CN107596442B - Preparation method of gradient biological coating on PET material surface, product and application thereof - Google Patents
Preparation method of gradient biological coating on PET material surface, product and application thereof Download PDFInfo
- Publication number
- CN107596442B CN107596442B CN201711050278.XA CN201711050278A CN107596442B CN 107596442 B CN107596442 B CN 107596442B CN 201711050278 A CN201711050278 A CN 201711050278A CN 107596442 B CN107596442 B CN 107596442B
- Authority
- CN
- China
- Prior art keywords
- coating
- pet
- hap
- gradient
- solution
- 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
Images
Abstract
The invention relates to a preparation method of a gradient biological coating on the surface of a PET material, a product and application thereof, and the preparation method comprises the preparation of nano hydroxyapatite, the surface pretreatment of the PET material and the preparation of the gradient HAp coating on the surface of the PET material by a dip-coating method. The method takes bone-like inorganic salt hydroxyapatite as a coating material, prepares nano HAp by a chemical precipitation method, and prepares a gradient HAp coating on the surface of PET by a dip-coating method. By changing the technological conditions of dip-coating and dip-coating, the biological coating material with different gradient gradual change modes is prepared. The material has good biocompatibility, bioactivity, osteoinductivity and gradient characteristics, the preparation method is simple and easy to implement, and the product can meet the requirements of biomedical application.
Description
Technical Field
The invention relates to a preparation method of a gradient biological coating on the surface of a PET material, a product and application thereof, in particular to a method for preparing a hydroxyapatite gradient coating on the surface of the PET material by using a dip-coating method. The invention belongs to the field of surface modification of biomedical materials.
Background
Polyethylene terephthalate (PET) is currently the most clinically used artificial ligament material. The PET material has poor hydrophilicity and lacks biological activity, so that the PET material is not beneficial to cell adhesion and proliferation; meanwhile, the bone conductivity is poor, and stable osseous combination is difficult to form on an interface with autologous bone tissues, so that the clinical repair effect is difficult to satisfy. To further advance the clinical application of PET materials, it is a crucial and imperative task to apply coating modification on the surface of PET materials to improve their bioactivity and osteoinductivity.
Hydroxyapatite (HAp) is the main inorganic component of human bones and teeth, and has good biocompatibility, bioactivity and osteoconductivity. After the calcium and phosphorus are implanted into the defect part of a human body, calcium and phosphorus can be dissociated from the surface of the material to form tight bonding with autologous bone tissues on the interface and be absorbed by the autologous bone tissues, so that the regeneration of new bone tissues is induced, and the effect of bone repair is enhanced. Therefore, HAp is a good material for tissue repair and tissue replacement, and is widely applied to the medical fields of orthopedics, dentistry, plastic surgery and the like. The preparation method of HAp can be basically summarized into two main types of dry preparation and wet preparation. The dry preparation is a solid-phase reaction method, and the wet preparation mainly comprises a hydrothermal synthesis method, a chemical precipitation method, a sol-gel method, a biomimetic synthesis method and the like. The preparation of HAp by coprecipitation of inorganic calcium salt and phosphorus salt is a good method for preparing nanoscale HAp with uniform particle size.
After the artificial ligament is implanted into a body, different parts need to perform different functions so as to achieve effective tissue repair. Compared with the PET material of the articular cavity, the PET material of the osseous part not only has good biocompatibility, but also needs to form good osseous combination with autologous bone tissues, induce the formation of new bones and promote the repair of defects. This is not possible with a uniform material, but a gradient functional material can achieve this by continuously changing the composition and structure of the material to achieve a gradual change in material properties and function. Meanwhile, the gradient material can also avoid the possible adverse effects caused by the property mutation of two different materials on the interface. Therefore, the hydroxyapatite coating treatment with gradient gradual change is carried out on the surface of the PET material of the artificial ligament, so that the best use of the material can be realized, the waste of economic cost caused by using a uniform full-coating material is avoided, the performance index of the PET material can be improved, and meanwhile, great economic benefit can be brought to the clinical application and conversion of the PET material.
In order to improve the poor bioactivity and osteoconductivity of the conventional PET artificial ligament material, a new technical solution is necessary to be provided.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to: provides a preparation method of a gradient hydroxyapatite coating on the surface of a PET material. Products and uses thereof
It is a further object of the present invention to provide a product prepared by the above method.
The invention also aims to provide application of the product prepared by the method.
The purpose of the invention is realized by the following scheme: a preparation method of a gradient biological coating on the surface of a PET material takes bone-like inorganic salt hydroxyapatite as a coating material, utilizes a chemical precipitation method to prepare nano HAp, and utilizes a dip-coating method to prepare the gradient HAp coating on the surface of the PET material, and comprises the following specific steps:
(1) preparation of nano-hydroxyapatite
500 mL of 0.5M Ca (NO) was prepared3)2Solution and 300 mL of 0.5M (NH)4)2HPO4Solution 50 mL of concentrated aqueous ammonia was diluted to 500 mL with Milli-Q ultrapure water, and Ca (NO) was added3)2The solution was added to a three-necked flask and added dropwise (NH) at room temperature using a peristaltic pump4)2HPO4Controlling the dropping rate of the solution to be 3 mL/min, simultaneously dropping ammonia water at the rate of 5 mL/min, keeping the pH value of the mixed solution between 9.5 and 10, carrying out magnetic stirring at the rotating speed of 500 rpm while dropping, continuing to carry out magnetic stirring for 5 hours after dropping, and then standing and aging for 24 hours;
removing supernatant, leaching and filtering with 1L of absolute ethyl alcohol, repeatedly cleaning and filtering with a large amount of ultrapure water until filtrate is neutral, dispersing and filtering with ethanol again after water washing is finished, drying filter residue in a 60 ℃ oven, grinding dried solid under an infrared lamp by using a mortar, and sieving by using a 150-mesh sieve to obtain a precursor of hydroxyapatite;
and (2) putting the precursor into a muffle furnace for calcination, firstly heating to 500 ℃ within 100min and maintaining for 5 min, then continuously heating to 1000 ℃ within 100min and maintaining for 180 min, putting the calcined product into a ball mill, placing 20g of large balls and 40 g of small balls, carrying out ball milling for 15 h at the rotating speed of 400 rpm, centrifuging for 10 min at the rotating speed of 5000 rpm at 15 ℃, then evaporating the solvent to dryness at 45 ℃ by using a rotary evaporator, and drying at 60 ℃. Grinding the dried HAp product by using a mortar, and drying and storing for later use;
(2) surface pretreatment of PET materials
Soaking a PET material in absolute ethyl alcohol, performing ultrasonic treatment for 30 min to remove impurities adhered to the surface of the material, taking out the material, repeatedly cleaning the material by using a large amount of ultrapure water to remove residual ethyl alcohol, drying at room temperature, preparing a 5 wt% sodium hydroxide solution, soaking the PET material in the solution, boiling for 1 h, repeatedly cleaning the material by using a large amount of ultrapure water until the pH value is about 7, and then drying at 60 ℃ to obtain the PET material with the terminal group being carboxyl;
(3) gradient HAp coating on PET surface prepared by dip-coating method
Weighing 0.4 g of hydroxyapatite powder, sequentially adding 100 mL of ethanol and 50 mL of ultrapure water, carrying out ultrasonic treatment for 30 min to uniformly disperse HAp in the solution, preparing an HAp coating by using an immersion dip coating machine, reducing the PET material into small blocks of 10 cm multiplied by 10 cm, vertically immersing the small blocks into the HAp dispersion liquid at a constant speed, immersing the small blocks into the solution for a certain time to achieve balance, then uniformly accelerating the PET material to be vertically pulled out of the liquid level at a certain initial speed and acceleration, drying the small blocks at room temperature for 24 h to completely volatilize ethanol, and forming the gradient HAp coating on the surface of the PET.
The invention prepares the biological coating material with different gradient gradual change modes by changing the technological conditions of dip-coating. The material has good biocompatibility, bioactivity, osteoinductivity and gradient characteristics, the preparation method is simple and easy to implement, and the product can meet the requirements of biomedical application.
The dipping time is 5-60 s.
The initial pulling speed is 0.2-5 mm/s.
The lifting acceleration is 1-10 mm/s2。
The invention provides a gradient biological coating on the surface of a PET material, which is prepared by any one of the methods. The product of the invention improves the bioactivity and the bone conductivity of the PET artificial ligament material, and is beneficial to the PET artificial ligament material to play different roles in different parts after being implanted into a body, in particular to the bone promoting function of a bone passage part.
The invention provides application of a gradient biological coating on the surface of a PET material as an artificial ligament material.
The invention has the advantages that:
(1) the invention takes the bone-like inorganic salt hydroxyapatite as a coating material, prepares the nano HAp by a chemical precipitation method, and prepares the gradient HAp coating on the PET surface by a dip-coating method. The biological safety of the used raw materials is high, and part of the raw materials are commercialized products.
(2) The coating material prepared by the invention has good biocompatibility, bioactivity, osteoinductivity and gradient characteristics.
(3) The method is simple and easy to implement, has strong operability, and can further meet the requirements of clinical application and industrial production.
Drawings
FIG. 1 is a scanning electron microscope picture of different areas of PET surface coating prepared in example 1;
FIG. 2 is a scanning electron microscope picture of different areas of PET surface coating prepared in example 2.
Detailed Description
The technical solution of the present invention is further described below by specific examples. The following examples are further illustrative of the present invention and do not limit the scope of the present invention.
Example 1
500 mL of 0.5M Ca (NO) was prepared3)2Solution and 300 mL of 0.5M (NH)4)2HPO4The solution was diluted to 500 mL with 50 mL of concentrated aqueous ammonia using Milli-Q ultrapure water. Mixing Ca (NO)3)2The solution was added to a three-necked flask and added dropwise (NH) at room temperature using a peristaltic pump4)2HPO4The solution was added while controlling the dropping rate at 3 mL/min and at 5 mL/minAqueous ammonia was added dropwise at a rate of 500 rpm while keeping the pH of the mixed solution between 9.5 and 10. After the dropwise addition, the magnetic stirring is continued for 5 hours, and then the mixture is kept stand and aged for 24 hours.
Discarding supernatant, leaching and filtering with 1L anhydrous ethanol, and repeatedly washing and filtering with a large amount of ultrapure water until the filtrate is neutral. After the water washing is finished, dispersing and filtering the filter residue by using ethanol again, and drying the filter residue in a 60 ℃ oven. And grinding the dried solid by using a mortar under an infrared lamp, and sieving the ground solid by using a 150-mesh sieve to obtain a precursor of the hydroxyapatite.
And (3) putting the precursor into a muffle furnace for calcination, firstly heating to 500 ℃ within 100min and maintaining for 5 min, and then continuously heating to 1000 ℃ within 100min and maintaining for 180 min. The calcined product was placed in a ball mill, and 20g of large balls and 40 g of small balls were placed and ball-milled at 400 rpm for 15 hours. Centrifugation is carried out at 5000 rpm for 10 min at 15 ℃, then the solvent is evaporated to dryness at 45 ℃ by a rotary evaporator and dried at 60 ℃. The dried HAp product was ground in a mortar and dried for storage.
And (3) soaking the PET material in absolute ethyl alcohol, and carrying out ultrasonic treatment for 30 min to remove impurities adhered to the surface of the material. After the material was taken out, the material was repeatedly washed with a large amount of ultrapure water to remove the residual ethanol, and dried at room temperature. 5 wt% sodium hydroxide solution is prepared, the PET material is soaked in the sodium hydroxide solution and boiled for 1 h. The material was repeatedly washed with a large amount of ultrapure water until the pH was about 7, and then dried at 60 ℃ to obtain a carboxyl-terminated PET material.
0.4 g of hydroxyapatite powder is weighed, 100 mL of ethanol and 50 mL of ultrapure water are sequentially added, and ultrasonic treatment is carried out for 30 min to uniformly disperse HAp in the solution. The HAp coating was prepared by dip-coating a PET material in 10 cm by 10 cm pieces, immersed vertically in the HAp dispersion at a constant speed for 10 s to reach equilibrium, and then immersed in the solution at an initial speed of 0.2mm/s and 10 mm/s2The acceleration of the lifting device is uniform, so that the PET material is vertically lifted out of the liquid level. Drying for 24 h at room temperature to completely volatilize ethanol and form a gradient HAp coating on the PET surface.
FIG. 1 is a scanning electron microscope photograph of different areas of PET surface coating prepared in example 1.
Example 2
500 mL of 0.5M Ca (NO) was prepared3)2Solution and 300 mL of 0.5M (NH)4)2HPO4The solution was diluted to 500 mL with 50 mL of concentrated aqueous ammonia using Milli-Q ultrapure water. Mixing Ca (NO)3)2The solution was added to a three-necked flask and added dropwise (NH) at room temperature using a peristaltic pump4)2HPO4While controlling the dropping rate of the solution to 3 mL/min, ammonia water was dropped at a rate of 5 mL/min, and the solution was magnetically stirred at a rotational speed of 500 rpm while maintaining the pH of the mixed solution between 9.5 and 10. After the dropwise addition, the magnetic stirring is continued for 5 hours, and then the mixture is kept stand and aged for 24 hours.
Discarding supernatant, leaching and filtering with 1L anhydrous ethanol, and repeatedly washing and filtering with a large amount of ultrapure water until the filtrate is neutral. After the water washing is finished, dispersing and filtering the filter residue by using ethanol again, and drying the filter residue in a 60 ℃ oven. And grinding the dried solid by using a mortar under an infrared lamp, and sieving the ground solid by using a 150-mesh sieve to obtain a precursor of the hydroxyapatite.
And (3) putting the precursor into a muffle furnace for calcination, firstly heating to 500 ℃ within 100min and maintaining for 5 min, and then continuously heating to 1000 ℃ within 100min and maintaining for 180 min. The calcined product was placed in a ball mill, and 20g of large balls and 40 g of small balls were placed and ball-milled at 400 rpm for 15 hours. Centrifugation is carried out at 5000 rpm for 10 min at 15 ℃, then the solvent is evaporated to dryness at 45 ℃ by a rotary evaporator and dried at 60 ℃. The dried HAp product was ground in a mortar and dried for storage.
And (3) soaking the PET material in absolute ethyl alcohol, and carrying out ultrasonic treatment for 30 min to remove impurities adhered to the surface of the material. After the material was taken out, the material was repeatedly washed with a large amount of ultrapure water to remove the residual ethanol, and dried at room temperature. 5 wt% sodium hydroxide solution is prepared, the PET material is soaked in the sodium hydroxide solution and boiled for 1 h. The material was repeatedly washed with a large amount of ultrapure water until the pH was about 7, and then dried at 60 ℃ to obtain a carboxyl-terminated PET material.
0.4 g of hydroxyapatite powder is weighed, 100 mL of ethanol and 50 mL of ultrapure water are sequentially added, and ultrasonic treatment is carried out for 30 min to uniformly disperse HAp in the solution. The HAp coating was prepared by using a dip-coating machine, reducing the PET material into 10 cm by 10 cm pieces, dipping it vertically into the HAp dispersion at a constant speed, dipping it in the solution for 30 s to reach equilibrium, and then dipping it at an initial speed of 1 mm/s and 5 mm/s2The acceleration of the lifting device is uniform, so that the PET material is vertically lifted out of the liquid level. Drying for 24 h at room temperature to completely volatilize ethanol and form a gradient HAp coating on the PET surface.
FIG. 2 is a scanning electron microscope picture of different areas of PET surface coating prepared in example 2.
Example 3
500 mL of 0.5M Ca (NO) was prepared3)2Solution and 300 mL of 0.5M (NH)4)2HPO4The solution was diluted to 500 mL with 50 mL of concentrated aqueous ammonia using Milli-Q ultrapure water. Mixing Ca (NO)3)2The solution was added to a three-necked flask and added dropwise (NH) at room temperature using a peristaltic pump4)2HPO4While controlling the dropping rate of the solution to 3 mL/min, ammonia water was dropped at a rate of 5 mL/min, and the solution was magnetically stirred at a rotational speed of 500 rpm while maintaining the pH of the mixed solution between 9.5 and 10. After the dropwise addition, the magnetic stirring is continued for 5 hours, and then the mixture is kept stand and aged for 24 hours.
Discarding supernatant, leaching and filtering with 1L anhydrous ethanol, and repeatedly washing and filtering with a large amount of ultrapure water until the filtrate is neutral. After the water washing is finished, dispersing and filtering the filter residue by using ethanol again, and drying the filter residue in a 60 ℃ oven. And grinding the dried solid by using a mortar under an infrared lamp, and sieving the ground solid by using a 150-mesh sieve to obtain a precursor of the hydroxyapatite.
And (3) putting the precursor into a muffle furnace for calcination, firstly heating to 500 ℃ within 100min and maintaining for 5 min, and then continuously heating to 1000 ℃ within 100min and maintaining for 180 min. The calcined product was placed in a ball mill, and 20g of large balls and 40 g of small balls were placed and ball-milled at 400 rpm for 15 hours. Centrifugation is carried out at 5000 rpm for 10 min at 15 ℃, then the solvent is evaporated to dryness at 45 ℃ by a rotary evaporator and dried at 60 ℃. The dried HAp product was ground in a mortar and dried for storage.
And (3) soaking the PET material in absolute ethyl alcohol, and carrying out ultrasonic treatment for 30 min to remove impurities adhered to the surface of the material. After the material was taken out, the material was repeatedly washed with a large amount of ultrapure water to remove the residual ethanol, and dried at room temperature. 5 wt% sodium hydroxide solution is prepared, the PET material is soaked in the sodium hydroxide solution and boiled for 1 h. The material was repeatedly washed with a large amount of ultrapure water until the pH was about 7, and then dried at 60 ℃ to obtain a carboxyl-terminated PET material.
0.4 g of hydroxyapatite powder is weighed, 100 mL of ethanol and 50 mL of ultrapure water are sequentially added, and ultrasonic treatment is carried out for 30 min to uniformly disperse HAp in the solution. The HAp coating was prepared by dip-coating a PET material in 10 cm by 10 cm pieces, immersed vertically in the HAp dispersion at a constant speed for 60 s to reach equilibrium, and then immersed at an initial speed of 5 mm/s and 2mm/s2The acceleration of the lifting device is uniform, so that the PET material is vertically lifted out of the liquid level. Drying for 24 h at room temperature to completely volatilize ethanol and form a gradient HAp coating on the PET surface.
Claims (4)
1. A preparation method of a gradient biological coating on the surface of a PET material is characterized by comprising the following steps: the preparation method comprises the following steps of taking bone-like inorganic salt hydroxyapatite as a coating material, preparing nano HAp by using a chemical precipitation method, and preparing a gradient HAp coating on the surface of PET by using a dip-coating method:
(1) preparation of nano-hydroxyapatite
500 mL of 0.5M Ca (NO) was prepared3)2Solution and 300 mL of 0.5M (NH)4)2HPO4Solution 50 mL of concentrated aqueous ammonia was diluted to 500 mL with Milli-Q ultrapure water, and Ca (NO) was added3)2The solution was added to a three-necked flask and added dropwise (NH) at room temperature using a peristaltic pump4)2HPO4Controlling the dropping rate of the solution to be 3 mL/min, simultaneously dropping ammonia water at the rate of 5 mL/min, keeping the pH value of the mixed solution between 9.5 and 10, and dropping while 500 rpPerforming magnetic stirring at the rotating speed of m, continuing the magnetic stirring for 5 hours after the dropwise adding is finished, and then standing and aging for 24 hours;
removing supernatant, leaching and filtering with 1L of anhydrous ethanol, repeatedly cleaning and filtering with a large amount of ultrapure water until filtrate is neutral, dispersing and filtering with ethanol again after water washing is finished, drying filter residue in a 60 ℃ oven, grinding dried solid under an infrared lamp by using a mortar, and sieving by using a 150-mesh sieve to obtain a precursor of hydroxyapatite;
placing the precursor in a muffle furnace for calcination, firstly heating to 500 ℃ within 100min and maintaining for 5 min, then continuously heating to 1000 ℃ within 100min and maintaining for 180 min, placing the calcined product in a ball mill, placing 20g of large balls and 40 g of small balls, carrying out ball milling for 15 h at the rotating speed of 400 rpm, centrifuging for 10 min at the rotating speed of 5000 rpm at 15 ℃, then evaporating the solvent to dryness at 45 ℃ by using a rotary evaporator, drying at 60 ℃, grinding the dried HAp product by using a mortar, and drying and storing for later use;
(2) surface pretreatment of PET materials
Soaking a PET material in absolute ethyl alcohol, performing ultrasonic treatment for 30 min to remove impurities adhered to the surface of the material, taking out the material, repeatedly cleaning the material by using a large amount of ultrapure water to remove residual ethyl alcohol, drying at room temperature, preparing a 5 wt% sodium hydroxide solution, soaking the PET material in the solution, boiling for 1 h, repeatedly cleaning the material by using a large amount of ultrapure water until the pH value is about 7, and then drying at 60 ℃ to obtain the PET material with the terminal group being carboxyl;
(3) gradient HAp coating on PET surface prepared by dip-coating method
Weighing 0.4 g of hydroxyapatite powder, sequentially adding 100 mL of ethanol and 50 mL of ultrapure water, performing ultrasonic treatment for 30 min to uniformly disperse HAp in the solution, preparing an HAp coating by using an immersion dip coating machine, cutting a PET material into small blocks of 10 cm multiplied by 10 cm, vertically immersing the small blocks into the HAp dispersion liquid at a constant speed, immersing the small blocks into the solution for a certain time to achieve balance, then uniformly accelerating the PET material to be vertically pulled out of the liquid level at a certain initial speed and acceleration, drying the small blocks at room temperature for 24 h to completely volatilize ethanol, and forming a gradient HAp coating on the surface of PET;
the initial pulling speed is 0.2-5 mm/s;
the lifting acceleration is 1-10 mm/s2。
2. The method for preparing the gradient biological coating on the surface of the PET material according to claim 1, wherein the dipping time is 5-60 s.
3. A gradient bio-coating on the surface of PET material, characterized in that it is prepared according to the method of claim 1 or 2.
4. The use of the gradient biological coating on the surface of the PET material according to claim 3 as an artificial ligament material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711050278.XA CN107596442B (en) | 2017-10-31 | 2017-10-31 | Preparation method of gradient biological coating on PET material surface, product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711050278.XA CN107596442B (en) | 2017-10-31 | 2017-10-31 | Preparation method of gradient biological coating on PET material surface, product and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107596442A CN107596442A (en) | 2018-01-19 |
| CN107596442B true CN107596442B (en) | 2020-10-27 |
Family
ID=61084558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711050278.XA Active CN107596442B (en) | 2017-10-31 | 2017-10-31 | Preparation method of gradient biological coating on PET material surface, product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107596442B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231845B (en) * | 2018-08-03 | 2020-12-11 | 大连理工大学 | Hybrid membrane material with gradient color effect and preparation method thereof |
| CN111450316B (en) * | 2020-03-04 | 2021-07-20 | 深圳市迈捷生命科学有限公司 | Integrated bracket for simulating bone-tendon-bone mineralization-non-mineralization gradient structure |
| CN111921010A (en) * | 2020-07-16 | 2020-11-13 | 复旦大学 | Nano-hydroxyapatite modified artificial ligament and modification method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993023091A1 (en) * | 1992-05-20 | 1993-11-25 | Sherwood Medical Company | Artificial windpipe |
| CN1589161A (en) * | 2001-10-12 | 2005-03-02 | 美国英佛曼公司 | Coating, coated articles and methods of manufacture thereof |
| WO2005110508A3 (en) * | 2004-04-30 | 2006-05-26 | Advanced Cardiovascular System | Modulating properties of coatings on implantable devices |
| CN101912317A (en) * | 2009-02-19 | 2010-12-15 | 拜欧麦特制造公司 | Medical implant with drug delivery coating |
| CN101703798B (en) * | 2009-11-05 | 2013-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Nano hydroxyapatite coating and preparation method thereof and electrostatic atomization device |
| CN103110979A (en) * | 2013-02-09 | 2013-05-22 | 复旦大学 | High molecular porous material with surface deposited bone-like hydroxyapatite as well as preparation method and application thereof |
| CN103803519A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lamellar porous calcium phosphate powder with micro-nano multilevel structure |
| CN104119551A (en) * | 2014-07-29 | 2014-10-29 | 复旦大学附属华山医院 | Preparation method of calcium-strontium/gelatin biomimetic coating modified artificial ligament |
| CN104288836A (en) * | 2014-09-09 | 2015-01-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Active coating layer modified polyethylene terephthalate material and preparation method thereof |
| CN105220451A (en) * | 2015-10-16 | 2016-01-06 | 上海纳米技术及应用国家工程研究中心有限公司 | There is the preparation method of the polyethylene terephthalate braided material of antibacterial and short mineralization function coating |
| CN105979976A (en) * | 2013-12-10 | 2016-09-28 | 法国国家健康医学研究院 | Methods for adhering tissue surfaces and materials and biomedical uses thereof |
| CN106729991A (en) * | 2016-11-22 | 2017-05-31 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of segmentation coating for body implanting material |
-
2017
- 2017-10-31 CN CN201711050278.XA patent/CN107596442B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993023091A1 (en) * | 1992-05-20 | 1993-11-25 | Sherwood Medical Company | Artificial windpipe |
| CN1589161A (en) * | 2001-10-12 | 2005-03-02 | 美国英佛曼公司 | Coating, coated articles and methods of manufacture thereof |
| WO2005110508A3 (en) * | 2004-04-30 | 2006-05-26 | Advanced Cardiovascular System | Modulating properties of coatings on implantable devices |
| CN101912317A (en) * | 2009-02-19 | 2010-12-15 | 拜欧麦特制造公司 | Medical implant with drug delivery coating |
| CN101703798B (en) * | 2009-11-05 | 2013-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Nano hydroxyapatite coating and preparation method thereof and electrostatic atomization device |
| CN103803519A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lamellar porous calcium phosphate powder with micro-nano multilevel structure |
| CN103110979A (en) * | 2013-02-09 | 2013-05-22 | 复旦大学 | High molecular porous material with surface deposited bone-like hydroxyapatite as well as preparation method and application thereof |
| CN105979976A (en) * | 2013-12-10 | 2016-09-28 | 法国国家健康医学研究院 | Methods for adhering tissue surfaces and materials and biomedical uses thereof |
| CN104119551A (en) * | 2014-07-29 | 2014-10-29 | 复旦大学附属华山医院 | Preparation method of calcium-strontium/gelatin biomimetic coating modified artificial ligament |
| CN104288836A (en) * | 2014-09-09 | 2015-01-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Active coating layer modified polyethylene terephthalate material and preparation method thereof |
| CN105220451A (en) * | 2015-10-16 | 2016-01-06 | 上海纳米技术及应用国家工程研究中心有限公司 | There is the preparation method of the polyethylene terephthalate braided material of antibacterial and short mineralization function coating |
| CN106729991A (en) * | 2016-11-22 | 2017-05-31 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of segmentation coating for body implanting material |
Non-Patent Citations (1)
| Title |
|---|
| Augmentation of Bone Tunnel Healing in Anterior Cruciate Ligament Grafts: Application of Calcium Phosphates and OtherMaterials;F. R. Baxter;《Journal of Tissue Engineering》;20101231;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107596442A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hossan et al. | Preparation and characterization of gelatin-hydroxyapatite composite for bone tissue engineering | |
| CN107596442B (en) | Preparation method of gradient biological coating on PET material surface, product and application thereof | |
| CN108404203B (en) | Preparation method of reduced graphene oxide/biological glass nanofiber scaffold | |
| CN105457099B (en) | The double-deck crystal whisker-shaped Fluorin doped hydroxyapatite coating layer and its microwave preparation on magnesium alloy | |
| CN114452439B (en) | Hydroxyapatite/whitlockite bioactive ceramic scaffold consisting of bionic natural bone minerals and preparation method thereof | |
| CN101385873B (en) | Preparation method of nano hydroxylapatite biology composite coating | |
| US20210038760A1 (en) | Biomimetic bone composite material, a preparation method and uses thereof | |
| CN100584389C (en) | Hollow ball shaped nanometer hydroxylapatite material and the preparing method | |
| CN109385658A (en) | Hydroxyapatite nano stick array configuration coating of titanium-based surface multiple element codope and its preparation method and application | |
| CN106620840A (en) | Silk fibroin modified bone cement porous scaffold and preparation and application thereof | |
| TWI529152B (en) | A degradable magnesium-calcium silicate bone cement and producing method thereof | |
| CN107823716A (en) | Preparation method of 3D printing Invasive lumbar fusion device composite and products thereof and application | |
| Malau et al. | Synthesis of hydrokxyapatite based duck egg shells using precipitation method | |
| Wan et al. | Biomimetically precipitated nanocrystalline hydroxyapatite | |
| WO2007003968A1 (en) | Novel morphological form of divalent metal ion phosphates | |
| KR100787526B1 (en) | Synthesis of spherical shaped hydroxyapatite, alpha-tricalcium phosphate and beta-tricalcium phosphate nano powders depending on the ph by microwave assisted process | |
| CN109279885A (en) | A kind of preparation method of the bone bracket based on the Biocomposite material containing strontium | |
| CN101401951A (en) | Calcium phosphate biological active ceramic material containing silicon dioxide and preparation method thereof | |
| CN1251768C (en) | Method for preparing full natural material for renovating rigid tissue formed in vitro | |
| CN108677180B (en) | Method for preparing beta-tricalcium phosphate coating on titanium surface | |
| CN106540328A (en) | The preparation method of hydroxyapatite polymeric lactic acid compound film | |
| CN106729969A (en) | A kind of hanging method of zirconium dioxide multiporous biological bone repairing support | |
| CN103785062A (en) | Bone repair material of coating hydroxyapatite and preparation method of bone repair material | |
| CN1765821A (en) | Porous beta-TCP and its preparation method | |
| CN108273128A (en) | Self-cured calcium phosphate bone-rehabilitating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |