CN1911203A - Prepn. method of carbon fiber biological composite material - Google Patents
Prepn. method of carbon fiber biological composite material Download PDFInfo
- Publication number
- CN1911203A CN1911203A CN 200610105020 CN200610105020A CN1911203A CN 1911203 A CN1911203 A CN 1911203A CN 200610105020 CN200610105020 CN 200610105020 CN 200610105020 A CN200610105020 A CN 200610105020A CN 1911203 A CN1911203 A CN 1911203A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- acrylic acid
- minutes
- methyl methacrylate
- methyl ester
- 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.)
- Granted
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A process for preparing a dental material from carbon fibers includes such steps as sequentially immersing carbon fibers in HNO3 and H2O2, mixing them with distilled water, adding emulsifier OP-10 and tributyl phosphate, adding the mixture of benzoyl peroxide, methyl methylacrylate and methyl acrylate, suspended polymerizing reaction, and moulding. It has high antiflex cracking strength (50.4-87.1 MPa) and high bending modulus (580-883 MPa).
Description
Technical field
The present invention relates to a kind of preparation method of Biocomposite material, particularly a kind of preparation method of carbon fiber biological composite material.
Background technology
Tooth section base material mainly contains a series of materials such as methyl methacrylate base, cochrome casting frame base, pure titanium casting support base at present.But it all has some shortcomings, and for example the metal material aesthetic property can not be satisfied the demand; Ceramic material fragility is big, easily bursts apart; Macromolecular material is low not wear-resisting because of its hardness.Polymer matrix composites have specific strength and specific stiffness height, and designability is strong, and the fatigue crack-resistant performance is good, and is corrosion-resistant, and physical dimension good stability and be convenient to the integrally formed distinct advantages of large tracts of land can be used for preparing tooth section biomaterial.The German at first proposed to use the heat curing-type methyl methacrylate to substitute the vulcanite that generally adopted at that time in 1936, made denture base material, and the quality of artificial tooth has obtained significant raising.Because polymethyl methacrylate is simple to operate, biocompatibility is good, and is with low cost, by wide clinical application, is the main material of making basal seat area at present in recent years.Gingiva and oral cavity mucous membrane tissue but it is easily burnt, color is single, and easy to change in using.Especially for a long time the fracture of basal seat area, especially easy to crack always the failing of the total basal seat area of the upper jaw is well solved.Adopting fiber to strengthen resin-based base is a reasonable selection.Effectively way is with employing Aramid (Kevlar) fiber, glass fibre, aramid fiber, superhigh molecular weight polyethylene fibers and heat reactive resin fiber etc. at present.But the Aramid fiber makes base present yellow respectively, and is exposed to base when surface and is difficult for polishing; Heat reactive resin fiber and heat reactive resin base are bonding, but operation inconvenience, so the heat reactive resin fiber seldom uses; Superhigh molecular weight polyethylene fibers and heat reactive resin bad adhesion need surface treatment.Glass fibre is attractive in appearance, studies morely at present, but that the shortcoming of its maximum is hardness is too low.Adopting carbon fiber to strengthen then is a kind of more satisfactory selection.
Carbon fibre reinforced composite (CFC) is generally the carbon fiber reinforced polymer material, or carbon fibre reinforced plastic, be to strengthen various thermosettings or thermoplastic resin matrix with short that cut or continuous carbon fibre, and a kind of composite that forms.This material has than glass fiber compound material more performance, is the ideal material that is used for aerospace flight vehicles such as aircraft, rocket, satellite, airship.As a kind of new material, carbon fiber enhancement resin base composite material extremely favor of material subject with characteristics such as its good mechanical performance, corrosion-resistant and lighter weight becomes the emphasis of current materialogy area research development.Carbon fibre composite starts from the seventies in 20th century in the application of medical domain, begin to attempt the hard tissue repairing material that uses composite to make the eighties, as hard tissue repairing material, the carbon fiber reinforced polymer composite is because of having good mechanical performance and histocompatibility, elastic modelling quantity is near the human body cortical bone, no electrochemical reaction and erosion, fatigue resistance is good, weight obviously is lighter than advantages (being used for hard tissue repairing material) such as metal material and radiolucency, at present as the heart-lung machine, the artificial hip prosthesis, the repair materials of defect of skull and blade plate etc. are used to some extent.
Xue Feng etc. are by strengthening the biomechanics test of composite polyolefine material to medical continuous carbon fibre, discovery can improve mechanical property [Xue Feng etc. such as its hot strength as hard tissue repairing material, compressive strength, bending strength greatly, medical continuous carbon fibre strengthens the biomechanics characteristic test of composite polyolefine material, 2005,20 (1): 11～13]; Discovery carbon fiber composite resin stake nuclears and the cast metal stake nuclear phase damage intensity lower such as Gao Hong than having, under the effect of shock loading prior to root of the tooth splitting, buffering stress, can the better protect dummy root of the tooth [Gao Hong, Zhang Zhen front yard, carbon fiber composite resin stake nuclear and metal pile nuclear are repaired the experimentation of dental defect, oral and maxillofacial surgery prosthodontics magazine, 2005,6 (1): 26～19]; The compound polymethyl methacrylate artificial skull of discovery carbon fiber plates such as Zhang Shihu are a kind of novel human skull's repair materials, this artificial skull plate has the body avirulence, to advantages such as tissue, skin nonirritants, be a kind of comparatively ideal bio-medical material [Zhang Shihu, Ni Feng, Wang Hailin, the compound polymethyl methacrylate artificial skull of carbon fiber plate Study on biocompatibility, biomedical engineering and clinical, 19982 (1): 14～18]; Sun Yupu etc. are matrix with NYLON610,610+PP and phenolic resins etc., made carbon fiber enhancement resin base composite material, discovery can it improve anti-wear performance [Sun Yupu, Wang Haiqing, Li Li greatly, carbon fiber enhancement resin base composite material, Shandong Polytechnic Univ's journal, 1997,27 (3): 244～249]; Cheng Xianhua etc. have prepared a kind of rare earth modified carbon fiber/epoxy resin composite material, find that composite has good mechanical property [Cheng Xianhua, the pretty Gorgon euryale of Shangguan, Wu Ju, rare earth modified carbon fiber/epoxy resin composite material preparation method, application (patent) number: 200410053662.1]; Suzuki celebrating should wait then prepared vinyl ester resin etc. for the carbon fiber-reinforced resin composite materials of matrix [Suzuki celebrate should, three Pus are abundant, carbon fiber-reinforced resin composite materials is applied for (patent) number: 200480003100.4].
Summary of the invention
The object of the present invention is to provide the preparation method of the simple carbon fiber biological composite material of a kind of preparation technology, prepared composite has mechanical properties such as higher rupture strength and bending modulus.
For achieving the above object, the preparation method that the present invention adopts is: at first that 1mm is long carbon fiber mass concentration is 63% HNO
3Soaked 5～15 minutes, the reuse mass concentration is 30% H
2O
2Soaked 30～60 minutes, standby 100 ℃ of dry down backs; Then with benzoyl peroxide, methyl methacrylate, that the acrylic acid methyl ester is made mixed liquor according to the ratio uniform mixing of methyl methacrylate/acrylic acid methyl ester/benzoyl peroxide=8-15ml: 1ml: 0.09-0.48g is standby; Secondly will be through HNO
3And H
2O
2Carbon fiber after the immersion and distilled water are made into liquid according to the ratio of carbon fiber/distilled water=1g: 350-450ml, the emulsifier op-10 and 0.3～0.6% defoamer tributyl phosphate that in this liquid, add liquid quality 0.2～0.4% then, stir, be uniformly dispersed into homogenous emulsion fully to carbon fiber; Mass ratio according to carbon fiber/(methyl methacrylate+acrylic acid methyl ester)=0.5-1.5% adds prepared mixed liquor in emulsion, stir, and is warmed up to 70～90 ℃ then and carries out suspension polymerisation, reacts and takes out polymer after 30～50 minutes; Polymer with above-mentioned taking-up moves into die for molding at last, and at 35-45 ℃, vacuum is solidified 8-10h down for the 0.09MPa environment, at room temperature leave standstill 24h, at 85-95 ℃, vacuum is ripening 2-3h under the 0.09MPa environment, promptly can obtain needed product then.
Because the present invention is raw material with acrylic acid methyl ester, methyl methacrylate, carbon fiber, adopt the method for suspension polymerisation, the composite that has synthesized has higher rupture strength and bending modulus.The composite rupture strength is 50.4-87.1MPa, bending modulus reaches 580-883MPa, the rupture strength of material and toughness all than single methyl methacrylate and polypropylene acid methyl ester height, also are higher than the composite that carbon fiber strengthens single polymethyl acrylate matrix; Its result of use obviously is better than traditional bio-medical resin sill and resin based composites (as PMMA, epoxy resin, glass fibre resin based composites, aramid fiber resin based composites etc.).And the fiber dispersion of composite is even, and fiber combines well with basal body interface, is a kind of comparatively ideal dental material.
The specific embodiment
Embodiment 1: at first that 1mm is long carbon fiber mass concentration is 63% HNO
3Soaked 15 minutes, the reuse mass concentration is 30% H
2O
2Soaked 30 minutes, standby 100 ℃ of dry down backs; Then with benzoyl peroxide, methyl methacrylate, that the acrylic acid methyl ester is made mixed liquor according to the ratio uniform mixing of methyl methacrylate/acrylic acid methyl ester/benzoyl peroxide=8ml: 1ml: 0.09g is standby; Secondly will be through HNO
3And H
2O
2Carbon fiber after the immersion and distilled water are made into liquid according to the ratio of carbon fiber/distilled water=1g: 350ml, the emulsifier op-10 and the 0.3% defoamer tributyl phosphate that in this liquid, add liquid quality 0.2% then, stir, be uniformly dispersed into homogenous emulsion fully to carbon fiber; Mass ratio according to carbon fiber/(methyl methacrylate+acrylic acid methyl ester)=0.5% adds the mixed liquor of making in emulsion, stir, and is warmed up to 70 ℃ then and carries out suspension polymerisation, reacts and takes out polymer after 50 minutes; Polymer with above-mentioned taking-up moves into die for molding at last, and at 35 ℃, vacuum at room temperature leaves standstill 24h for the 0.09MPa environment solidifies 10h down, and then at 85 ℃, vacuum is ripening 3h under the 0.09MPa environment, promptly can obtain needed product.
Embodiment 2: at first that 1mm is long carbon fiber mass concentration is 63% HNO
3Soaked 5 minutes, the reuse mass concentration is 30% H
2O
2Soaked 60 minutes, standby 100 ℃ of dry down backs; Then with benzoyl peroxide, methyl methacrylate, that the acrylic acid methyl ester is made mixed liquor according to the ratio uniform mixing of methyl methacrylate/acrylic acid methyl ester/benzoyl peroxide=15ml: 1ml: 0.48g is standby; Secondly will be through HNO
3And H
2O
2Carbon fiber after the immersion and distilled water are made into liquid according to the ratio of carbon fiber/distilled water=1g: 450ml, the emulsifier op-10 and the 0.6% defoamer tributyl phosphate that in this liquid, add liquid quality 0.4% then, stir, be uniformly dispersed into homogenous emulsion fully to carbon fiber; Mass ratio according to carbon fiber/(methyl methacrylate+acrylic acid methyl ester)=1.5% adds the mixed liquor of making in emulsion, stir, and is warmed up to 90 ℃ then and carries out suspension polymerisation, reacts and takes out polymer after 30 minutes; Polymer with above-mentioned taking-up moves into die for molding at last, and at 45 ℃, vacuum at room temperature leaves standstill 24h for the 0.09MPa environment solidifies 8h down, and then at 95 ℃, vacuum is ripening 2h under the 0.09MPa environment, promptly can obtain needed product.
Embodiment 3: at first that 1mm is long carbon fiber mass concentration is 63% HNO
3Soaked 10 minutes, the reuse mass concentration is 30% H
2O
2Soaked 45 minutes, standby 100 ℃ of dry down backs; Then with benzoyl peroxide, methyl methacrylate, that the acrylic acid methyl ester is made mixed liquor according to the ratio uniform mixing of methyl methacrylate/acrylic acid methyl ester/benzoyl peroxide=12ml: 1ml: 0.09-0.35g is standby; Secondly will be through HNO
3And H
2O
2Carbon fiber after the immersion and distilled water are made into liquid according to the ratio of carbon fiber/distilled water=1g: 400ml, the emulsifier op-10 and the 0.45% defoamer tributyl phosphate that in this liquid, add liquid quality 0.3% then, stir, be uniformly dispersed into homogenous emulsion fully to carbon fiber; Mass ratio according to carbon fiber/(methyl methacrylate+acrylic acid methyl ester)=1.0% adds the mixed liquor of making in emulsion, stir, and is warmed up to 80 ℃ then and carries out suspension polymerisation, reacts and takes out polymer after 40 minutes; Polymer with above-mentioned taking-up moves into die for molding at last, and at 40 ℃, vacuum at room temperature leaves standstill 24h for the 0.09MPa environment solidifies 9h down, and then at 90 ℃, vacuum is ripening 2.5h under the 0.09MPa environment, promptly can obtain needed product.
Claims (4)
1, a kind of preparation method of carbon fiber biological composite material is characterized in that:
1) the carbon fiber mass concentration of at first 1mm being grown is 63% HNO
3Soaked 5～15 minutes, the reuse mass concentration is 30% H
2O
2Soaked 30～60 minutes, standby 100 ℃ of dry down backs;
2) then with benzoyl peroxide, methyl methacrylate, that the acrylic acid methyl ester is made mixed liquor according to the ratio uniform mixing of methyl methacrylate/acrylic acid methyl ester/benzoyl peroxide=8-15ml: 1ml: 0.09-0.48g is standby;
3) secondly will be through HNO
3And H
2O
2Carbon fiber after the immersion and distilled water are made into liquid according to the ratio of carbon fiber/distilled water=1g: 350-450ml, the emulsifier op-10 and 0.3～0.6% defoamer tributyl phosphate that in this liquid, add liquid quality 0.2～0.4% then, stir, be uniformly dispersed into homogenous emulsion fully to carbon fiber;
4) mass ratio according to carbon fiber/(methyl methacrylate+acrylic acid methyl ester)=0.5-1.5% adds mixed liquor prepared in the step 2 in emulsion, stirs, and is warmed up to 70～90 ℃ then and carries out suspension polymerisation, reacts and takes out polymer after 30～50 minutes;
5) at last with the polymer immigration die for molding of above-mentioned taking-up, at 35-45 ℃, vacuum is that the 0.09MPa environment solidifies 8-10h down, at room temperature leave standstill 24h, at 85-95 ℃, vacuum is ripening 2-3h under the 0.09MPa environment, promptly can obtain needed product then.
2, the preparation method of carbon fiber biological composite material according to claim 1 is characterized in that: at first that 1mm is long carbon fiber mass concentration is 63% HNO
3Soaked 15 minutes, the reuse mass concentration is 30% H
2O
2Soaked 30 minutes, standby 100 ℃ of dry down backs; Then with benzoyl peroxide, methyl methacrylate, that the acrylic acid methyl ester is made mixed liquor according to the ratio uniform mixing of methyl methacrylate/acrylic acid methyl ester/benzoyl peroxide=8ml: 1ml: 0.09g is standby; Secondly will be through HNO
3And H
2O
2Carbon fiber after the immersion and distilled water are made into liquid according to the ratio of carbon fiber/distilled water=1g: 350ml, the emulsifier op-10 and the 0.3% defoamer tributyl phosphate that in this liquid, add liquid quality 0.2% then, stir, be uniformly dispersed into homogenous emulsion fully to carbon fiber; Mass ratio according to carbon fiber/(methyl methacrylate+acrylic acid methyl ester)=0.5% adds the mixed liquor of making in emulsion, stir, and is warmed up to 70 ℃ then and carries out suspension polymerisation, reacts and takes out polymer after 50 minutes; Polymer with above-mentioned taking-up moves into die for molding at last, and at 35 ℃, vacuum at room temperature leaves standstill 24h for the 0.09MPa environment solidifies 10h down, and then at 85 ℃, vacuum is ripening 3h under the 0.09MPa environment, promptly can obtain needed product.
3, the preparation method of carbon fiber biological composite material according to claim 1 is characterized in that: at first that 1mm is long carbon fiber mass concentration is 63% HNO
3Soaked 5 minutes, the reuse mass concentration is 30% H
2O
2Soaked 60 minutes, standby 100 ℃ of dry down backs; Then with benzoyl peroxide, methyl methacrylate, that the acrylic acid methyl ester is made mixed liquor according to the ratio uniform mixing of methyl methacrylate/acrylic acid methyl ester/benzoyl peroxide=15ml: 1ml: 0.48g is standby; Secondly will be through HNO
3And H
2O
2Carbon fiber after the immersion and distilled water are made into liquid according to the ratio of carbon fiber/distilled water=1g: 450ml, the emulsifier op-10 and the 0.6% defoamer tributyl phosphate that in this liquid, add liquid quality 0.4% then, stir, be uniformly dispersed into homogenous emulsion fully to carbon fiber; Mass ratio according to carbon fiber/(methyl methacrylate+acrylic acid methyl ester)=1.5% adds the mixed liquor of making in emulsion, stir, and is warmed up to 90 ℃ then and carries out suspension polymerisation, reacts and takes out polymer after 30 minutes; Polymer with above-mentioned taking-up moves into die for molding at last, and at 45 ℃, vacuum at room temperature leaves standstill 24h for the 0.09MPa environment solidifies 8h down, and then at 95 ℃, vacuum is ripening 2h under the 0.09MPa environment, promptly can obtain needed product.
4, the preparation method of carbon fiber biological composite material according to claim 1 is characterized in that: at first that 1mm is long carbon fiber mass concentration is 63% HNO
3Soaked 10 minutes, the reuse mass concentration is 30% H
2O
2Soaked 45 minutes, standby 100 ℃ of dry down backs; Then with benzoyl peroxide, methyl methacrylate, that the acrylic acid methyl ester is made mixed liquor according to the ratio uniform mixing of methyl methacrylate/acrylic acid methyl ester/benzoyl peroxide=12ml: 1ml: 0.09-0.35g is standby; Secondly will be through HNO
3And H
2O
2Carbon fiber after the immersion and distilled water are made into liquid according to the ratio of carbon fiber/distilled water=1g: 400ml, the emulsifier op-10 and the 0.45% defoamer tributyl phosphate that in this liquid, add liquid quality 0.3% then, stir, be uniformly dispersed into homogenous emulsion fully to carbon fiber; Mass ratio according to carbon fiber/(methyl methacrylate+acrylic acid methyl ester)=1.0% adds the mixed liquor of making in emulsion, stir, and is warmed up to 80 ℃ then and carries out suspension polymerisation, reacts and takes out polymer after 40 minutes; Polymer with above-mentioned taking-up moves into die for molding at last, and at 40 ℃, vacuum at room temperature leaves standstill 24h for the 0.09MPa environment solidifies 9h down, and then at 90 ℃, vacuum is ripening 2.5h under the 0.09MPa environment, promptly can obtain needed product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101050200A CN100413486C (en) | 2006-08-18 | 2006-08-18 | Prepn. method of carbon fiber biological composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101050200A CN100413486C (en) | 2006-08-18 | 2006-08-18 | Prepn. method of carbon fiber biological composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1911203A true CN1911203A (en) | 2007-02-14 |
| CN100413486C CN100413486C (en) | 2008-08-27 |
Family
ID=37720371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101050200A Expired - Fee Related CN100413486C (en) | 2006-08-18 | 2006-08-18 | Prepn. method of carbon fiber biological composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100413486C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437202A (en) * | 2020-03-23 | 2020-07-24 | 点铂医疗科技（常州）有限公司 | Fiber-reinforced polymer denture gasket material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2724814C3 (en) * | 1977-06-02 | 1980-03-27 | Kulzer & Co Gmbh, 6380 Bad Homburg | Preliminary product for the preparation of bone cement |
| US4793809A (en) * | 1987-05-21 | 1988-12-27 | Myron International, Inc. | Fiber filled dental porcelain |
| CN1481777A (en) * | 2002-09-09 | 2004-03-17 | 徐君华 | Special-shaped artificial tooth powder |
| PT1737415E (en) * | 2004-04-15 | 2008-08-06 | Dentofit As | Ultrasonic curing of dental filling materials |
| US7649029B2 (en) * | 2004-05-17 | 2010-01-19 | 3M Innovative Properties Company | Dental compositions containing nanozirconia fillers |
| CN100353921C (en) * | 2005-07-28 | 2007-12-12 | 曹征旺 | Method for preparing implantation body possessing biological activity inside root of tooth |
-
2006
- 2006-08-18 CN CNB2006101050200A patent/CN100413486C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111437202A (en) * | 2020-03-23 | 2020-07-24 | 点铂医疗科技（常州）有限公司 | Fiber-reinforced polymer denture gasket material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100413486C (en) | 2008-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102961784B (en) | BC (Bacterial Cellulose)/PVA (Polyvinyl Alcohol) composite material, as well as preparation method and application thereof | |
| US8507578B2 (en) | Composite ceramic block | |
| CN102641522B (en) | Method for preparing medical three-dimensional gradient netlike carbon fiber/ hydroxyapatite (HA)/ medical stone composite material | |
| CN106178106A (en) | 3D prints the method that sodium alginate/polyvinyl alcohol is physical crosslinking double-network hydrogel support entirely | |
| CN1657483A (en) | Preparation method of calcium phosphate composite bone cement | |
| CN112111073B (en) | Anti-fatigue full-hydrogel composite material and preparation method and application thereof | |
| CN109010921B (en) | Bionic articular cartilage composite hydrogel with gradient rigidity and preparation method thereof | |
| CN100569494C (en) | The polymethyl methacrylate enhanced by 3 D weaving carbon fiber composite material and preparation method thereof | |
| CN100431517C (en) | Method for preparing fiber reinforced composite material used for artificial tooth base | |
| CN1927416A (en) | Composite porous calcium phosphate bone cement and method for making same | |
| CN101579261A (en) | Zirconia tenacity-increasing alumina oxide dental ceramics substrate crown gelcasting forming method | |
| CN100413486C (en) | Prepn. method of carbon fiber biological composite material | |
| Adams et al. | The response of bone to carbon-carbon composites | |
| CN106929704A (en) | A kind of preparation method of the biological magnesium base composite material of nano titanium carbide particle enhancing | |
| CN103693985B (en) | Preparation method of gradient carbon fiber/hydroxyapatite (HA) composite material | |
| CN112156227A (en) | Composition and preparation of bone filling material, and preparation method and application thereof | |
| CN110028333A (en) | Gear division reparation resin penetration zero dimension/one-dimensional porous ceramic composite and preparation method thereof | |
| CN106563808B (en) | A kind of passive middle ear implanted device and preparation method thereof | |
| Vallittu et al. | From body‐on‐frame to unibody constructions and designs mimicking biological structures–an overview | |
| CN109467719A (en) | Biological hybridization gradient hydrogel bracket and preparation method and application thereof | |
| CN106344969A (en) | Dental composite-resin high-strength fiber periodontal bundle band and preparation method thereof | |
| CN104095760B (en) | Fiber reinforced composite material for dental root canal post and preparation method thereof | |
| CN104173196B (en) | Dental denture base fibre reinforced composites and preparation method thereof | |
| CN101617962B (en) | Dental restoration thread fiber pole | |
| CN109880152B (en) | Preparation method of oriented communicated porous biomedical stent, stent prepared by preparation method and application of stent in preparation of medical products |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080827 Termination date: 20110818 |