present invention.By the magnetron sputtering technique parameter of optimizing, at the FHA bio-active gradient coating composite of the medical metal surface preparation heterogeneity Gradient distribution of passing through activation processing.The 6th is control sample carefully in the table 1.
Table 1 adopts the FHA biological gradient coating composite material of five groups of different Gradient distribution of the magnetron sputtering technique scheme preparation of optimizing
| The sample group # | FHA biological gradient coating composite material component gradient distribution mode | Matrix is selected | Sputtering power (w) | Sputtering atmosphere | Initial depression (Pa) | Sputter vacuum (Pa) | Sputtering time (h) | The atmosphere post-processing temperature (℃) |
| No 1 | (FHA-90wt％YSZ)+ (FHA-70wt％YSZ)+ (FHA-50wt％YSZ)+ (FHA-30wt％YSZ)+ (FHA-10wt％YSZ)+ 100％FHA | Ti, Ti6Al4V, Mg, magnesium alloy | 300 | Ar | 8×10 -5 | 9×10 -1 | 4.8 | 300～500 |
| No 2 | (FHA-80wt％YSZ)+ (FHA-60wt％YSZ)+ (FHA-40wt％YSZ)+ (FHA-20wt％YSZ)+ 100％FHA | Ti, Ti6Al4V, Mg, magnesium alloy | 300 | Ar | 8×10 -5 | 9×10 -1 | 4.0 | 300～500 |
| The sample group # | FHA biological gradient coating composite material component gradient distribution mode | Matrix is selected | Sputtering power (w) | Sputtering atmosphere | Initial depression (Pa) | Sputter vacuum (Pa) | Sputtering time (h) | The atmosphere post-processing temperature (℃) |
| No 3 | (FHA-75wt％YSZ)+ (FHA-50wt％YSZ)+ (FHA-25wt％YSZ)+ 100％FHA | Ti, Ti6Al4V, Mg, magnesium alloy | 300 | Ar | 8×10 -5 | 9×10 -1 | 3.2 | 300～500 |
| No 4 | (FHA-90wt％YSZ)+ (FHA-60wt％YSZ)+ (FHA-30wt％YSZ)+ 100％FHA | Ti, Ti6Al4V, Mg, magnesium alloy | 300 | Ar | 8×10 -5 | 9×10 -1 | 3.2 | 300～500 |
| No 5 | (FHA-70wt％YSZ)+ (FHA-40wt％YSZ)+ (FHA-10wt％YSZ)+ 100％FHA | Ti, Ti6Al4V, Mg, magnesium alloy | 300 | Ar | 8×10 -5 | 9×10 -1 | 3.2 | 300～500 |
| No 6 | 100％FHA | Ti, Ti6Al4V, Mg, magnesium alloy | 300 | Ar | 8×10 -5 | 9×10 -1 | 3.2～4.8 | 300～500 |
Above-mentioned bio-active gradient composite coating artificial bone implantation body performance characterization is (is example with the biological gradient coating artificial bone implantation body for preparing on the Ti6Al4V matrix) shown in the table 2.The 6th group is control sample in the table 2.
Table 2 (FHA+YSZ)/Ti6Al4V biological gradient coating artificial bone implantation body performance
| Specimen coding | Coating layer thickness | Adhesive strength (MPa) | FTIR analyzes | The XRD facies analysis | The SEM surface topography is observed | The SEM cross-section morphology is observed | Biocompatibility and antilysis |
| No 1 | 30～ 36μm | 55～65 | OH - PO 4 3- | FHA，YSZ CaO， | 30%～35% 0.5～4 μ m hole | The interface is in conjunction with closely and at the interface existing | The good biocompatibility antilysis is strong |
| β-Ca 3(PO 4) 2 | The composition diffusion | ||||||
| No 2 | 26～ 30μm | 53～60 | OH - PO 4 3- | FHA，YSZCaO，β-Ca 3(PO 4) 2 | 30%～35%0.5～4 μ m holes | The interface is in conjunction with closely and at the interface there being the composition diffusion | The good biocompatibility antilysis is strong |
| No 3 | 19～ 25μm | 53～59 | OH - PO 4 3- | FHA，YSZCaO，β-Ca 3(PO 4) 2 | 30%～35%0.5～4 μ m holes | The interface is in conjunction with closely and at the interface there being the composition diffusion | The good biocompatibility antilysis is strong |
| No 4 | 19～ 26μm | 51～57 | OH - PO 4 3- | FHA，YSZCaO，β-Ca 3(PO 4) 2 | 30%～35%0.5～4 μ m holes | The interface is in conjunction with closely and at the interface there being the composition diffusion | The good biocompatibility antilysis is strong |
| No 5 | 20～ 25μm | 51～57 | OH - PO 4 3- | FHA，YSZCaO，β-Ca 3(PO 4) 2 | 30%～35%0.5～4 μ m holes | The interface is in conjunction with closely and at the interface there being the composition diffusion | The good biocompatibility antilysis is strong |
| No 6 | 20～ 27μm | 46～55 | OH - PO 4 3- | Amorphous FHACaO, β-Ca 3(PO 4) 2 | 30%～45%0.5～5 μ m holes | The interface is in conjunction with closely and at the interface there being the composition diffusion | The good biocompatibility antilysis is relatively poor |
Claims (2)
1. the preparation method of a bioactivity gradient hard tissue alternate material, concrete steps are:
(1) magnetic control spattering target preparation
Adopt nanoscale fluoridated hydroxyapatite powder body, vacuum heating-press sintering prepares pure fluoridated hydroxyapatite target; In the fluoridated hydroxyapatite powder body, add Y
2O
3Stable ZrO
2Powder body, the composite granule of configuration heterogeneity adds Y
2O
3Stable ZrO
2The powder quality percentage composition accounts for 10%～90% of composite granule gross mass, and hot pressed sintering prepares composite target material;
(2) medical metal matrix surface activation processing
The medical metal matrix sample that the line cutting is obtained polishes and cleans with abrasive paper for metallograph, and the substrate after cleaning carries out acid etching earlier, carries out the alkali heat treatment again, thereby obtains the substrate of activation processing;
(3) magnetron sputtering technique process
The composite target material of respectively organizing heterogeneity and the medical metal matrix of pure fluoridated hydroxyapatite target, preparation are inserted main sputtering chamber and Sample Room respectively, and main sputtering chamber and Sample Room are evacuated to 5 * 10
-5～8 * 10
-5Pa; At Sample Room the medical metal matrix was carried out pre-sputter clean after 20～40 minutes, it is sent into main sputtering chamber, in main sputtering chamber vacuum to 5 * 10
-1～9 * 10
-1Regulate the sputter of power build-up of luminance during Pa, sputter was taken out sample from main sputtering chamber after 2～5 hours, in heat-treatment furnace, carry out post processing, 300～500 ℃ of post-processing temperatures, temperature retention time 2～4 hours, what obtain after the post processing is bioactivity gradient hard tissue alternate material based on the medical metal surface.
2. the preparation method of the described a kind of bioactivity gradient hard tissue alternate material of claim 1, it is characterized by: utilize the composite target material of pure fluoridated hydroxyapatite target, heterogeneity on the medical metal matrix, to make up sputter, wherein one deck of the corresponding sputter gradient coating of each piece target, according to 4～6 layers of target composition combination cosputterings, each layer sputter 0.5～1 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101906600A CN101185773B (en) | 2007-11-28 | 2007-11-28 | Method for preparing bioactivity gradient hard tissue alternate material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101906600A CN101185773B (en) | 2007-11-28 | 2007-11-28 | Method for preparing bioactivity gradient hard tissue alternate material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101185773A CN101185773A (en) | 2008-05-28 |
| CN101185773B true CN101185773B (en) | 2010-09-15 |
Family
ID=39478527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101906600A Active CN101185773B (en) | 2007-11-28 | 2007-11-28 | Method for preparing bioactivity gradient hard tissue alternate material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101185773B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10138545B2 (en) * | 2016-02-05 | 2018-11-27 | Sci Engineered Materials, Inc. | Process for the removal of contaminants from sputtering target substrates |
| CN106109059A (en) * | 2016-08-05 | 2016-11-16 | 北京爱康宜诚医疗器材有限公司 | Borrowed structure |
| CN112391600B (en) * | 2021-01-21 | 2021-04-02 | 中南大学湘雅医院 | Corrosion-resistant medical magnesium alloy surface hydroxyapatite coating and preparation method thereof |
| CN112522674B (en) * | 2021-02-18 | 2021-05-04 | 中南大学湘雅医院 | Titanium alloy surface composite coating and preparation method thereof |
| CN114525488B (en) * | 2022-04-21 | 2022-07-08 | 中南大学湘雅医院 | Magnetron sputtering zirconium oxide doped hydroxyapatite coating and application thereof |
-
2007
- 2007-11-28 CN CN2007101906600A patent/CN101185773B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101185773A (en) | 2008-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101185773B (en) | Method for preparing bioactivity gradient hard tissue alternate material | |
| CN101437978B (en) | Method for preparing nickle titanium alloy medical instrument surface coating | |
| CN102312128B (en) | Method for preparing titanium niobium tantalum zirconium biomedical titanium alloys by discharge plasma sintering | |
| CN104857566B (en) | A kind of preparation method of titanium niobium zirconium base titanium/hydroxyl apatite biological composite material | |
| CN104894420B (en) | A kind of preparation method of titanium niobium zirconium base calcium pyrophosphate Biocomposite material | |
| CN100577858C (en) | Magnetron sputtering method for preparing HA/YSZ/Ti6Al4V gradient bioactive composite material | |
| Prashar et al. | Performance of thermally sprayed hydroxyapatite coatings for biomedical implants: a comprehensive review | |
| CN106967956B (en) | A kind of porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of maskable harmful ion release | |
| CN104138616A (en) | Medicinal titanium and titanium alloy surface oxidation-carbon plated-diamond-like composite film and manufacturing method thereof | |
| CN102580154A (en) | Antifriction and toughening metal/ceramic bionic multilayer-film artificial joint | |
| CN102049065A (en) | Bone substitute material for Ca3ZrSi2O9 coating-titanium alloy and preparation method of bone substitute material | |
| CN100341587C (en) | Biomedicine material of titanium or titanium alloy in use for artificial bones, and preparation method | |
| CN102499773A (en) | Titanium surface processing method capable of improving titanium and ceramic bonding strength | |
| CN104857562B (en) | A kind of titanium alloy/calcium pyrophosphate surface layer Biocomposite material and preparation method thereof | |
| Lo et al. | Hydroxyapatite thin films deposited onto uncoated and (Ti, Al, V) N‐coated Ti alloys | |
| CN108546156A (en) | The carbon/carbon compound material and preparation method that silicon carbide is modified with hydroxylapatite gradient coating | |
| JP3629573B2 (en) | A new artificial bone grafting method combining biocompatibility control of biomaterial surface by surface polishing treatment and adhesion of cultured osteoblasts | |
| CN115142026B (en) | Method for obtaining compact calcium-phosphorus coating on magnesium alloy surface | |
| CN1995450A (en) | Magnetron sputtering method for preparing HA/YSZ/polyimide bioactive composite material | |
| CN112870456A (en) | Cardiovascular implantation instrument wear-resistant coating and preparation method thereof | |
| CN105951048A (en) | Ta2N nanocrystalline coating with biological activity and preparing method of Ta2N nanocrystalline coating | |
| CN107586146B (en) | Method for toughening hydroxyapatite biological ceramic material by carbon fiber | |
| CN107254657B (en) | A kind of sodium tetraborate catalysis oxidation preparation array-like TiO of pure Ti2Method | |
| CN101791434B (en) | Method for preparing hydroxyapatite coat/surface activated titanium-based composite coat | |
| CN113953515B (en) | Biomedical metal porous coating capable of replacing bone cement and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |