CN108126245A - A kind of orthopaedics titanium alloy implantation material and preparation method thereof - Google Patents

A kind of orthopaedics titanium alloy implantation material and preparation method thereof Download PDF

Info

Publication number
CN108126245A
CN108126245A CN201810118097.4A CN201810118097A CN108126245A CN 108126245 A CN108126245 A CN 108126245A CN 201810118097 A CN201810118097 A CN 201810118097A CN 108126245 A CN108126245 A CN 108126245A
Authority
CN
China
Prior art keywords
titanium alloy
matrix
orthopaedics
implantation material
solution treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810118097.4A
Other languages
Chinese (zh)
Other versions
CN108126245B (en
Inventor
毛佳
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.)
Yongchuan Hospital of Chongqing Medical University
Original Assignee
Yongchuan Hospital of Chongqing Medical University
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 Yongchuan Hospital of Chongqing Medical University filed Critical Yongchuan Hospital of Chongqing Medical University
Priority to CN201810118097.4A priority Critical patent/CN108126245B/en
Publication of CN108126245A publication Critical patent/CN108126245A/en
Application granted granted Critical
Publication of CN108126245B publication Critical patent/CN108126245B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/06Titanium or titanium alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/20Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602Type of release, e.g. controlled, sustained, slow

Landscapes

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

Abstract

The invention discloses a kind of orthopaedics titanium alloy implantation materials and preparation method thereof, it is related to medical material tech field, material is implanted into using the medical titanium alloy through solution treatment as matrix, the temperature of matrix solution treatment is 935 983 DEG C, the surface modification of matrix has chitosan, beta cyclodextrin is grafted on chitosan, being loaded on beta cyclodextrin has hydrophobic drug, the surface of matrix is formed with hydroxyapatite coating layer, and hydroxyapatite coating layer is the micro porous coating formed using differential arc oxidization technique.The present invention can be more nearly the hardness of titanium alloy and bone hardness, the injury after human body to bone is implanted into avoid titanium alloy, be conducive to the raising of biological fixation after improving in titanium alloy implantation human body, and growing into bone tissue, drug ingedient is slowly released in bone wound agglutination simultaneously, is made by the drug for maintaining effective concentration in medicine body system for a long time, promotion skeletonization and revascularization that can be lasting, accelerate bone wound healing, prevent the patient's condition such as wound inflammation.

Description

A kind of orthopaedics titanium alloy implantation material and preparation method thereof
Technical field
The present invention relates to medical material tech field more particularly to a kind of orthopaedics titanium alloy implantation material and its preparation sides Method.
Background technology
Medical pure titanium or titanium alloy is due to its relatively low elasticity modulus, high specific strength, excellent corrosion resistance and biofacies The features such as capacitive, since the 1940s, being gradually widely used in joint prosthesis, (hip, shoulder, ankle, elbow, wrist, refers to pass at knee Section etc.), bone wound product (intramedullary nail, nail, bone plate etc.), backbone correcting fixed system, tooth implant, denture fixing device, tooth it is orthopedic The implanted medical devices such as silk, heart valve prosthesis, intervention support.Wherein, the Ti-6Al-4V titaniums developed using aerospace applications as background Alloy since the 1970s be applied in the field of medicine, be up to the present still using most in orthopaedics Medical titanium alloy material.But the biologically inert that Ti-6Al-4V alloys itself are shown makes its conformability with implant site poor, Easily because the factors such as fine motion, infection, inflammatory stimulus cause implant to loosen, and then therapeutic effect can be influenced, may finally caused Graft failure, this, which has become, needs urgently solve major issue in medical titanium alloy implantation instrument clinical practice.
Ideal orthopaedics implant should have the biological function for promoting skeletonization, can be achieved with bone tissue and implantation material in this way Interface realization in terms of machinery with biology two is more perfect to be combined, and then accelerate bone uptake process, promotion bone remoulding and reparation.Together When, the formation of bone is inseparable with abundant blood supply.Blood can be provided for bone tissue abundant nutriment, transport growth because Son, biochemical signals etc., and the waste that can be generated is discharged by blood.Therefore, if implantation material itself has simultaneously The Biomedical function of skeletonization and angiogenesis (activity) will undoubtedly greatly promote the repair ability and speed of bone tissue, contracting Short bone is rebuild and repair time, the integrated intensity of enhancing implantation material and bone tissue.
Invention content
In view of this, the object of the present invention is to provide a kind of orthopaedics titanium alloy implantation material and preparation method thereof, close titanium The surface bioactive of gold is good, and has the function of to promote skeletonization and revascularization.
The present invention solves above-mentioned technical problem by following technological means:
A kind of orthopaedics titanium alloy is implanted into material, and implantation material is using the medical titanium alloy through solution treatment as matrix, matrix The temperature of solution treatment is 935-983 DEG C, and the surface modification of matrix has chitosan, and beta-cyclodextrin, β-ring are grafted on chitosan Load has hydrophobic drug on dextrin, and the surface of matrix is formed with hydroxyapatite coating layer, and hydroxyapatite coating layer is using micro- The micro porous coating that arc oxidation technology is formed, the thickness of micro porous coating is 25-50nm, and the porosity of micro porous coating is 35%-43%.
Further, hydrophobic drug is being total to for the one or several kinds in resveratrol, rutin, Kaempferol, vancomycin Mixed object.
In addition, the preparation method the present invention also provides a kind of orthopaedics titanium alloy implantation material, which is characterized in that including such as Lower step:
S1. one layer of Zinc oxide powder, the zinc oxide of formation are uniformly sprayed in titanium alloy substrate with static plastic spraying machine The thickness of powder bed is 0.03-0.10mm;Zinc oxide can be closed as " classical " metal oxide by a variety of methods Into low-dimensional or the micron and nanostructured of higher-dimension, such as nanobelt, nanometer rods, nanometer sheet, micron tower and hierarchical structure microballoon, And zinc oxide has the characteristics that cheap, stable structure and morphology controllable are strong;Zinc oxide powder is applied with static plastic spraying machine After material sprays to the surface of titanium alloy, under electrostatic interaction, Zinc oxide powder can uniformly be adsorbed in titanium alloy surface, and from group Dress forms nanostructured, and nanostructured can play the role of soft template in the forming process of titanium alloy crystal grain, and then guide The crystallographic direction of titanium alloy crystal grain and grain shape size;
S2. the titanium alloy substrate for being coated with oxide powder and zinc last layer is passed through into solid solution with the speed of service of 5.3-10.5m/min Treatment furnace, run time of the titanium alloy substrate in Solution Treatment Furnace are 60s-120s;
S3. by the titanium alloy substrate after coming out of the stove from Solution Treatment Furnace quickly with water-bath cooling to room temperature;
S4. the titanium alloy substrate of room temperature is will be cooled to by sodium hydroxide solution, thoroughly removes titanium alloy substrate surface Zinc oxide film;
S5. using surface self-organization technology and thick position surface chemical modification technology in titanium surface covalence graft chitosan;
S6. hydrophobic drug is included in the hydrophobic cavity of beta-cyclodextrin, then with epoxy chlorine using chemiadsorption Propane, will be on grafted by beta cyclodextrin to chitosan as crosslinking agent;
S7. medical titanium alloy matrix is surface-treated using pulse dc power is microarc oxidation equipment provided, makes its surface Form one layer of hydroxyapatite micro porous coating.
Further, Zinc oxide powder is nano bar-shape structure, and the length of nanometer rods is 100-300nm.Nanometer rods zinc oxide Powder induction titanium alloy surface forms nano bar-shape crystal grain, can improve polylactic acid-glycolic base apatite film layer in titanium alloy table The stability in face prevents polylactic acid-glycolic base apatite film layer from coming off.
Further, it is quickly cooled to room temperature after titanium alloy substrate is come out of the stove from Solution Treatment Furnace with alkaline bath, alkaline bath is carbonic acid The aqueous solution of hydrogen sodium and sodium nitrate.The titanium alloy substrate of high temperature makes the sodium bicarbonate fast decoupled in alkaline bath, generates a large amount of dioxies Change carbon, the volatilization of carbon dioxide can take away a large amount of heat in solution, and then accelerate the cooling of titanium alloy substrate;While alkaline bath, Salt made from earth containing a comparatively high percentage of sodium chloride good fluidity, temperature uniformly reach ± 2 DEG C, and temperature fluctuation is small, and thermal capacity is big, and thermal conductivity is high, and heat loss is small, and treated Titanium alloy substrate any surface finish, non-oxidation color.
Further, in the aqueous solution of sodium bicarbonate and sodium nitrate, sodium bicarbonate 40-60g, sodium nitrate 20 are contained in every liter of water ~50g.
Further, electrolyte used is surface-treated as calcium glycerophosphate and the deionized water mixed solution of calcium acetate, In, a concentration of 0.05mol/L of calcium glycerophosphate, a concentration of 0.25mol/L of calcium acetate.
Further, being surface-treated the microarc oxidation equipment provided parameter of pulse dc power used is:Constant voltage mode, voltage 350V, electrolysis time 8min, duty ratio 50%, frequency 50Hz.
Beneficial effects of the present invention:The present invention guides titanium alloy crystal grain using Nanometer-sized Rods ZnO particle as soft template The nano bar-shape crystal grain that direction is orderly, grain size is uniform is formed, the hardness and bone hardness for making titanium alloy are more nearly, to avoid Injury after titanium alloy implantation human body to bone, while titanium can be improved by the hydroxyapatite coating layer that differential arc oxidation is formed and closed The surface bioactive of gold, and the micropore that differential arc oxidation layer is formed is combined the hole to be formed formation size with stephanoporate titanium bead layer Continuous porous structure, and by porosity control in 35%-43%, it is solid that this is conducive to biology after improving in titanium alloy implantation human body It qualitatively improves and freshman bone tissue grows into, and by titanium alloy surface grafted chitosan, and be crosslinked on chitosan Grafting carry medicine beta-cyclodextrin, make titanium alloy implantation material slowly release drug ingedient in bone wound agglutination, make by The drug of effective concentration is maintained in medicine body system for a long time, promotion skeletonization and revascularization that can be lasting be accelerated bone wound healing, prevented Only there are the patient's condition such as wound inflammation.
Specific embodiment
By embodiment, the present invention is described in detail below:
Embodiment one
A kind of orthopaedics titanium alloy is implanted into material, and implantation material is using the medical titanium alloy through solution treatment as matrix, matrix The temperature of solution treatment is 935 DEG C, and the surface modification of matrix has chitosan, and beta-cyclodextrin, beta-cyclodextrin are grafted on chitosan Upper load has hydrophobic drug, and the surface of matrix is formed with hydroxyapatite coating layer, and hydroxyapatite coating layer is using differential of the arc oxygen The micro porous coating that change technology is formed, the thickness of micro porous coating is 25-50nm, and the porosity of micro porous coating is 35%-43%.It is made Preparation Method is as follows:
With static plastic spraying machine one layer of Zinc oxide powder, the Zinc oxide powder of formation are uniformly sprayed in titanium alloy substrate The thickness of layer is 0.03-0.10mm;By the titanium alloy substrate for being coated with oxide powder and zinc last layer with the operation speed of 5.3-10.5m/min For degree by Solution Treatment Furnace, run time of the titanium alloy substrate in Solution Treatment Furnace is 60s-120s;It will be from Solution Treatment Furnace In come out of the stove after titanium alloy substrate quickly with water-bath cooling to room temperature;The titanium alloy substrate that will be cooled to room temperature passes through sodium hydroxide Solution thoroughly removes the zinc oxide film on titanium alloy substrate surface;Changed using surface self-organization technology and thick position surface chemistry Property technology is in titanium surface covalence graft chitosan;Using chemiadsorption by hydrophobic drug include beta-cyclodextrin hydrophobicity It, will be on grafted by beta cyclodextrin to chitosan in cavity, then using epoxychloropropane as crosslinking agent;Using the pulse dc power differential of the arc Oxidation furnaces are surface-treated medical titanium alloy matrix, its surface is made to form one layer of hydroxyapatite micro porous coating, Wherein the microarc oxidation equipment provided parameter of pulse dc power be constant voltage mode, voltage 350V, electrolysis time 8min, duty ratio 50%, frequency 50Hz, electrolyte used are the deionized water mixed solution of calcium glycerophosphate and calcium acetate, wherein, glycerine phosphorus A concentration of 0.05mol/L of sour calcium, a concentration of 0.25mol/L of calcium acetate.
Embodiment two
A kind of orthopaedics titanium alloy is implanted into material, and implantation material is using the medical titanium alloy through solution treatment as matrix, matrix The temperature of solution treatment is 983 DEG C, and the surface modification of matrix has chitosan, and beta-cyclodextrin, beta-cyclodextrin are grafted on chitosan Upper load has hydrophobic drug, and the surface of matrix is formed with hydroxyapatite coating layer, and hydroxyapatite coating layer is using differential of the arc oxygen The micro porous coating that change technology is formed, the thickness of micro porous coating is 25-50nm, and the porosity of micro porous coating is 35%-43%.It is made Preparation Method is as follows:
With static plastic spraying machine one layer of Nanometer-sized Rods ZnO, the length of nanometer rods are uniformly sprayed in titanium alloy substrate For 100-300nm, the thickness of the oxide powder and zinc last layer of formation is 0.03-0.10mm;The titanium for being coated with oxide powder and zinc last layer is closed Auri body with the speed of service of 5.3-10.5m/min by Solution Treatment Furnace, operation of the titanium alloy substrate in Solution Treatment Furnace Time is 60s-120s;By the titanium alloy substrate after coming out of the stove from Solution Treatment Furnace quickly with water-bath cooling to room temperature;It will cooling The zinc oxide film for passing through sodium hydroxide solution, thoroughly removing titanium alloy substrate surface to the titanium alloy substrate of room temperature;Using table Face self-assembling technique and thick position surface chemical modification technology are in titanium surface covalence graft chitosan;It will be dredged using chemiadsorption Aqueous pharmaceutical is included in the hydrophobic cavity of beta-cyclodextrin, then using epoxychloropropane as crosslinking agent, by grafted by beta cyclodextrin Onto chitosan;Medical titanium alloy matrix is surface-treated using pulse dc power is microarc oxidation equipment provided, makes its surface One layer of hydroxyapatite micro porous coating is formed, the wherein microarc oxidation equipment provided parameter of pulse dc power is constant voltage mode, Voltage 350V, electrolysis time 8min, duty ratio 50%, frequency 50Hz, electrolyte used are calcium glycerophosphate and calcium acetate Deionized water mixed solution, wherein, a concentration of 0.05mol/L of calcium glycerophosphate, a concentration of 0.25mol/L of calcium acetate.
Embodiment three
A kind of orthopaedics titanium alloy is implanted into material, and implantation material is using the medical titanium alloy through solution treatment as matrix, matrix The temperature of solution treatment is 950 DEG C, and the surface modification of matrix has chitosan, and beta-cyclodextrin, beta-cyclodextrin are grafted on chitosan Upper load has hydrophobic drug, and the surface of matrix is formed with hydroxyapatite coating layer, and hydroxyapatite coating layer is using differential of the arc oxygen The micro porous coating that change technology is formed, the thickness of micro porous coating is 25-50nm, and the porosity of micro porous coating is 35%-43%.It is made Preparation Method is as follows:
With static plastic spraying machine one layer of Nanometer-sized Rods ZnO, the length of nanometer rods are uniformly sprayed in titanium alloy substrate For 100-300nm, the thickness of the oxide powder and zinc last layer of formation is 0.03-0.10mm;The titanium for being coated with oxide powder and zinc last layer is closed Auri body with the speed of service of 5.3-10.5m/min by Solution Treatment Furnace, operation of the titanium alloy substrate in Solution Treatment Furnace Time is 60s-120s;Titanium alloy substrate after coming out of the stove from Solution Treatment Furnace is quickly water-soluble with sodium bicarbonate and sodium nitrate Liquid is cooled to room temperature, wherein, in the aqueous solution of sodium bicarbonate and sodium nitrate, sodium bicarbonate 40-60g, nitric acid are contained in every liter of water 20~50g of sodium;The titanium alloy substrate of room temperature be will be cooled to by sodium hydroxide solution, thoroughly remove the oxygen on titanium alloy substrate surface Change zinc film layer;Using surface self-organization technology and thick position surface chemical modification technology in titanium surface covalence graft chitosan;It adopts Hydrophobic drug is included in the hydrophobic cavity of beta-cyclodextrin with chemiadsorption, then using epoxychloropropane as crosslinking Agent, will be on grafted by beta cyclodextrin to chitosan;Medical titanium alloy matrix is carried out using pulse dc power is microarc oxidation equipment provided Surface treatment, makes its surface form one layer of hydroxyapatite micro porous coating, and wherein pulse dc power is microarc oxidation equipment provided Parameter for constant voltage mode, voltage 350V, electrolysis time 8min, duty ratio 50%, frequency 50Hz, electrolyte used is glycerine The deionized water mixed solution of calcium phosphate and calcium acetate, wherein, a concentration of 0.05mol/L of calcium glycerophosphate, calcium acetate it is dense It spends for 0.25mol/L.
The present invention is more nearly the hardness of titanium alloy and bone hardness, is implanted into after human body to bone to avoid titanium alloy It injures, while the surface bioactive of titanium alloy can be improved by the hydroxyapatite coating layer that differential arc oxidation is formed, and micro- The micropore that arc oxide layer is formed is combined the hole to be formed with stephanoporate titanium bead layer and forms the continuous porous structure of size, this is conducive to The raising of biological fixation and growing into bone tissue after improving in titanium alloy implantation human body, and by titanium alloy surface Grafted chitosan, and cross-linked graft carries the beta-cyclodextrin of medicine on chitosan, and titanium alloy implantation material is made to heal in bone wound Drug ingedient is slowly released in journey, is made by the drug for maintaining effective concentration in medicine body system for a long time, promotion skeletonization that can be lasting With revascularization, accelerate bone wound healing, prevent the patient's condition such as wound inflammation.
The above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to preferred embodiment to this hair It is bright to be described in detail, it will be understood by those of ordinary skill in the art that, it can modify to technical scheme of the present invention Or equivalent replacement, without departing from the objective and range of technical solution of the present invention, the claim in the present invention should all be covered In range.The present invention be not described in detail technology, shape, construction part be known technology.

Claims (8)

1. a kind of orthopaedics titanium alloy is implanted into material, which is characterized in that the implantation material is with the medical titanium alloy through solution treatment As matrix, the temperature of described matrix solution treatment is 935-983 DEG C, and the surface modification of described matrix has chitosan, chitosan On be grafted with beta-cyclodextrin, on beta-cyclodextrin load have hydrophobic drug, the surface of described matrix is formed with hydroxyapatite coat Layer, the hydroxyapatite coating layer are the micro porous coating formed using differential arc oxidization technique, and the thickness of the micro porous coating is 25- 50nm, the porosity of the micro porous coating is 35%-43%.
2. a kind of orthopaedics titanium alloy implantation material according to claim 1, which is characterized in that the hydrophobic drug is white One or several kinds of blends in veratryl alcohol, rutin, Kaempferol, vancomycin.
It is 3. a kind of such as the preparation method of the implantation material of orthopaedics titanium alloy according to claim 1, which is characterized in that including as follows Step:
S1. one layer of Zinc oxide powder, the Zinc oxide powder of formation are uniformly sprayed in titanium alloy substrate with static plastic spraying machine The thickness of layer is 0.03-0.10mm;
S2. the titanium alloy substrate for being coated with oxide powder and zinc last layer is passed through into solution treatment with the speed of service of 5.3-10.5m/min Stove, run time of the titanium alloy substrate in Solution Treatment Furnace are 60s-120s;
S3. by the titanium alloy substrate after coming out of the stove from Solution Treatment Furnace quickly with water-bath cooling to room temperature;
S4. the titanium alloy substrate of room temperature is will be cooled to by sodium hydroxide solution, thoroughly removes the oxidation on titanium alloy substrate surface Zinc film layer;
S5. using surface self-organization technology and thick position surface chemical modification technology in titanium surface covalence graft chitosan;
S6. hydrophobic drug is included in the hydrophobic cavity of beta-cyclodextrin, then with epoxychloropropane using chemiadsorption It, will be on grafted by beta cyclodextrin to chitosan as crosslinking agent;
S7. medical titanium alloy matrix is surface-treated using pulse dc power is microarc oxidation equipment provided, forms its surface One layer of hydroxyapatite micro porous coating.
A kind of 4. preparation method of orthopaedics titanium alloy implantation material according to claim 3, which is characterized in that the oxidation Zinc powder is nano bar-shape structure, and the length of the nanometer rods is 100-300nm.
5. the preparation method of a kind of orthopaedics titanium alloy implantation material according to claim 4, which is characterized in that the titanium closes Auri body is quickly cooled to room temperature after coming out of the stove from Solution Treatment Furnace with alkaline bath, and the alkaline bath is sodium bicarbonate and the water of sodium nitrate Solution.
A kind of 6. preparation method of orthopaedics titanium alloy implantation material according to claim 5, which is characterized in that the carbonic acid In the aqueous solution of hydrogen sodium and sodium nitrate, sodium bicarbonate 40-60g, 20~50g of sodium nitrate are contained in every liter of water.
A kind of 7. preparation method of orthopaedics titanium alloy implantation material according to claim 3, which is characterized in that the surface Processing electrolyte used is the deionized water mixed solution of calcium glycerophosphate and calcium acetate, wherein, the concentration of calcium glycerophosphate For 0.05mol/L, a concentration of 0.25mol/L of calcium acetate.
A kind of 8. preparation method of orthopaedics titanium alloy implantation material according to claim 3, which is characterized in that the surface Handling the microarc oxidation equipment provided parameter of pulse dc power used is:Constant voltage mode, voltage 350V, electrolysis time 8min are accounted for Empty ratio 50%, frequency 50Hz.
CN201810118097.4A 2018-02-06 2018-02-06 Titanium alloy implant material for orthopedics department and preparation method thereof Expired - Fee Related CN108126245B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810118097.4A CN108126245B (en) 2018-02-06 2018-02-06 Titanium alloy implant material for orthopedics department and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810118097.4A CN108126245B (en) 2018-02-06 2018-02-06 Titanium alloy implant material for orthopedics department and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108126245A true CN108126245A (en) 2018-06-08
CN108126245B CN108126245B (en) 2020-12-18

Family

ID=62430392

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810118097.4A Expired - Fee Related CN108126245B (en) 2018-02-06 2018-02-06 Titanium alloy implant material for orthopedics department and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108126245B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110541099A (en) * 2019-07-02 2019-12-06 山东大学 Magnesium alloy surface degradable composite film layer and preparation method and application thereof
CN112842582A (en) * 2020-12-31 2021-05-28 深圳新致美精密齿研有限公司 Surface treatment method for denture implant

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268711A (en) * 2011-06-22 2011-12-07 沈阳理工大学 Method for preparing biological composite coating on surface of magnesium-based material
CN102863553A (en) * 2012-04-01 2013-01-09 金陵科技学院 Chitosan derivative with cross-linking polymerization and containing drug ligand
CN105596043A (en) * 2016-01-25 2016-05-25 北京天助畅运医疗技术股份有限公司 Titanium nail and soft tissue fixation device containing titanium nail

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268711A (en) * 2011-06-22 2011-12-07 沈阳理工大学 Method for preparing biological composite coating on surface of magnesium-based material
CN102863553A (en) * 2012-04-01 2013-01-09 金陵科技学院 Chitosan derivative with cross-linking polymerization and containing drug ligand
CN105596043A (en) * 2016-01-25 2016-05-25 北京天助畅运医疗技术股份有限公司 Titanium nail and soft tissue fixation device containing titanium nail

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MADHAV PRASAD NEUPANE等: ""Surface characterization and corrosion behavior of micro-arc oxidized Ti surface modified with hydrothermal treatment and chitosan coating"", 《THIN SOLID FILMS》 *
王国卿等: "微弧氧化法制备钛基HA/CS涂层及其生物学特性", 《稀有金属材料与工程》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110541099A (en) * 2019-07-02 2019-12-06 山东大学 Magnesium alloy surface degradable composite film layer and preparation method and application thereof
CN110541099B (en) * 2019-07-02 2021-04-06 山东大学 Magnesium alloy surface degradable composite film layer and preparation method and application thereof
CN112842582A (en) * 2020-12-31 2021-05-28 深圳新致美精密齿研有限公司 Surface treatment method for denture implant
CN112842582B (en) * 2020-12-31 2022-04-29 深圳新致美精密齿研有限公司 Surface treatment method for denture implant

Also Published As

Publication number Publication date
CN108126245B (en) 2020-12-18

Similar Documents

Publication Publication Date Title
Sarraf et al. A state-of-the-art review of the fabrication and characteristics of titanium and its alloys for biomedical applications
Wilson Metallic biomaterials: State of the art and new challenges
Zhu et al. Advances in implant surface modifications to improve osseointegration
Jiang et al. Advanced surface engineering of titanium materials for biomedical applications: From static modification to dynamic responsive regulation
US8545625B2 (en) Materials for dental and biomedical application
Alipal et al. An updated review on surface functionalisation of titanium and its alloys for implants applications
Myakinin et al. In vitro evaluation of electrochemically bioactivated Ti6Al4V 3D porous scaffolds
JP6289708B2 (en) Biological implant
Wang et al. Porous construction and surface modification of titanium-based materials for osteogenesis: A review
CN103463685B (en) Preparation method of degradable porous structural tissue engineering bracket with high strength
Wei et al. An overview of surface modification, a way toward fabrication of nascent biomedical Ti–6Al–4V alloys
CN111218706A (en) Preparation method of antibacterial three-dimensional porous bone implant material
Aufa et al. Surface enhancement of Ti–6Al–4V fabricated by selective laser melting on bone-like apatite formation
Fathyunes Effect of ultrasonic waves on the electrochemical deposition of calcium phosphate/nano-sized silica composite coating
CN108126245A (en) A kind of orthopaedics titanium alloy implantation material and preparation method thereof
Huang et al. Biomechanical and biochemical compatibility in innovative biomaterials
Zhou et al. Novel coatings for the continuous repair of human bone defects
Wang et al. Enhanced biocompatibility and osseointegration of calcium titanate coating on titanium screws in rabbit femur
Heydariyan et al. A comprehensive review: Different approaches for encountering of bacterial infection of dental implants and improving their properties
Lewis Nanostructured hydroxyapatite coating on bioalloy substrates: current status and future directions
KR101822255B1 (en) A method for preparation of a metallic implant comprising biocompatable fluoride ceramic coating
Shah et al. Surface Modification on Titanium Alloy for Biomedical Application
EP2300642B1 (en) Electrochemical immersion method in an aqueous electrolyte for producing a biologically degradation stable surface layer on base bodies made of titanium or titanium based alloys
Maher et al. Nanoengineered titania nanotube arrays for localized drug delivery and enhanced osseointegration
WO2019076603A1 (en) Method for biomimetic growth of calcium phosphates ceramics on metal implants

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
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20201218

Termination date: 20220206