CN101974212B - Polycaprolactone/calcium sulfate composite material and preparation method thereof - Google Patents
Polycaprolactone/calcium sulfate composite material and preparation method thereof Download PDFInfo
- Publication number
- CN101974212B CN101974212B CN2010105225681A CN201010522568A CN101974212B CN 101974212 B CN101974212 B CN 101974212B CN 2010105225681 A CN2010105225681 A CN 2010105225681A CN 201010522568 A CN201010522568 A CN 201010522568A CN 101974212 B CN101974212 B CN 101974212B
- Authority
- CN
- China
- Prior art keywords
- calcium sulfate
- polycaprolactone
- minutes
- ethyl alcohol
- absolute ethyl
- 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 discloses a polycaprolactone/calcium sulfate composite material and a preparation method thereof, belonging to the field of macromolecule modification. The method comprises the following steps: utilizing biosurfactant to carry out surface modification on anhydrous calcium sulfate or calcium sulfate whiskers; and adopting a coprecipitation and mould pressing method to prepare anhydrous calcium sulfate or calcium sulfate whiskers reinforced polycaprolactone composite material. The composite material prepared by the method in the invention has the advantages of high mechanical strength and adjustable performance, thereby laying a foundation for the application thereof.
Description
Technical field
The invention belongs to macromolecule modified field, be specifically related to polycaprolactone/calcium sulfate composite material and preparation method thereof.
Background technology
Polycaprolactone has water-fast, oil resistant, and anti-muriatic performance, and have lower fusing point (about 60 ℃) and melt viscosity, this makes its easy machine-shaping.Polycaprolactone is applied to fields such as bone tissue engineer, medicament slow release because of having biocompatibility, biological degradability and hypotoxicity.Though above-mentioned all advantages are arranged, in practical application, the mechanical strength of polycaprolactone is low can not to meet the demands, and need carry out enhancing modified to it.
Domestic be used for strengthening polycaprolactone mainly contain calcium phosphate salt and Win 40350, but the degradation speed of calcium phosphate salt is slow, Win 40350 can not be absorbed in vivo basically.And therefore polycaprolactone, needs to add the enhancement component faster of degrading because the high-crystallinity degraded is very slow.Domestic less about the patent of invention that strengthens polycaprolactone, Chinese invention patent CN101693773A adopts the acorn nut powder that polycaprolactone is carried out enhancing modified, but the adding of acorn nut powder has influenced the biocompatibility and the degradation property of polycaprolactone, limits its Application Areas.Chinese invention patent CN1593673A adopts melt blending or mould pressing method to strengthen polycaprolactone with chitin fiber; But traditional melt blending technology needs to carry out being higher than under the temperature of melting point polymer; Shearing force that screw rod is stronger and high temperature can make the part poly-caprolactone degradation, thereby influence the mechanical property of material.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, a kind of polycaprolactone/calcium sulfate composite material and preparation method thereof is provided, the bar-shaped and whisker structure of calcium sulfate is not destroyed in the course of processing; The intensity of polycaprolactone is improved significantly.
The object of the invention is realized through following proposal:
Polycaprolactone/calcium sulfate composite material, the composition of this material is mainly: polycaprolactone 5g~19g, calcium sulfate 1g~15g.
Said calcium sulfate is anhydrous calciumsulphate or calcium sulfate crystal whiskers through surface-treated; Properties-correcting agent adopts a kind of in Yelkin TTS, rhamnolipid, the lipopeptid or more than one.
The preparation method of above-mentioned polycaprolactone/calcium sulfate composite material, following steps:
(1) coprecipitation method prepares polycaprolactone and calcium sulfate composite material
Taking by weighing the 16g polycaprolactone stirs in 50~60 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing 2.4g calcium sulfate, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of calcium sulfate and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Pour into fast in the beaker that fills the 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 35~50 ℃ of vacuum drying ovens, obtains the blend of powdered polycaprolactone and calcium sulfate;
(2) compression molding of polycaprolactone and anhydrous calciumsulphate matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 70~75 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, the die sinking sampling.
In the aforesaid method, said calcium sulfate is anhydrous calciumsulphate or calcium sulfate crystal whiskers through surface-treated,
(1) surface-treated of anhydrous calciumsulphate: take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 30~35 ℃, suction filtration is removed until impurity for 5 times.Add 15g calcium sulfate then, stirred restir 30 minutes 30 minutes ultrasonic 10 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of anhydrous calciumsulphates that obtain surface-treated down after dry 20 hours in vacuum drying oven.
(2) surface-treated of calcium sulfate crystal whiskers: take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 30~35 ℃, suction filtration is removed until impurity for 5 times.Add the 15g calcium sulfate crystal whiskers then, stirred restir 30 minutes 30 minutes ultrasonic 10 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of calcium sulfate crystal whiskers that obtain surface-treated down after dry 20 hours in vacuum drying oven.
The properties-correcting agent that said anhydrous calciumsulphate or calcium sulfate crystal whiskers surface-treated are adopted also comprises a kind of in rhamnolipid or the lipopeptid or more than one.
Polycaprolactone/calcium sulfate composite material of the present invention can be applicable to the bone reparation.
The present invention compared with prior art, advantage and effect be, adopts the preparation method of polycaprolactone/calcium sulfate composite material of the present invention, and the bar-shaped and whisker structure of calcium sulfate is not destroyed in the course of processing, the intensity of polycaprolactone is improved significantly; In whole technological process, can not make poly-caprolactone degradation; Technology of the present invention is simple, and is extensive in the clinical application field for it.
Calcium sulfate has HS, hypotoxicity, and advantages such as good biocompatibility adopt calcium sulfate powder and whisker modified polycaprolactone, can improve the strength and toughness of polycaprolactone simultaneously.The degradation speed of calcium sulfate is very fast, after the adding, can improve the slower deficiency of poly-caprolactone degradation.In addition; General industry is compared with tensio-active agent; Advantages such as that the bioactivity surface promoting agent has is nontoxic, biocompatibility adopt bioactivity surface promoting agent such as Yelkin TTS to calcium sulfate powder and the whisker modified powder oleophylic value surperficial with whisker that improve, and make the interfacial adhesion increase of calcium sulfate powder and whisker and polycaprolactone; Improve the mechanical property of matrix material, but matrix material can not receive application limitations because of having toxicity.
Adopt that calcium sulfate crystal whiskers and polycaprolactone are compound then to show tangible advantage.Itself has excellent biological compatibility calcium sulfate crystal whiskers, can degradation in vivo absorb.And the calcium sulfate crystal whiskers similar joins in the polycaprolactone in the structure of short glass fiber, can effectively improve the modulus and the shock strength of material, and improves material stiffness simultaneously and toughness is that most of powder body material reinforced effects is unapproachable.Therefore, this patent has adopted the enhancing matrix of calcium sulfate crystal whiskers as polycaprolactone.
Description of drawings
Fig. 1 is the electron scanning micrograph that the anhydrous calciumsulphate of the embodiment of the invention 1 strengthens polycaprolactone composite material.
Fig. 2 is the electron scanning micrograph that the calcium sulfate crystal whiskers of the embodiment of the invention 2 strengthens polycaprolactone composite material.
Fig. 3 is the electron scanning micrograph that the modification anhydrous calciumsulphate of the embodiment of the invention 3 strengthens polycaprolactone composite material.
Fig. 4 is the electron scanning micrograph that the wastewaters with modified calcium sulfate whiskers of the embodiment of the invention 4 strengthens polycaprolactone composite material.
Fig. 5 is the electron scanning micrograph that the wastewaters with modified calcium sulfate whiskers of the embodiment of the invention 5 strengthens polycaprolactone composite material.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further explain, but embodiment of the present invention is not limited thereto.
Embodiment 1
(1) coprecipitation method prepares polycaprolactone and anhydrous calciumsulphate matrix material
Taking by weighing the 16g polycaprolactone stirs in 58 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing 2.4g anhydrous slufuric acid calcium powder, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of anhydrous calciumsulphate and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 45 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and anhydrous calciumsulphate.
(2) compression molding of polycaprolactone and anhydrous calciumsulphate matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 75 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Embodiment 2
(1) coprecipitation method prepares polycaprolactone and calcium sulfate crystal whiskers matrix material
Taking by weighing the 16g polycaprolactone stirs in 50 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing the modification anhydrous slufuric acid calcium powder of 2.4g, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of calcium sulfate crystal whiskers and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 35 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and calcium sulfate crystal whiskers.
(2) compression molding of polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 70 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Embodiment 3
(1) surface-treated of anhydrous calciumsulphate
Take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration is removed until impurity for 5 times.Add 15g calcium sulfate then, stirred 30 minutes, ultrasonic 10 minutes, restir 30 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 50 ℃ of anhydrous calciumsulphates that obtain surface-treated down after dry 20 hours in vacuum drying oven.
(2) coprecipitation method prepares polycaprolactone and modification anhydrous calciumsulphate matrix material
Taking by weighing the 16g polycaprolactone stirs in 60 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing the modification anhydrous slufuric acid calcium powder of 2.4g, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of anhydrous calciumsulphate and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 30 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and modification anhydrous calciumsulphate.
(3) compression molding of polycaprolactone and modification anhydrous calciumsulphate matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 71 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Embodiment 4
(1) surface-treated of calcium sulfate crystal whiskers
Take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration is removed until impurity for 5 times.Add the 15g calcium sulfate crystal whiskers then, stirred 30 minutes, ultrasonic 10 minutes, restir 30 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of calcium sulfate crystal whiskers that obtain surface-treated down after dry 20 hours in vacuum drying oven.
(2) coprecipitation method prepares polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
Taking by weighing the 16g polycaprolactone stirs in 55 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing the wastewaters with modified calcium sulfate whiskers of 2.4g, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of wastewaters with modified calcium sulfate whiskers and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 45 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and wastewaters with modified calcium sulfate whiskers.
(3) compression molding of polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 70 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Embodiment 5
(1) surface-treated of calcium sulfate crystal whiskers
Take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration is removed until impurity for 5 times.Add the 15g calcium sulfate crystal whiskers then, stirred 30 minutes, ultrasonic 10 minutes, restir 30 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of calcium sulfate crystal whiskers that obtain surface-treated down after dry 20 hours in vacuum drying oven.
(2) coprecipitation method prepares polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
Taking by weighing the 16g polycaprolactone stirs in 60 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing the wastewaters with modified calcium sulfate whiskers of 4g, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of wastewaters with modified calcium sulfate whiskers and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Just pour into fast in ultrasonic, fill in the beaker of 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 40 ℃ of vacuum drying ovens, obtains the mixture of powdered polycaprolactone and wastewaters with modified calcium sulfate whiskers.
(3) compression molding of polycaprolactone and wastewaters with modified calcium sulfate whiskers matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 73 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, die sinking sampling (160 * 10 * 4mm
3).
Following table is: embodiment 1~5 pure polycaprolactone and composite materials property
The foregoing description is merely preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other are any not to deviate from change, the modification done under spirit of the present invention and the principle, substitute, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (3)
1. the preparation method of polycaprolactone/calcium sulfate composite material is characterized in that following steps:
(1) coprecipitation method prepares polycaprolactone and calcium sulfate composite material
Taking by weighing the 16g polycaprolactone stirs in 50~60 ℃ of waters bath with thermostatic control and made it be dissolved in the THF fully in 1 hour; Take by weighing 2.4g calcium sulfate, stir at normal temperatures it is dispersed in the THF; The tetrahydrofuran solution of polycaprolactone is poured in the THF suspension-s of calcium sulfate and mixed, magneton stirs 2h under the normal temperature; Behind the ultrasonic 15min, restir 2 hours; Pour into fast in the beaker that fills the 750ml absolute ethyl alcohol, separate out white depositions; With absolute ethyl alcohol washing and precipitating thing repeatedly; Drying is 1 day in 35~50 ℃ of vacuum drying ovens, obtains the blend of powdered polycaprolactone and calcium sulfate;
(2) compression molding of polycaprolactone and anhydrous calciumsulphate matrix material
The blend of coprecipitation method preparation was made its complete fusion in 45 minutes 70~75 ℃ of following preheatings, and hot pressing is 5 minutes under 15MPa, and repeatedly exhaust was colded pressing 3 minutes in normal temperature, 15MPa then, the die sinking sampling.
2. preparation method according to claim 1 is characterized in that, said calcium sulfate is anhydrous calciumsulphate or calcium sulfate crystal whiskers through surface-treated;
Said anhydrous calciumsulphate through surface-treated prepares as follows: take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration 5 times is removed until impurity; Add 15g calcium sulfate then, stirred restir 30 minutes 30 minutes ultrasonic 10 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of anhydrous calciumsulphates that obtain surface-treated down after dry 20 hours in vacuum drying oven;
Said calcium sulfate crystal whiskers through surface-treated prepares as follows: take by weighing 0.75g Yelkin TTS and be dissolved in the 220ml absolute ethyl alcohol, stirred 5 hours down in 35 ℃, suction filtration 5 times is removed until impurity; Add the 15g calcium sulfate crystal whiskers then, stirred restir 30 minutes 30 minutes ultrasonic 10 minutes; Use the absolute ethyl alcohol suction filtration, clean 5 times; 45 ℃ of calcium sulfate crystal whiskers that obtain surface-treated down after dry 20 hours in vacuum drying oven.
3. preparation method according to claim 2 is characterized in that, the said properties-correcting agent that anhydrous calciumsulphate or calcium sulfate crystal whiskers adopted through surface-treated also comprises a kind of in rhamnolipid or the lipopeptid or more than one.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010105225681A CN101974212B (en) | 2010-10-26 | 2010-10-26 | Polycaprolactone/calcium sulfate composite material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010105225681A CN101974212B (en) | 2010-10-26 | 2010-10-26 | Polycaprolactone/calcium sulfate composite material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101974212A CN101974212A (en) | 2011-02-16 |
CN101974212B true CN101974212B (en) | 2012-08-22 |
Family
ID=43574123
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2010105225681A Active CN101974212B (en) | 2010-10-26 | 2010-10-26 | Polycaprolactone/calcium sulfate composite material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101974212B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102212204B (en) * | 2011-05-16 | 2013-01-16 | 刘立文 | Modified anhydrous calcium sulfate and preparation method thereof |
CN102634847B (en) * | 2012-04-25 | 2015-04-22 | 昆明理工大学 | Method for surface modification of calcium sulfate crystal whisker |
CN103352396B (en) * | 2013-06-09 | 2015-10-28 | 华东理工大学 | A kind of method being prepared crystal whisker of gypsum by the modification of organic/inorganic compound coating |
CN103319866B (en) * | 2013-07-16 | 2015-12-23 | 暨南大学 | Magnesia crystal whisker/biodegradable polyester composite material and its preparation method and application |
CN105820522B (en) * | 2016-04-01 | 2017-12-26 | 安徽理工大学 | A kind of calcium sulfate crystal whiskers activeness and quietness lactic acid composite material and preparation method thereof |
CN108373585A (en) * | 2018-03-05 | 2018-08-07 | 湖北民族学院 | α-half-H 2 O calcium sulphate/aliphatic poly resin composite material and preparation method thereof |
CN108721702B (en) * | 2018-06-29 | 2021-06-29 | 江西理工大学 | Preparation method of magnesium/L-polylactic acid composite bone scaffold |
CN112675365A (en) * | 2020-11-19 | 2021-04-20 | 宁波宝亭生物科技有限公司 | Preparation method of high-strength absorbable bone nail |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1344538A1 (en) * | 2002-03-14 | 2003-09-17 | Degradable Solutions AG | Porous biodegradable implant material and method for its fabrication |
CN1724081A (en) * | 2005-07-07 | 2006-01-25 | 天津大学 | Material of porous composite calcium sulfate with polymer for support and preparation process thereof |
CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
-
2010
- 2010-10-26 CN CN2010105225681A patent/CN101974212B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1344538A1 (en) * | 2002-03-14 | 2003-09-17 | Degradable Solutions AG | Porous biodegradable implant material and method for its fabrication |
CN1724081A (en) * | 2005-07-07 | 2006-01-25 | 天津大学 | Material of porous composite calcium sulfate with polymer for support and preparation process thereof |
CN101760037A (en) * | 2008-12-23 | 2010-06-30 | 金发科技股份有限公司 | Completely degraded plant powder modified thermoplastics composite material and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
宋斐.聚己内酯(PCL)的共混改性研究.《中国优秀博硕士学位论文全文数据库(硕士)工程科技I辑》.2007,(第6期),第25-39页. * |
Also Published As
Publication number | Publication date |
---|---|
CN101974212A (en) | 2011-02-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101974212B (en) | Polycaprolactone/calcium sulfate composite material and preparation method thereof | |
Gu et al. | Effects of incorporation of HA/ZrO2 into glass ionomer cement (GIC) | |
CN107303397B (en) | A kind of biologically active Injectable compound bone cement and its preparation method and application | |
Wei et al. | 3D-printed hydroxyapatite microspheres reinforced PLGA scaffolds for bone regeneration | |
Cui et al. | An injectable borate bioactive glass cement for bone repair: preparation, bioactivity and setting mechanism | |
Christy et al. | Nano zinc oxide and nano bioactive glass reinforced chitosan/poly (vinyl alcohol) scaffolds for bone tissue engineering application | |
CN101991881B (en) | Controllablely degradable internal fixation composite material and preparation method and application thereof | |
CN105504715A (en) | Chitin whisker/magnesium oxide whisker/biodegradable polyester composite material as well as preparation method and application thereof | |
Pahlevanzadeh et al. | Apatite‐forming ability, cytocompatibility, and mechanical properties enhancement of poly methyl methacrylate‐based bone cements by incorporating of baghdadite nanoparticles | |
CN101422632A (en) | Preparation method of hydroxyapatite/sodium alginate nano composite material | |
Boroujeni et al. | Development of multi-walled carbon nanotubes reinforced monetite bionanocomposite cements for orthopedic applications | |
CN103386150B (en) | Preparation method and application of glucomannan/chitosan composite membrane for conducting tissue regeneration | |
CN104591679A (en) | Modified magnesium oxychloride bone cement as well as preparation method and application thereof | |
CN101698117B (en) | Bone-repairing composite material and method for preparing the same | |
Miao et al. | Engineered bone tissues using biomineralized gelatin methacryloyl/sodium alginate hydrogels | |
Rakmae et al. | Influence of heat-treated bovine bone-derived hydroxyapatite on physical properties and in vitro degradation behavior of poly (lactic acid) composites | |
Song et al. | Macro-and microporous polycaprolactone/duck’s feet collagen scaffold fabricated by combining facile phase separation and particulate leaching techniques to enhance osteogenesis for bone tissue engineering | |
Tavakoli et al. | Incorporation of graphene oxide as a coupling agent in a 3D printed polylactic acid/hardystonite nanocomposite scaffold for bone tissue regeneration applications | |
CN108219680A (en) | For the adhesive composition of sclerotin historical relic reparation | |
Yang et al. | Preparation and mineralization of a biocompatible double network hydrogel | |
Miyazaki | Design of bone-integrating organic-inorganic composite suitable for bone repair | |
CN101199869A (en) | Liquid crystal hydroxyl apatite/polymer compound aeolotropy bone substitute material and preparing method thereof | |
CN105536069A (en) | Hydroxyapatite-graphene-chitosan tri-crosslinking reduction compound material and preparing method thereof | |
Yang et al. | A study on in vitro and in vivo bioactivity of nano hydroxyapatite/polymer biocomposite | |
Nezafati et al. | EVALUATION OF A PREPARED SOL-GEL BIOACTIVE GLASS FIBRE-REINFORCED CALCIUM PHOSPHATE CEMENT |
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 |