CN112717198A - Degradable nano hydroxyapatite magnesium-based composite material and preparation method thereof - Google Patents

Degradable nano hydroxyapatite magnesium-based composite material and preparation method thereof Download PDF

Info

Publication number
CN112717198A
CN112717198A CN202011435874.1A CN202011435874A CN112717198A CN 112717198 A CN112717198 A CN 112717198A CN 202011435874 A CN202011435874 A CN 202011435874A CN 112717198 A CN112717198 A CN 112717198A
Authority
CN
China
Prior art keywords
powder
magnesium
composite material
nano hydroxyapatite
based composite
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.)
Pending
Application number
CN202011435874.1A
Other languages
Chinese (zh)
Inventor
袁玉春
李康
陈怡斐
王欢
刘欢
吴玉娜
宋丹
江静华
马爱斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hohai University HHU
Original Assignee
Hohai University HHU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hohai University HHU filed Critical Hohai University HHU
Priority to CN202011435874.1A priority Critical patent/CN112717198A/en
Publication of CN112717198A publication Critical patent/CN112717198A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0089—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with other, not previously mentioned inorganic compounds as the main non-metallic constituent, e.g. sulfides, glass
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412—Tissue-regenerating or healing or proliferative agents
    • 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
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Dermatology (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a degradable nano hydroxyapatite magnesium-based composite material and a preparation method thereof, and the degradable nano hydroxyapatite magnesium-based composite material comprises the following components in percentage by weight: zn4 wt.%, nano hydroxyapatite powder (HA)5 wt.% to 20 wt.%, and Mg in balance. According to the invention, 4 wt.% of alloy element Zn is added, so that the alloying degree, strength and corrosion resistance of Mg/Zn powder are improved; hydroxyapatite (HA) is selected as a reinforcement, and a powder metallurgy method is adopted to effectively fill the pores between Mg/Zn powder, so that the compactness and the toughness of the material are further improved. The HA can effectively adsorb hydrogen generated by corrosion of an alloy matrix, and can induce the formation of a protective layer to control the degradation rate of the alloy. The addition of HA also relieves the alkalization of magnesium matrix corrosion to surrounding matrix tissues, and improves the living environment of cells. The Mg-Zn/HA composite material with uniform and compact tissue, good alloying and better corrosion resistance is prepared by designing the component proportion of Mg/Zn and Mg-Zn/HA and the powder metallurgy process parameters, and HAs the value of being used as a biological bone implant material for clinical application.

Description

Degradable nano hydroxyapatite magnesium-based composite material and preparation method thereof
Technical Field
The invention relates to a degradable nano hydroxyapatite magnesium-based composite material and a preparation method thereof, belonging to the technical field of preparation and application of magnesium-based biomedical materials.
Background
Biomedical materials are high-tech materials applied to diagnosis, repair or enhancement of functions of human tissues and organs, are natural or artificial materials used for replacing and repairing living tissues, and have the function irreplaceable to medicines. Among them, hard tissue implant materials, including various repair and replacement materials for human bone, such as bones, teeth, joints, etc., have become a major field of biomaterials in the medical field due to their wide application and large demand. The hard tissue implant material in an ideal state has the characteristics of good biocompatibility, equivalent bending strength, lower stress shielding effect, smaller influence on bone blood circulation and the like.
Compared with any other metal or polymer implant material, the magnesium alloy as a biodegradable bone implant material has the advantages of combined application of biodegradability and biocompatibility, mechanical property, density and elastic modulus similar to those of cortical bone, similarity to those of human bone, and the like. Magnesium ions are obtained after corrosion and degradation of magnesium and magnesium alloy, are abundant cations in human bodies and cells, and are indispensable nutrient elements in human bodies, so that the magnesium-based material serving as a degradable bone implant material has a good medical safety foundation. However, the relatively poor corrosion resistance hinders the use of pure magnesium, and the low corrosion resistance results in a significant decrease in the mechanical properties of the implant with implantation time, and the body tissue cannot be cured in time. In addition, hydrogen evolution occurs during magnesium erosion, hydrogen gas actively accumulates around in vivo implants, and hydrogen gas and the subsequent formation of hydrogen bubbles can significantly impair other clinical applications of magnesium. Therefore, it is necessary to control the suitable corrosion resistance and mechanical properties of magnesium and its alloys to meet both requirements of implant biodegradation and new bone formation.
Mg-based composite materials (MMCs) prepared with natural human bone constituents such as Hydroxyapatite (HA) and beta-tricalcium phosphate (beta-TCP) as ceramic fiber reinforcement phases are being extensively studied as the most promising biomaterials due to their higher specific stiffness, strength and less sensitivity to galvanic corrosion10(PO4)6(OH)2HA) HAs a chemical composition and a crystal structure similar to those of human bone, HAs biological activity, and can form chemical bonds with bone tissues, and these characteristics make it promising for application in the field of bone implant materials. Therefore, when the Mg/HA composite material is manufactured, the HA serving as the second phase is considered to be a promising choice, the advantages of the magnesium alloy and the HA can be fully combined, the corrosion rate of the magnesium alloy material is controlled, the magnesium alloy material is prevented from being rapidly corroded and degraded in body fluid, the mechanical property requirement is met, and the growth and the repair of bone tissue cells are promoted.
Disclosure of Invention
The invention provides a degradable nano hydroxyapatite magnesium-based composite material and a preparation method thereof, aiming at the problem of over-high corrosion rate of the existing magnesium alloy bone implant material. The invention selects Hydroxyapatite (HA) which is a main mineral component in human bones as a reinforcement, adopts a powder metallurgy method, reasonably optimizes the component proportion of Mg/Zn and Mg-Zn/HA and the powder metallurgy process parameters, and prepares the Mg-Zn/HA composite material with uniform and compact tissue, good alloying and better corrosion resistance.
The invention specifically adopts the following technical scheme: the degradable biological nano hydroxyapatite magnesium-based composite material comprises the following components in percentage by weight: zn4 wt.%, HA5 wt.% to 20 wt.% and Mg in balance.
As a preferred embodiment, the Mg is high-purity magnesium powder, the purity is more than or equal to 99.9%, and the particle size is 50-70 μm.
In a preferred embodiment, the Zn is high-purity magnesium powder, the purity is greater than or equal to 99.9%, and the particle size is 5-20 μm.
As a preferred embodiment, the purity of the nano hydroxyapatite powder HA is analytically pure, and the particle size of the nano hydroxyapatite powder HA is not more than 60 nm.
The invention also provides a preparation method of the degradable biological nano hydroxyapatite magnesium-based composite material, which comprises the following steps:
step SS 1: the composite material is selected and weighed into powder according to the following weight percentage: 4 wt% of Zn, 5 wt% to 20 wt% of HA of nano hydroxyapatite powder, and the balance of Mg;
step SS 2: mixing the powder weighed in the step SS1 together, pouring the mixture into a powder mixer, mixing for a certain time, closing the powder mixer, taking out the raw material powder which is uniformly mixed according to the proportion, and bagging;
step SS 3: pouring the wrapped powder obtained in the step SS2 into a cold extrusion die, filling the die, applying pressure and keeping to obtain a sample; the sample is pressed and demoulded to obtain a cylindrical sample with the size of the diameter
Figure RE-GDA0002974530550000031
The thickness d is 1 cm;
step SS 4: and (4) sintering the cylindrical sample obtained in the step SS3 and preserving heat for a period of time to obtain the nano hydroxyapatite magnesium-based composite material.
As a preferred embodiment, the rotation speed of the powder mixer in the step SS2 is set to be 20r/min, and the mixing time is set to be 80 hours.
As a preferred embodiment, the cold pressure in step SS3 is 250-300MPa, and the holding time is 5-10 min.
As a preferred embodiment, the sintering temperature in the step SS4 is 430 ℃ and the holding time is 10 hours.
As a preferred embodiment, the weight ratio of Zn, the nano hydroxyapatite powder HA, and Mg is 4: 5: 91.
as a preferred embodiment, the weight ratio of Zn, the nano hydroxyapatite powder HA, and Mg is 4: 10: 86.
the invention achieves the following beneficial effects: the invention provides a degradable nano hydroxyapatite magnesium-based composite material and a preparation method thereof, and 4 wt.% of alloy element Zn is added, so that the alloying degree and strength of Mg/Zn powder are improved; meanwhile, the body fluid corrodes Zn on the surface of the material in the environment2+The corrosion of the material is inhibited to a certain extent by the release of the corrosion inhibitor, and the corrosion resistance of the material is improved. The nano-scale Hydroxyapatite (HA) powder is added to effectively fill the pores between the Mg/Zn powder, so that the compactness and the toughness of the material are further improved. The HA can effectively adsorb hydrogen generated by corrosion of an alloy matrix, and can induce the formation of a protective layer to control the degradation rate of the alloy. The addition of HA also relieves the alkalization of magnesium matrix corrosion to surrounding matrix tissues, and improves the living environment of cells. Along with the gradual degradation of the matrix magnesium alloy, the growth of cell reproduction is facilitated, new bone tissues with vitality and related functions are formed with the HA which cannot be degraded, the mechanical property is exerted, the mechanical property of the original bone tissues at different parts of an organism is adapted, and the stress shielding effect is relieved or avoided.
Drawings
FIG. 1 is an SEM microstructure of a Mg-4Zn/5HA composite of example 1 of the present invention;
FIG. 2 is an SEM microstructure of a Mg-4Zn/10HA composite of example 2 of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
(1) Preparing raw materials: high-purity magnesium powder (the purity is more than or equal to 99.9%) with the particle size of about 60 mu m, high-purity zinc powder (the purity is more than or equal to 99.9%) with the particle size of about 10 mu m and analytically pure nano hydroxyapatite powder (HA) with the particle size of less than or equal to 60nm are selected. According to the weight ratio of 91: 4: 5, weighing and preparing.
(2) Mixing powder: the weighed powder is mixed together and poured into the star-ball type powder mixer, because the magnesium powder has active chemical property, the powder mixer is easy to cause danger when rotating too fast, and is difficult to achieve the purpose of uniform mixing when rotating too slow, so the rotating speed of the powder mixer is set to be 20r/min, and the mixing time is set to be 80 hours. And (5) closing the powder mixer, taking out the raw material powder which is uniformly mixed according to the proportion, and bagging.
(3) Cold extrusion: pouring the wrapped powder into a cold extrusion die, installing the die, applying pressure and keeping the pressure, wherein the cold pressure is 250-300MPa, and the keeping time is 5-10 min. The sample is pressed and demoulded to obtain a cylindrical sample with the size of the diameter
Figure RE-GDA0002974530550000041
The thickness d is 1 cm.
(4) And (3) sintering: the melting point of magnesium is 649 ℃, the melting point of zinc is 419.5 ℃, the temperature of magnesium-zinc eutectic is 340 ℃, the sintering process of the powder metallurgy process is carried out at the temperature lower than the melting point of each component element, the final sintering temperature is 430 ℃ and the heat preservation time is 10 hours through experimental optimization of different sintering temperatures.
(5) The Mg-Zn/5HA composite material is prepared according to the procedures, the microstructure of the Mg-Zn/5HA composite material is shown in figure 1, the magnesium powder and the zinc powder have good alloying degree, an XRD test shows that an MgZn2 phase is formed, the HA powder is uniformly filled in alloy pores and does not react with the alloy powder after being sintered, the bioactivity of the HA powder is kept and is still uniformly distributed at a matrix crystal boundary, and the alloy hardness is 51 HRB. The results of electrochemical tests and full-soaking experiments in body fluid Hanks solution simulated at constant temperature of 37 ℃ show that the corrosion resistance of the Mg-Zn/5HA composite material added with 5 percent of HA powder is slightly inferior to that of the Mg-Zn composite sintered material only added with 4 percent of zinc powder, but is superior to pure magnesium.
Example 2
(1) Preparing raw materials: high-purity magnesium powder (the purity is more than or equal to 99.9%) with the particle size of about 60 mu m, high-purity zinc powder (the purity is more than or equal to 99.9%) with the particle size of about 10 mu m and analytically pure nano hydroxyapatite powder (HA) with the particle size of less than or equal to 60nm are selected. According to the weight ratio of 86: 4: 10 are weighed separately and prepared.
(2) The powder mixing, cold pressing and sintering were carried out in accordance with the procedures (2) to (4) in example 1.
(3) The Mg-Zn/10HA composite material is prepared according to the procedures, the microstructure of the Mg-Zn/10HA composite material is shown in figure 2, the magnesium powder and the zinc powder have good alloying degree, an XRD test shows that an MgZn2 phase is formed, the HA powder is uniformly filled in alloy pores and does not react with the alloy powder after being sintered, the bioactivity of the HA powder is kept and is still uniformly distributed at a matrix crystal boundary, and the alloy hardness is 56 HRB. The results of electrochemical tests and full-soaking experiments in body fluid Hanks solution simulated at constant temperature of 37 ℃ show that the corrosion resistance of the Mg-Zn/5HA composite material added with 10 percent of HA powder is obviously superior to that of the Mg-Zn composite sintered material containing 4 percent of zinc powder.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The degradable biological nano hydroxyapatite magnesium-based composite material is characterized by comprising the following components in percentage by weight: zn4 wt.%, HA5 wt.% to 20 wt.% and Mg in balance.
2. The degradable biological nano hydroxyapatite magnesium-based composite material according to claim 1, wherein Mg is high-purity magnesium powder, the purity is greater than or equal to 99.9%, and the particle size is 50-70 μm.
3. The degradable biological nano hydroxyapatite magnesium-based composite material according to claim 1, wherein Zn is high-purity magnesium powder, the purity is greater than or equal to 99.9%, and the particle size is 5-20 μm.
4. The degradable biological nano hydroxyapatite magnesium-based composite material according to claim 1, wherein the nano hydroxyapatite powder HA HAs an analytically pure purity and a particle size of not more than 60 nm.
5. The preparation method of the degradable biological nano hydroxyapatite magnesium-based composite material based on claim 1 is characterized by comprising the following steps:
step SS 1: the composite material is selected and weighed into powder according to the following weight percentage: zn4 wt%, HA5 wt-20 wt% of nano hydroxyapatite powder, and the balance of Mg;
step SS 2: mixing the powder weighed in the step SS1 together, pouring the mixture into a powder mixer, mixing for a certain time, closing the powder mixer, taking out the raw material powder which is uniformly mixed according to the proportion, and bagging;
step SS 3: pouring the wrapped powder obtained in the step SS2 into a cold extrusion die, filling the die, applying pressure and keeping to obtain a sample; the sample is pressed and demoulded to obtain a cylindrical sample with the size of the diameter
Figure FDA0002828156890000011
The thickness d is 1 cm;
step SS 4: and (4) sintering the cylindrical sample obtained in the step SS3 and preserving heat for a period of time to obtain the nano hydroxyapatite magnesium-based composite material.
6. The method for preparing the degradable biological nano hydroxyapatite magnesium-based composite material according to the claim 5, wherein the rotation speed of the powder mixer in the step SS2 is set to be 20r/min, and the mixing time is set to be 80 hours.
7. The preparation method of the degradable biological nano hydroxyapatite magnesium-based composite material according to claim 5, wherein the cold pressure in the step SS3 is 250-300MPa, and the retention time is 5-10 min.
8. The preparation method of the degradable biological nano hydroxyapatite magnesium-based composite material according to the claim 5, wherein the sintering temperature in the step SS4 is 430 ℃ and the heat preservation time is 10 hours.
9. The preparation method of the degradable biological nano hydroxyapatite magnesium-based composite material according to claim 5, wherein the weight ratio of Zn to nano hydroxyapatite powder HA to Mg is 4: 5: 91.
10. the preparation method of the degradable biological nano hydroxyapatite magnesium-based composite material according to claim 5, wherein the weight ratio of Zn to nano hydroxyapatite powder HA to Mg is 4: 10: 86.
CN202011435874.1A 2020-12-10 2020-12-10 Degradable nano hydroxyapatite magnesium-based composite material and preparation method thereof Pending CN112717198A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011435874.1A CN112717198A (en) 2020-12-10 2020-12-10 Degradable nano hydroxyapatite magnesium-based composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011435874.1A CN112717198A (en) 2020-12-10 2020-12-10 Degradable nano hydroxyapatite magnesium-based composite material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112717198A true CN112717198A (en) 2021-04-30

Family

ID=75598882

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011435874.1A Pending CN112717198A (en) 2020-12-10 2020-12-10 Degradable nano hydroxyapatite magnesium-based composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112717198A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114086011A (en) * 2021-10-25 2022-02-25 江苏理工学院 Preparation method of component gradient magnesium-based implant material with controllable degradation

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101185777A (en) * 2007-12-14 2008-05-28 天津理工大学 Biological degradable nano hydroxyapatite/magnesium alloy blood vessel inner bracket material
CN101347639A (en) * 2007-07-20 2009-01-21 中国科学院金属研究所 Medical magnesium alloy/calcium orthophosphate composite material
US20090068285A1 (en) * 2003-10-01 2009-03-12 Legeros Racquel Z Calcium phosphate-based materials containing zinc, magnesium, fluoride and carbonate
CN101411891A (en) * 2008-12-01 2009-04-22 天津理工大学 Degradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material
CN101524559A (en) * 2009-03-11 2009-09-09 重庆大学 Biodegradable nano hydroxylapatite-magnesium metallic matrix composite
CN107855528A (en) * 2017-10-31 2018-03-30 太原理工大学 A kind of preparation method of porous zinc magnesium alloy/hydroxyapatite composite material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090068285A1 (en) * 2003-10-01 2009-03-12 Legeros Racquel Z Calcium phosphate-based materials containing zinc, magnesium, fluoride and carbonate
CN101347639A (en) * 2007-07-20 2009-01-21 中国科学院金属研究所 Medical magnesium alloy/calcium orthophosphate composite material
CN101185777A (en) * 2007-12-14 2008-05-28 天津理工大学 Biological degradable nano hydroxyapatite/magnesium alloy blood vessel inner bracket material
CN101411891A (en) * 2008-12-01 2009-04-22 天津理工大学 Degradable nano calcium phosphorous compound reinforced magnesium-zinc alloy bone fracture internal fixation material
CN101524559A (en) * 2009-03-11 2009-09-09 重庆大学 Biodegradable nano hydroxylapatite-magnesium metallic matrix composite
CN107855528A (en) * 2017-10-31 2018-03-30 太原理工大学 A kind of preparation method of porous zinc magnesium alloy/hydroxyapatite composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
周世权等: "《机械制造工艺基础》", 31 January 2016 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114086011A (en) * 2021-10-25 2022-02-25 江苏理工学院 Preparation method of component gradient magnesium-based implant material with controllable degradation
CN114086011B (en) * 2021-10-25 2022-07-08 江苏理工学院 Preparation method of component gradient magnesium-based implant material with controllable degradation

Similar Documents

Publication Publication Date Title
Nasr Azadani et al. A review of current challenges and prospects of magnesium and its alloy for bone implant applications
EP2422821B2 (en) Biodegradable implant and method for manufacturing same
CN105143483B (en) Magnesium alloy with adjustable degradation rate
CN103357063B (en) The metallic composite of a kind of bootable osteogenesis and application thereof
Hong et al. Mechanical and biocorrosive properties of magnesium-aluminum alloy scaffold for biomedical applications
CN103599561B (en) A kind of preparation method of magnesium alloy/hydroxyapatite composite
Esen et al. Titanium–magnesium based composites: mechanical properties and in-vitro corrosion response in Ringer's solution
US20130150227A1 (en) Composite Bio-Ceramic Dental Implant and Fabricating Method Thereof
CN102258806B (en) Degradable magnesium-base biomedical material for implantation in orthopaedics, and preparation method thereof
CN104674093A (en) Medical high-toughness corrosion-resistant magnesium based composite material and preparation method thereof
Lai et al. Effect of pore structure regulation on the properties of porous TiNbZr shape memory alloys for biomedical application
WO2013158869A2 (en) Thixotropic processing of magnesium composites with a nanoparticles-haloed grain structure for biomedical implant applications
Wang et al. Progress in partially degradable titanium-magnesium composites used as biomedical implants
CN112717198A (en) Degradable nano hydroxyapatite magnesium-based composite material and preparation method thereof
Ibrahim et al. Partially biodegradable Ti-based composites for biomedical applications subjected to intense and cyclic loading
Sukhodub et al. The design criteria for biodegradable magnesium alloy implants
CN101698116A (en) Method for preparing biodegradable magnesium or magnesium alloy and tricalcium phosphate composite material
CN114411014B (en) In-situ synthesized ZnO reinforced composite material under GPa grade high pressure and preparation method thereof
de Castro et al. Mg-based composites for biomedical applications
Shrivas et al. Studies on Microstructure, Mechanical Properties, and Corrosion Behavior, of Partially Open-Cell Magnesium Foam through Powder Metallurgy Route
He et al. Characterizations on Mechanical Properties and In Vitro Bioactivity of Biomedical Ti–Nb–Zr–CPP Composites Fabricated by Spark Plasma Sintering
Carvalho et al. In-vitro evaluation of Zn-42mg-4ca alloy fabricated by powder metallurgy as a biodegradable biomaterial
CA2584896A1 (en) Silicon structure
Xue et al. Strengthening Mechanisms of Ti–Mg Composite for Biomaterials: A Review
Gonzaga et al. Production of biodegradable Mg-based alloys by mechanical alloying.

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20210430

RJ01 Rejection of invention patent application after publication