CN107261203A - A kind of nano-bioactive glass material and preparation method thereof - Google Patents

A kind of nano-bioactive glass material and preparation method thereof Download PDF

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Publication number
CN107261203A
CN107261203A CN201710510718.9A CN201710510718A CN107261203A CN 107261203 A CN107261203 A CN 107261203A CN 201710510718 A CN201710510718 A CN 201710510718A CN 107261203 A CN107261203 A CN 107261203A
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nano
glass material
bioactive glass
added
nitrate
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王海霞
王之霖
潘宏梅
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Changzhou Jie Xuan Textile Technology Co Ltd
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Changzhou Jie Xuan Textile Technology Co Ltd
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/002—Hollow glass particles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/08—Methods for forming porous structures using a negative form which is filled and then removed by pyrolysis or dissolution
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a kind of nano-bioactive glass material and preparation method thereof, belong to medical material preparing technical field.Tetraethyl orthosilicate is added in ethanol solution and uses nitre acid for adjusting pH after dissolving by the present invention, add triethyl phosphate, zinc nitrate, template mixes to obtain sol solutionses, then calcium nitrate is mixed with deionized water, and add the obtained dispersion liquid of dispersant, after sol solutionses are mixed with dispersion liquid again pH is adjusted with ammoniacal liquor, being centrifuged after standing to precipitate, it is finally that precipitation is lyophilized, cooling discharging after calcining, nano-bioactive glass material can be obtained, bioactivity glass produced by the present invention has uniform particle sizes, good dispersion, the characteristics of apparent porosity height and big specific surface area, effectively increase the bioactivity of material, and with preferable medicine delivered payload capability, it is a kind of preferable medical material.

Description

A kind of nano-bioactive glass material and preparation method thereof
Technical field
The invention discloses a kind of nano-bioactive glass material and preparation method thereof, belong to medical material technology of preparing Field.
Background technology
Bioactivity glass is one of focus of current osseous tissue renovating material research, it have good bioactivity and Biocompatibility.It is main by SiO2、Na2O, CaO and P2O5After composition, implantation human body, pass through the circulation of body fluid, bioactivity Occur ion exchange between glass energy and soft tissue and bone, make to form chemical bonding between material interface and body bone tissue, This ion exchange serves mineralization, ultimately forms the hydroxyapatite as the mineral matter form of normal bone tissues Layer, so as to induce more rapid Bone Defect Repari and regeneration.Therefore, bioactivity glass has good potential applicability in clinical practice.
At present, bioactivity glass can be synthesized with two kinds of conventional methods：Conventional melt derivatization method and sol-gel Method.Melting derivatization method is used in traditional glass technology, and glass ingredient is mixed with the crystal grain of oxide or carbonate form, Ran Hou Melt and homogenize under high temperature, then melten glass is sprinkled into steel or graphite jig and carries out batch grinding or polishing.If needed Bioactivity glass powder is wanted, then by pouring into a mould melten glass into liquid medium, so that small fragment is made in pressure break refrigeration glass. Then using grinding and size separating step, to realize powder control in certain size scope.However, traditional glass derives Method prepares bioactivity glass in the presence of some shortcomings.For example, the bio-vitric prepared using this method it is closely knit it is non-porous, compare surface Product is small, simultaneously because high fusion temperature and process step evaporates volatile ingredient P2O5, make it difficult to possess optimal biology Activity.
In recent years, sol-gel technique turns into the important method for preparing new material, molten different from traditional fusion method Glue-gel method is a kind of new method for preparing inorganic material at room temperature, and the bio-vitric that particularly prepared by this method has a large amount of Micro-nano hole so that due to high-specific surface area and high bioactivity.At present, sol-gel technique is gradually substituted Melt derivatization method, the method the most frequently used as bio-vitric is prepared.But the simple bio-vitric prepared using sol-gel process Grain is still in bond state, it is difficult to scatter, and what is obtained by grinding after screening is the irregular micron particles of pattern, it is difficult to Obtain morphology controllable, the micro/nano level bio-vitric of particle size uniformity.
Therefore, above-mentioned technical problem how is solved, research and development are a kind of to have nano-scale particle sizes and good dispersion, and raw Thing activity preferably bioactivity glass, for preparing high bioactivity bone repair, bone tissue engineering scaffold and pharmaceutical carrier With important theoretical and practical significance.
The content of the invention
Present invention mainly solves technical problem：The bioactivity glass presence prepared for existing sol-gel process Grain bad dispersibility, size are uneven, and there is provided a kind of nano-bioactive glass material and its preparation for the uncontrollable defect of pattern Method.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of nano-bioactive glass material, including silica, calcium oxide, phosphorus pentoxide, zinc oxide, the nanometer life Thing activity glass material is caged tiny balloon, and its surface texture is rendered as the apatite layer with nano-pore level.
Cage-like hollow microsphere structure is tetraethyl orthosilicate, triethyl phosphate, nitre by being supported by kernel of template Colloidal sol prepared by sour zinc and calcium nitrate is skeleton, and dispersant is shell, and sintering is made.
The template is one or both of chitosan, gelatin, glucose, maltose, and consumption is zinc nitrate quality 10~30 times.
The tetraethyl orthosilicate, triethyl phosphate, zinc nitrate, the mol ratio of calcium nitrate are (60~80)：（8~10）：（1 ~2）：(16~36).
The dispersant is one kind in polyvinyl alcohol P6000, polyvinyl alcohol P10000, polyvinyl alcohol P20000, consumption For 40~120 times of zinc nitrate quality.
A kind of preparation method of nano-bioactive glass material, specific preparation process is：
S1. in molar ratio (60~80)：（8~10）：（1~2）：(16~36), take tetraethyl orthosilicate, triethyl phosphate, nitric acid Zinc, calcium nitrate；
S2. tetraethyl orthosilicate is added in ethanol solution and dissolved, and tricresyl phosphate second is added to 0.8~1.0 with nitre acid for adjusting pH Ester, zinc nitrate, template, continue to stir 20~30min, obtain sol solutionses；
S3. calcium nitrate is added in deionized water and be well mixed, add dispersant, stir to obtain dispersion liquid；
S4. sol solutionses are instilled in dispersion liquid and continues stirring until completion of dropping, added ammoniacal liquor and adjust pH to 12.0~12.5, it is quiet Put and centrifuge and must precipitate after 1~2h, 20~24h of freeze-drying at -30~-20 DEG C will be deposited in, freeze-dried powder is obtained；
S5. freeze-dried powder is placed in Muffle furnace, 600~650 DEG C is heated to 1~5 DEG C/min, calcined 4~6h, be cooled to room temperature After discharge, obtain nano-bioactive glass material.
The beneficial effects of the invention are as follows：
（1）The present invention it is spherical in shape by template adion, the agent of drying and sintering rear pattern plate oxidation leave one it is hollow, here it is The reason for there is hollow ball-shape body, while the hydroxyl contained using dispersant forms stronger hydrogen bond, ether with forerunner's precipitating ion Key also easily produces affinity interaction with precipitating ion surface, makes dispersant adsorption in ion surface, so that a floor height molecular film is formed, Forerunner's precipitating ion is wrapped up, causes space steric effect, interionic attraction is slackened significantly, so as to effectively prevent ion Growth, suppress particle reunion, in refrigerating process, take full advantage of water icing when volume become it is big the characteristics of, colloidal sol is cold During jelly, ice crystal is condensed precipitation, form special duct, intensive is distributed between ice crystal gap, formed after drying and sintering Cage structure；
（2）The present invention has nano-scale particle sizes and with good dispersion, and contains Zn-ef ficiency, can be thin by activating skeletonization The synthesis of born of the same parents' protein, stimulates bon e formation to improve atpase activity, can promote the doped calcium of mescenchymal stem cell, can also bear A variety of bone growth factors are carried, the support of the bone tissue engineer of preparation can support bone cell growth.
Embodiment
Take 0.6~0.8mol tetraethyl orthosilicates, add during 2.4~3.6L mass fractions are 25% ethanol solution, with 300~ 400r/min stirs 10~20min, and adds 0.08~0.10mol triethyl phosphates to 0.8~1.0 with nitre acid for adjusting pH, 0.01~0.02mol zinc nitrates, 60~90g templates continue to stir 20~30min, obtain sol solutionses, take 0.16~0.36mol Calcium nitrate, is added in 1.8~2.4L deionized waters, and 20~30min is stirred with 300~400r/min, adds 240~360g points Powder, continues to stir 20~30min, obtains dispersion liquid, sol solutionses are instilled in dispersion liquid with 5~10mL/min, and with 300~ 400r/min continues stirring until completion of dropping, adds ammoniacal liquor regulation pH to 12.0~12.5, is centrifuged after standing 1~2h Precipitation, precipitation is placed in vacuum freezing drying oven, and 20~24h is dried at -30~-20 DEG C, freeze-dried powder is obtained, freeze-dried powder is put In Muffle furnace, 600~650 DEG C are heated to 1~5 DEG C/min, 4~6h is calcined, is cooled to after room temperature and discharges, obtain nano biological Activity glass material.The template is one or both of chitosan, gelatin, glucose, maltose.The dispersant is One kind in polyvinyl alcohol P6000, polyvinyl alcohol P10000, polyvinyl alcohol P20000.
Example 1
0.6mol tetraethyl orthosilicates are taken, 2.4L mass fractions are added in 25% ethanol solution, 10min is stirred with 300r/min, and With nitre acid for adjusting pH to 0.8,0.08mol triethyl phosphates are added, 0.01mol zinc nitrates, 60g chitosans continue to stir 20min, obtains sol solutionses, takes 0.16mol calcium nitrate, adds in 1.8L deionized waters, stirs 20min with 300r/min, adds 240g polyvinyl alcohol P6000, continue to stir 20min, obtain dispersion liquid, sol solutionses are instilled in dispersion liquid with 5mL/min, and with 300r/min continues stirring until completion of dropping, adds ammoniacal liquor regulation pH to 12.0, centrifuges and must precipitate after standing 1h, will be heavy Shallow lake is placed in vacuum freezing drying oven, at -30 DEG C dry 20h, obtain freeze-dried powder, freeze-dried powder be placed in Muffle furnace, with 1 DEG C/ Min is heated to 600 DEG C, calcines 4h, is cooled to after room temperature and discharges, obtains nano-bioactive glass material.
Example 2
0.7mol tetraethyl orthosilicates are taken, 3.0L mass fractions are added in 25% ethanol solution, 15min is stirred with 350r/min, and With nitre acid for adjusting pH to 0.9,0.09mol triethyl phosphates are added, 0.01mol zinc nitrates, 75g gelatin continues to stir 25min, obtains sol solutionses, takes 0.26mol calcium nitrate, adds in 2.1L deionized waters, stirs 25min with 350r/min, adds 300g polyvinyl alcohol P10000, continue to stir 25min, obtain dispersion liquid, sol solutionses are instilled in dispersion liquid with 8mL/min, and with 350r/min continues stirring until completion of dropping, adds ammoniacal liquor regulation pH to 12.3, centrifuges and must precipitate after standing 1h, will be heavy Shallow lake is placed in vacuum freezing drying oven, at -25 DEG C dry 22h, obtain freeze-dried powder, freeze-dried powder be placed in Muffle furnace, with 3 DEG C/ Min is heated to 625 DEG C, calcines 5h, is cooled to after room temperature and discharges, obtains nano-bioactive glass material.
Example 3
0.8mol tetraethyl orthosilicates are taken, 3.6L mass fractions are added in 25% ethanol solution, 20min is stirred with 400r/min, and With nitre acid for adjusting pH to 1.0,0.10mol triethyl phosphates are added, 0.02mol zinc nitrates, 90g glucose continues to stir 30min, obtains sol solutionses, takes 0.36mol calcium nitrate, adds in 2.4L deionized waters, stirs 30min with 400r/min, adds 360g polyvinyl alcohol P20000, continue to stir 30min, obtain dispersion liquid, sol solutionses are instilled in dispersion liquid with 10mL/min, and with 400r/min continues stirring until completion of dropping, adds ammoniacal liquor regulation pH to 12.5, centrifuges and must precipitate after standing 2h, will be heavy Shallow lake is placed in vacuum freezing drying oven, at -20 DEG C dry 24h, obtain freeze-dried powder, freeze-dried powder be placed in Muffle furnace, with 5 DEG C/ Min is heated to 650 DEG C, calcines 6h, is cooled to after room temperature and discharges, obtains nano-bioactive glass material.
By nano-bioactive glass material made from example 1~3 and commercially available nanometer level bioactive glass material（Contrast Example）Performance comparison is carried out, its result is as shown in table 1：
Table 1
Detection project Example 1 Example 2 Example 3 Comparative example
Aperture size（nm） 2~11 2~10 2~8 10~20
Specific surface area（m2/g） 860 950 1040 660
Apparent porosity（%） 87.5 89.6 91.4 86.7
Compression strength（MPa） 6.7 7.0 7.5 6.2
In summary, nano-bioactive glass material particle size uniformity produced by the present invention, and there is good dispersion, together When material have higher apparent porosity and specific surface area, be larger biomolecule absorption with separating there is provided splendid load Body, therefore with preferable bioactivity.

Claims (6)

1. a kind of nano-bioactive glass material, including silica, calcium oxide, phosphorus pentoxide, zinc oxide, its feature exist In the nano-bioactive glass material is caged tiny balloon, and its surface texture is rendered as the phosphorus ash with nano-pore level Rock layers.
2. a kind of nano-bioactive glass material as claimed in claim 1, it is characterised in that cage-like tiny balloon knot Structure is that, by being supported by kernel of template, colloidal sol prepared by tetraethyl orthosilicate, triethyl phosphate, zinc nitrate and calcium nitrate is bone Frame, dispersant is shell, and sintering is made.
3. a kind of nano-bioactive glass material as claimed in claim 1, it is characterised in that the template is poly- for shell One or both of sugar, gelatin, glucose, maltose, consumption are 10~30 times of zinc nitrate quality.
4. a kind of nano-bioactive glass material as claimed in claim 1, it is characterised in that the tetraethyl orthosilicate, phosphorus Triethylenetetraminehexaacetic acid ester, zinc nitrate, the mol ratio of calcium nitrate are (60~80)：（8~10）：（1~2）：(16~36).
5. a kind of nano-bioactive glass material as claimed in claim 1, it is characterised in that the dispersant is polyethylene One kind in alcohol P6000, polyvinyl alcohol P10000, polyvinyl alcohol P20000, consumption is 40~120 times of zinc nitrate quality.
6. a kind of preparation method of nano-bioactive glass material as described in any one of Claims 1 to 5, its feature exists In specific preparation process is：
S1. in molar ratio (60~80)：（8~10）：（1~2）：(16~36), take tetraethyl orthosilicate, triethyl phosphate, nitric acid Zinc, calcium nitrate；
S2. tetraethyl orthosilicate is added in ethanol solution and dissolved, and tricresyl phosphate second is added to 0.8~1.0 with nitre acid for adjusting pH Ester, zinc nitrate, template, continue to stir 20~30min, obtain sol solutionses；
S3. calcium nitrate is added in deionized water and be well mixed, add dispersant, stir to obtain dispersion liquid；
S4. sol solutionses are instilled in dispersion liquid and continues stirring until completion of dropping, added ammoniacal liquor and adjust pH to 12.0~12.5, it is quiet Put and centrifuge and must precipitate after 1~2h, 20~24h of freeze-drying at -30~-20 DEG C will be deposited in, freeze-dried powder is obtained；
S5. freeze-dried powder is placed in Muffle furnace, 600~650 DEG C is heated to 1~5 DEG C/min, calcined 4~6h, be cooled to room temperature After discharge, obtain nano-bioactive glass material.
CN201710510718.9A 2017-06-28 2017-06-28 A kind of nano-bioactive glass material and preparation method thereof Pending CN107261203A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108892145A (en) * 2018-07-17 2018-11-27 佛山今兰生物科技有限公司 A kind of SiO2The quantization production method of based bioactive tissue renovation material
CN110151784A (en) * 2019-04-19 2019-08-23 浙江科技学院 It is a kind of for the load iodine bioactivity glass of wound care and its application
CN111217523A (en) * 2020-01-15 2020-06-02 北京纯粹主义科技有限公司 Nano mesoporous bioactive glass and preparation method thereof
CN111544318A (en) * 2020-04-30 2020-08-18 四川三泰医药科技有限公司 Assembled jade activating material for maintaining beauty and keeping young, and assembling synthesis method and application thereof
CN113372131A (en) * 2021-04-26 2021-09-10 西安理工大学 Micro-nano pore channel structure tetragonal phase BaTiO3Preparation method of/HA hollow microspheres
CN116874976A (en) * 2023-07-20 2023-10-13 成都美益博雅材料科技有限公司 Bioglass-polyether-ether-ketone composite material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US20110021336A1 (en) * 2009-07-24 2011-01-27 Ivoclar Vivadent Ag Phosphosilicate Glass Ceramic
CN103239756A (en) * 2012-02-03 2013-08-14 佛山兰赛特生物科技有限公司 Biological active microsphere and preparation method thereof
CN104724922A (en) * 2014-12-22 2015-06-24 东莞市鸿元医药科技有限公司 Bioglass granular material and preparation technique thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110021336A1 (en) * 2009-07-24 2011-01-27 Ivoclar Vivadent Ag Phosphosilicate Glass Ceramic
CN103239756A (en) * 2012-02-03 2013-08-14 佛山兰赛特生物科技有限公司 Biological active microsphere and preparation method thereof
CN104724922A (en) * 2014-12-22 2015-06-24 东莞市鸿元医药科技有限公司 Bioglass granular material and preparation technique thereof

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108892145A (en) * 2018-07-17 2018-11-27 佛山今兰生物科技有限公司 A kind of SiO2The quantization production method of based bioactive tissue renovation material
CN110151784A (en) * 2019-04-19 2019-08-23 浙江科技学院 It is a kind of for the load iodine bioactivity glass of wound care and its application
CN111217523A (en) * 2020-01-15 2020-06-02 北京纯粹主义科技有限公司 Nano mesoporous bioactive glass and preparation method thereof
CN111217523B (en) * 2020-01-15 2022-08-12 北京纯粹主义科技有限公司 Nano mesoporous bioactive glass and preparation method thereof
CN111544318A (en) * 2020-04-30 2020-08-18 四川三泰医药科技有限公司 Assembled jade activating material for maintaining beauty and keeping young, and assembling synthesis method and application thereof
CN111544318B (en) * 2020-04-30 2021-09-21 四川三泰医药科技有限公司 Assembled jade activating material for maintaining beauty and keeping young, and assembling synthesis method and application thereof
CN113372131A (en) * 2021-04-26 2021-09-10 西安理工大学 Micro-nano pore channel structure tetragonal phase BaTiO3Preparation method of/HA hollow microspheres
CN116874976A (en) * 2023-07-20 2023-10-13 成都美益博雅材料科技有限公司 Bioglass-polyether-ether-ketone composite material and preparation method thereof
CN116874976B (en) * 2023-07-20 2024-04-26 成都美益博雅材料科技有限公司 Bioglass-polyether-ether-ketone composite material and preparation method thereof

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Application publication date: 20171020