CN113797396B - Preparation method of porous zinc biological composite coating for degradable bone scaffold - Google Patents

Preparation method of porous zinc biological composite coating for degradable bone scaffold Download PDF

Info

Publication number
CN113797396B
CN113797396B CN202111170985.9A CN202111170985A CN113797396B CN 113797396 B CN113797396 B CN 113797396B CN 202111170985 A CN202111170985 A CN 202111170985A CN 113797396 B CN113797396 B CN 113797396B
Authority
CN
China
Prior art keywords
sleeve
template material
zinc
gear
groove
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111170985.9A
Other languages
Chinese (zh)
Other versions
CN113797396A (en
Inventor
麻健丰
林继兴
童先
朱莉
黄盛斌
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.)
SCHOOL & HOSPITAL OF STOMATOLOGY WENZHOU MEDICAL UNIVERSITY
Original Assignee
SCHOOL & HOSPITAL OF STOMATOLOGY WENZHOU 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 SCHOOL & HOSPITAL OF STOMATOLOGY WENZHOU MEDICAL UNIVERSITY filed Critical SCHOOL & HOSPITAL OF STOMATOLOGY WENZHOU MEDICAL UNIVERSITY
Priority to CN202111170985.9A priority Critical patent/CN113797396B/en
Publication of CN113797396A publication Critical patent/CN113797396A/en
Application granted granted Critical
Publication of CN113797396B publication Critical patent/CN113797396B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • A61L27/50—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
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—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
    • A61L27/50—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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • 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
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic 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
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606—Coatings
    • A61L2300/608—Coatings having two or more layers

Landscapes

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

Abstract

The invention relates to a preparation method of a porous zinc biological composite coating for a degradable bone scaffold, which comprises the following steps of a, preparing a template material; b. degreasing the template material, adopting hydrochloric acid to etch the surface of the template material, and finally washing and drying in a vacuum box; c. taking out the dried template material, taking the template material as an anode and the stainless steel sheet as a cathode, and carrying out anodic oxidation in a zinc liquid tank by a direct current power supply to prepare a zinc oxide layer; d. c, immersing the template material prepared in the step c into the phosphate bath under the action of ultrasonic waves to prepare a zinc phosphate layer; e. taking out the template material, respectively cleaning the template material in alcohol solution and deionized water, and drying the template material in a vacuum drying oven; f. the sample was taken out. The invention has the beneficial effects that: the mixed coating of zinc oxide and zinc phosphate has good bonding strength with a substrate, compact structure, and excellent cell compatibility and antibacterial property on the basis of good mechanical property and proper biodegradability.

Description

Preparation method of porous zinc biological composite coating for degradable bone scaffold
Technical Field
The invention relates to the technical field of biomedical metals, in particular to a preparation method of a porous zinc biological composite coating for a degradable bone scaffold.
Background
In the field of medical devices, porous degradable biomaterials with appropriate scaffold structure are able to accommodate tissue formation and promote diffusion and transport of nutrients and metabolites from the cell/scaffold structure. Due to the biodegradability, biocompatibility and processability of such materials, degradable biopolymers are widely used as scaffold materials. However, due to the limited mechanical strength of degradable biopolymers, most porous polymer structures are relatively weak and may suddenly lose mechanical integrity during in vivo service. Therefore, the degradable biopolymer cannot achieve sufficient strength required for the bone scaffold, i.e., the application of the bone implant. In order to enhance the strength and ductility of porous degradable biological materials, degradable metals including magnesium, zinc, iron and their alloys have been proposed as new bone scaffold materials in recent years. Porous zinc has been shown to play an important role in cell growth and proliferation at present due to the higher surface contact area and greater interconnectivity of cell expansion within pores, and its degradation rate can be varied by adjusting pore size and porosity and can match the mechanical performance requirements of different bone tissue applications, meeting the requirements of mechanical support and degradation rate during tissue healing. However, pure zinc has a low cell viability when in direct contact with cells due to an excessively fast degradation rate. Therefore, improving the bioactivity of degradable zinc alloys remains a key to the development of suitable clinical medical implants. Furthermore, another challenge associated with medical implants is the risk of infection from microbial growth on the implant, and the development of bacterial biofilms and compromised immunity at the implant/tissue interface may lead to persistent infection, particularly on high surface area implants such as stents, bone pegs, and acetabular cups.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a porous zinc biological composite coating for a degradable bone scaffold, so as to solve the problems.
The technical scheme of the invention is realized as follows: a preparation method of a porous zinc biological composite coating for a degradable bone scaffold comprises the following operation steps:
a. preparing a template material A by an electrodeposition method, a seepage method and an additive manufacturing method;
b. the template material A is respectively placed in acetone and alcohol solution for ultrasonic oscillation for degreasing, 1 to 3mol/L hydrochloric acid (HCl) is adopted for etching the surface of the template material A for 15 to 30min, and finally deionized water is adopted for washing and drying in a vacuum box;
c. taking out the dried template material A, taking the template material A as an anode and a stainless steel sheet as a cathode, and placing the template material A in a zinc liquid tank for anodic oxidation for 1-60min to form a zinc oxide layer, wherein the distance between the two electrodes is 2-10mm;
d. c, immersing the template material A prepared in the step c into phosphate bath liquid at the temperature of 20-80 ℃ under the action of ultrasonic waves, and carrying out chemical deposition for 2-60min to prepare a zinc phosphate layer;
e. after chemical deposition, taking out the template material A, respectively cleaning in an alcohol solution and deionized water, and finally drying in a vacuum drying oven;
f. and taking out the sample to obtain a finished product.
By adopting the technical scheme, the invention can anodically oxidize a zinc oxide antibacterial coating on a foam metal A template (template material A) and chemically deposit a zinc phosphate active coating on the surface of the zinc oxide, successfully prepares the foam metal with the composite coating which has the functions of promoting the proliferation of osteocytes and resisting bacteria, has good bonding strength with a substrate and compact structure, has better mechanical property and proper biodegradability and gives consideration to excellent cell compatibility and antibacterial property, has more corrected corrosion potential and lower corrosion current density and corrosion rate compared with a pure zinc template without the protection of a coating, can be used for a novel porous zinc biological material of a bone implant, and has good use effect.
The invention is further configured to: the template material A includes but is not limited to porous pure zinc, and can also be porous alloys such as zinc-magnesium, zinc-copper, zinc-manganese, zinc-carbon nanotubes and the like.
By adopting the technical scheme, the template material is ensured to have higher mechanical properties including strength, elongation, hardness and the like, and the preparation of the composite coating is facilitated.
The invention is further configured to: in the step c, the anodic oxidation process is that the anode is oxidized in a zinc liquid tank containing the anodic oxidation plating solution by adopting a direct current power supply with the voltage of 5.0 to 10.0V at the temperature of 30 to 60 ℃.
By adopting the technical scheme, the generated zinc oxide layer is tightly combined with the template material A, and the combination strength of the template material A and the zinc oxide layer is improved.
The invention is further configured to: in the step c, the anodic oxidation plating solution contains 0.1 to 2g/L of sodium carbonate (Na) 2 CO 3 ) And 0.1 to 1g/L of sodium bicarbonate (NaHCO) 3 ) And adjusting the pH value to 8 to 10 by using a dilute sodium hydroxide solution (NaOH).
By adopting the technical scheme, the zinc oxide prepared by the proportion has good bonding strength with a matrix, has a dense structure, can effectively control bacterial adhesion and prevent biofilm formation, and meets various performances of biomedical materials.
The invention is further configured to: in the step d, the phosphate bath contains 2 to 30g/L of phosphoric acid (H) 3 PO 4 ) 5 to 40g/L of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 •6H 2 O) and 0.5 to 5g/L of Graphene Oxide (GO) or Carbon Nanotubes (CNTs), and adjusting the pH value to 1.5 to 3.5 by using a dilute hydrochloric acid solution.
By adopting the technical scheme, the zinc phosphate layer prepared by the proportion has excellent corrosion resistance and meets various performances of biomedical materials.
The invention is further configured to: and b, placing the template material A washed by the deionized water in a vacuum drying oven for swinging, heating and drying.
By adopting the technical scheme, the residual deionized water residual liquid on the template material A can be quickly and completely removed, and the influence of the local residual of the deionized water on the preparation of the zinc oxide layer in the step c is prevented.
The invention is further configured to: and e, placing the template material A washed by the alcohol solution and the deionized water in a vacuum drying oven for swinging, heating and drying.
By adopting the technical scheme, the residual liquid after the alcohol solution and the deionized water on the template material A composite coating are cleaned can be quickly and completely removed, and the using effect is good.
The invention is further configured to: the vacuum drying oven includes:
a box body;
the heating device is positioned on the side wall of the box body;
an air extraction device;
a first base connected to the lower end of the box body
The stepping motor is positioned in the first base, an output shaft of the stepping motor penetrates through the middle part in the box body, and the output shaft of the stepping motor is in rotary sealing connection with the box body;
the heating cavity is positioned in the box body;
the placing table is positioned in the box body, and a first gear is connected with the lower end of the placing table through a key;
the second base is connected to the bottom of the inner side of the box body, a circular groove is formed in the upper end of the second base, and a tooth groove meshed with the first gear is formed in the circular groove along the circumferential direction of the groove wall;
the lifting mechanism is connected to one side of the placing table;
one end of the supporting rod is connected to an output shaft of the stepping motor, and the other end of the supporting rod is connected to the lifting mechanism;
the first annular guide rail is arranged at the bottom of the circular groove;
the second annular guide rail is arranged at the bottom of the circular groove and is arranged at intervals with the first annular guide rail;
the step motor drives the placing table to move circumferentially in the box body, the first gear drives the placing table to rotate, the lifting mechanism drives the placing table to swing up and down circularly, the lower end of the first gear is fixedly connected with a first sliding block matched with the first annular guide rail, and the lower end of the lifting mechanism is fixedly connected with a second sliding block matched with the second annular guide rail.
Through adopting above-mentioned technical scheme, the setting of guide rail and slider plays the effect of auxiliary stay, place the bench and place template material A after, step motor starts, it places platform circumferential direction to drive through the bracing piece, because place the first gear and the tooth's socket intermeshing of platform lower extreme, first gear revolve this moment, place the platform rotation, make the process heating device that places template material A on the platform rotatory limit position in by, make template material can the omnidirectional quick drying, through avoiding local overheat, it makes and places the platform and do the vertical circulation swing to drive elevating system through first gear simultaneously, help template material A attached to the surface deionized water and the quick vibrations of alcohol residual liquid to throw away, drying effect has been improved, prevent that template material A from drying the preparation that influences composite coating not completely.
The invention is further configured to: the lifting mechanism comprises:
a second gear meshed with the first gear;
the first sleeve is positioned on the upper end face of the second gear, and a transmission cavity is formed in the first sleeve;
one end of the first transmission shaft is in keyed connection with the middle part of the upper end of the second gear, and the other end of the first transmission shaft penetrates through the lower end of the first sleeve and extends into the transmission cavity and is in keyed connection with a first bevel gear;
the second transmission shaft is rotatably connected to one side outside the upper end of the first sleeve, one end of the second transmission shaft extends into the transmission cavity and is in key connection with a second bevel gear;
the rotating disc is fixedly arranged at the other end, away from the first sleeve, of the second transmission shaft;
the rotating frame is connected to one end, away from the second transmission shaft, of the rotating disc through a connecting rod;
the third ring groove is formed in the lower end of the first sleeve;
the limiting plate is positioned at the left lower part of the rotating frame and is parallel to the rotary table, the limiting plate is fixedly connected with the first sleeve through a connecting plate, and the limiting plate is provided with a long groove arranged along the height direction of the limiting plate;
the clamping block is connected in the strip groove in a sliding manner;
wherein, be equipped with a plurality of first balls between third annular and the second gear, first bevel gear and the meshing of second bevel gear, the rotating turret is the isosceles triangle pipe support, the central axis of rotating turret is located the below of carousel center pin extension line and the mutual interval sets up, step motor passes through gear drive and drives the carousel rotation, one side edge that the carousel center pin extension line was kept away from to the rotating turret has seted up first opening, the rotating turret has kept away from first open-ended one side middle part and has seted up the second opening, when the carousel did not rotate, the second opening is located the top of carousel center pin extension line, fixture block one end extends to the rotating turret inboardly, other end fixed connection is on placing the platform.
By adopting the technical scheme, when the first gear rotates to drive the second gear to synchronously rotate, the second gear drives the first bevel gear to rotate through the first transmission shaft, the first bevel gear rotates to drive the second bevel gear to rotate, the second bevel gear rotates to drive the second transmission shaft to drive the turntable, the turntable drives the rotating frame to eccentrically rotate, when the rotating frame rotates, the clamping block is driven to enable the third sleeve to be upwards pulled and lifted, when the clamping block moves to the second opening, the clamping block slides out of the rotating frame, at the moment, the third sleeve downwards and rapidly moves under the action of gravity, when the third sleeve stops, deionized water or alcohol residual liquid on the template material A is thrown out due to inertia, when the clamping block slides out of the rotating frame, the rotating frame continuously rotates, then the first opening rotates to one side of the clamping block, and the clamping block enters the rotating frame again through the first opening to continuously circulate.
The invention is further configured to: the placing table comprises:
the second sleeve is connected to the upper end of the first gear;
the third sleeve is connected to the upper end of the second sleeve;
the first slot is positioned in the middle of the upper end of the second sleeve;
the second slot is positioned in the middle of the lower end of the third sleeve;
the fixed end of the elastic telescopic rod is fixedly arranged at the bottom of the first slot, and the movable end of the elastic telescopic rod is fixedly arranged at the bottom of the second slot;
the reset spring is sleeved outside the elastic telescopic rod, the upper end of the reset spring is fixedly connected to the bottom of the second slot, and the lower end of the reset spring is fixedly connected to the bottom of the first slot;
the fixing table is positioned above the third sleeve, a through hole is formed in the middle of the fixing table, an elastic net layer is embedded in the elastic through hole, and a clamping arm for clamping the template material A is hinged to the edge of the upper end of the fixing table;
the supporting column is fixedly connected between the fixed table and the third sleeve;
the first ring groove is formed in the outer side of the lower end of the third sleeve;
the clamping ring is clamped in the first annular groove, and a plurality of second balls are arranged between the clamping ring and the bottom of the first annular groove;
one end of the clamping block, which is far away from the rotary disc, is welded with the outer side of the clamping ring, and the rotating frame rotates to drive the clamping block to enable the third sleeve to do vertical linear circulating motion.
Through adopting above-mentioned technical scheme, through setting up elasticity telescopic link and reset spring, exert elastic force when the third sleeve falls, make the fall that the third sleeve can be faster, improve the separation effect of deionized water or alcohol residual liquid and template material A, still possess buffering shock attenuation effect through elasticity telescopic link and reset spring, make the third sleeve can not collide the second sleeve, excellent in use effect.
The invention is further configured to: the placing table further comprises:
two third slots are arranged, and the two third slots are oppositely arranged on two sides of the edge of the upper end of the second sleeve;
the positioning column is integrally formed at the bottom of the third slot;
the magnetic blocks are arranged in the positioning columns at intervals along the height direction of the positioning columns;
the two positioning rods are fixedly connected to the lower end of the third sleeve, and a fifth slot matched with the positioning column is formed in the lower end of each positioning rod;
the second annular groove is formed in the side wall of the third slot along the height direction of the third slot, a plurality of first conductors arranged at intervals are embedded in the groove bottoms on two sides of the second annular groove, and each first conductor and each magnetic block are arranged correspondingly;
two second conductors are arranged, the two second conductors are respectively welded with the two sides outside the lower end of the positioning rod, and the outer sides of the second conductors are abutted to the bottom of the second annular groove;
the electromagnet is embedded in the positioning rod;
the electromagnet is annular, the upper end of the electromagnet and the upper ends of the second conductors are located on the same horizontal plane, the water surface height of the lower end face of each first conductor is equal to the horizontal height of the upper end face of the adjacent magnetic block, wires for connecting the two second conductors are arranged on two sides of the electromagnet, the groove wall of the fifth slot and the outer side wall of the positioning column are arranged at intervals, and two air holes communicated with the two third slots are formed in two sides of the lower end of the second sleeve.
Through adopting above-mentioned technical scheme, when the third sleeve passes through fixture block and rotating turret and moves to the highest point, the level of terminal surface equals with the level of the magnetic path up end of the top in the locating lever under the electro-magnet, first conductor circular telegram thereupon, in-process when the third sleeve drives the locating lever whereabouts, the second conductor contacts with first conductor, make and form closed loop between first conductor, second conductor and the electro-magnet, the electro-magnet attracts mutually with the magnetic path opposite polarity of its below, a decurrent acceleration has been applyed to the locating column, make the speed of third sleeve whereabouts faster, further improve the separation effect of deionized water or alcohol residual liquid and template material A.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD pattern of a sample of a foam pure zinc template and composite coating according to an embodiment of the present invention;
FIG. 2 is an SEM image of the porous structure of a pure zinc template and a composite coating sample according to an embodiment of the invention;
FIG. 3 is a graph of the compressive stress strain of a sample of a pure zinc template and composite coating in accordance with an embodiment of the present invention;
FIG. 4 is a graph showing the potentiodynamic polarization of samples of pure zinc template and composite coating in Hank's solution according to an embodiment of the present invention;
FIG. 5 is a graph showing the degradation rate of a sample of a pure zinc template and a composite coating after being soaked in Hank's solution for 3 months according to an embodiment of the present invention;
FIG. 6 is a graph showing the cell viability of L929 cells cultured in pure zinc template and composite coating samples leach solutions of different concentrations at 72 h in accordance with the present invention;
FIG. 7 is a diameter chart of the inhibition zone of 24h for the co-culture of a pure zinc template and composite coating sample with Staphylococcus aureus according to an embodiment of the present invention;
FIG. 8 is a schematic view of a vacuum drying oven according to an embodiment of the present invention;
FIG. 9 is an enlarged view of a portion of a vacuum drying oven A according to an embodiment of the present invention;
FIG. 10 is a schematic view of a structure of a turret and a turntable according to an embodiment of the present invention;
fig. 11 is a partially enlarged view of a vacuum drying oven B according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1 to 7, example 1, the present invention discloses a method for preparing a porous zinc biocomposite coating for degradable bone scaffold, which uses electrodeposited foam pure zinc as a template, and ultrasonic vibration in acetone and alcohol solution respectively for degreasing treatment, then etching with 2mol/L hydrochloric acid for 20 minutes to remove surface oxides and burrs, and finally washing with deionized water and drying in a vacuum drying oven. A zinc oxide layer was prepared by anodizing in a plating bath using a DC power supply at a temperature of 50 ℃. Using foam pure zinc as an anode and a stainless steel sheet as a cathode, and anodizing for 5 minutes by adopting a direct current voltage of 8.0V. The anodizing bath contained 0.5g/L sodium carbonate and 0.5g/L sodium bicarbonate, and the pH was adjusted to 9 with a dilute sodium hydroxide solution, with a 5mm electrode spacing. The metal foam obtained in example 1 was subjected to electroless deposition in a phosphate bath to prepare a zinc phosphate layer. The foam metal is immersed into phosphoric acid solution heated to 30 ℃ under the action of ultrasonic waves for deposition for 10 minutes. The phosphating solution contains 15g/L phosphoric acid, 20g/L zinc nitrate hexahydrate and 1g/L graphene oxide, and the pH value is adjusted to 2.5 by using a dilute hydrochloric acid solution. And after chemical deposition, taking out the foam metal, respectively cleaning the foam metal in an alcohol solution and deionized water, and finally drying the foam metal in a vacuum drying oven and taking out the sample.
In summary, the following experimental data were obtained:
1. as can be seen from the XRD patterns of the foam pure zinc template and the composite coating sample in FIG. 1, the foam pure zinc template only consists of alpha-Zn phase, and the composite coating sample also has ZnO and Zn besides the alpha-Zn 3 (PO 4 ) 2 And a GO phase. Meanwhile, the diffraction peak intensity of the alpha-Zn phase of the sample after the composite coating treatment is slightly reduced, which shows that a compact biological coating is covered on the matrix phase.
2. As can be seen from SEM images of the porous structures of the pure zinc template in FIG. 2 (a) and the composite coating sample in FIG. 2 (b), the pure zinc template has a smooth surface, the framework diameter and the pore diameter are respectively 110.8 μm and 251.2 μm, and the porosity reaches 72.7%. Except for the porous structure of the composite coating sample, the surface of the sample has the square Zn 3 (PO 4 ) 2 And a fine needle-like ZnO coating. The framework diameter and pore size were 126.4 μm and 224.5 μm, respectively. The porosity was increased by a small amount, up to 78.4%, relative to the pure zinc template sample.
3. As can be seen from the compressive stress-strain curves of the pure zinc template and the composite coating sample in fig. 3 and the corresponding compressive performance data in table 1, the Compressive Yield Strengths (CYS) of the pure zinc template and the composite coating sample are 4.7MPa and 5.1MPa, the stable compressive strengths (CPS) are 9.5MPa and 9.8MPa, the elastic moduli (E) are 0.77GPa and 0.58GPa, and the compressive strains are 70% or more, respectively. The mechanical property of the composite coating sample is basically consistent with that of a pure zinc template and is between that of human cancellous bone and compact bone.
TABLE 1
Figure SMS_1
4. The data obtained from the potentiodynamic polarization curve diagrams of the pure zinc template and the composite coating sample in the Hank's solution and the fitting of Tafel interval in the chart 4 are shown in the table 2, and the corrosion potential, the corrosion current density and the corrosion rate of the pure zinc template are-1.001V and 8.4 muA/cm 2 And 122.4 μm/y, the composite coating samples are-0.989V, 7.1 μ A/cm 2 And 104.1 μm/y. Compared with a pure zinc template without the protection of the coating, the composite coating sample has more positive corrosion potential and lower corrosion current density and corrosion rate, and shows more excellent corrosion resistance.
TABLE 2
Figure SMS_2
5. From FIG. 5 which is a graph of the degradation rates of the pure zinc template and the composite coating sample after being soaked in Hank's solution for 3 months, it can be seen that the degradation rates of the pure zinc template and the composite coating sample are 152.1 μm/y and 137.3 μm/y, respectively.
6. FIG. 6 shows the cell survival rate of L929 cells cultured in 72 h of pure zinc template and composite coating sample leaching solutions with different concentrations, and it can be seen that the cell survival rate of L929 cells cultured in 72 h of 100% leaching solution is lower than 50%. The cytotoxicity rating was 3~4 according to ISO 10993-5, showing greater toxicity relative to the control. The survival rate of the L929 cells is gradually increased along with the continuous dilution of the metal leaching solution. The relative cell survival rate of the cells in the leaching liquor of the pure zinc template and the composite coating sample with the concentration of 25 percent is higher than 80 percent and is respectively 84.6 percent and 93.5 percent, and the non-toxicity is shown. While the relative cell viability in the leaching solutions of the pure zinc template and the composite coating samples with the concentration of 12.5 percent is 97.2 percent and 104.4 percent respectively. The relative cell survival rate in the composite coating sample leaching solution is more than 100 percent, and the effect of promoting cell proliferation is shown. The results show that the L929 cells have certain tolerance to the concentrations of the leaching liquor of the pure zinc template and the composite coating sample. In addition, in the leaching liquor with the same concentration, the cell survival rate of the leaching liquor of the composite coating sample is higher than that of the pure zinc template, and the composite coating sample has more excellent cell compatibility.
7. Fig. 7 shows the diameters of the inhibition zones of the pure zinc template and the composite coating sample, which are cultured together with staphylococcus aureus for 24 hours, and it can be seen that the sizes of the inhibition zones of the pure zinc template and the composite coating sample are respectively 6.52mm and 10.24mm, which indicates that the composite coating sample has more excellent antibacterial performance.
Example 2
Foam Zn-3Cu alloy is adopted as a template by a seepage method, ultrasonic oscillation is respectively carried out in acetone and alcohol solution for degreasing treatment, then 2mol/L hydrochloric acid is used for etching for 20 minutes to remove surface oxides and burrs, and finally deionized water is used for washing and drying in a vacuum drying box. A zinc oxide layer was prepared by anodizing in a plating bath using a DC power supply at a temperature of 40 ℃. Foam Zn-3Cu alloy is used as an anode, a stainless steel sheet is used as a cathode, and the anode is oxidized for 10 minutes by adopting a direct current voltage of 7.0V. The anodizing bath contained 0.5g/L sodium carbonate and 1.0g/L sodium bicarbonate, and the pH was adjusted to 8 with a dilute sodium hydroxide solution, the distance between the two electrodes being 5mm. The metal foam obtained in example 1 was subjected to electroless deposition in a phosphate bath to prepare a zinc phosphate layer. The foam metal is immersed into phosphoric acid solution heated to 30 ℃ under the action of ultrasonic waves for deposition for 15 minutes. The phosphating solution contains 20g/L of phosphoric acid, 15g/L of zinc nitrate hexahydrate and 1g/L of graphene oxide, and the pH value is adjusted to 2.0 by using a dilute hydrochloric acid solution. And after chemical deposition, taking out the foam metal, respectively cleaning the foam metal in an alcohol solution and deionized water, and finally drying the foam metal in a vacuum drying oven and taking out the sample.
The foam Zn-3Cu alloy consists of alpha-Zn and CuZn 5 Phase composition, and composite coating sample except for alpha-Zn and weak CuZn 5 In addition to the phase, znO and Zn are present 3 (PO 4 ) 2 And a GO phase. The Compressive Yield Strength (CYS) of the foam Zn-3Cu alloy and the composite coating sample is 6.8MPa and 6.9MPa respectively, the stable compressive strength (CPS) is 12.5MPa and 13.2MPa respectively, the elastic modulus (E) is 0.67GPa and 0.78GPa respectively, and the compressive strain is more than or equal to 70 percent. The corrosion potential, corrosion current density and corrosion rate of the foam Zn-3Cu alloy in Hank's solution are-0.958V and 10.6 muA/cm 2 And 154.4 μm/y, the composite coating samples were-0.928V, 8.5 μ A/cm, respectively 2 And 123.8 μm/y. The degradation rates of the foam Zn-3Cu alloy and the composite coating sample after soaking in Hank's solution for 3 months are 175.6 μm/y and 159.5 μm/y respectively. The relative cell survival rate of the L929 cells in the leaching liquor of the pure zinc template and the composite coating sample with the concentration of 25 percent is 82.2 percent and 94.2 percent respectively. While the relative cell viability in the leaching solutions of the pure zinc template and the composite coating samples with the concentration of 12.5 percent is 98.2 percent and 109.1 percent respectively. The sizes of the inhibition zones of the foam Zn-3Cu alloy and the composite coating sample are respectively 7.68mm and 12.15mm.
As shown in fig. 8 to 11, in the embodiment of the present invention: the vacuum drying oven includes:
a box body 1;
the heating device is positioned on the side wall of the box body 1;
an air extraction device;
a first base 101, the first base 101 is connected to the lower end of the box body 1
The stepping motor 2 is positioned in the first base 101, an output shaft of the stepping motor 2 penetrates through the middle part in the box body 1, and the output shaft of the stepping motor 2 is in rotary sealing connection with the box body 1;
the heating cavity 3 is positioned in the box body 1;
the placing table 4 is positioned in the box body 1, and the lower end of the placing table 4 is in keyed connection with a first gear 41;
the second base 102 is connected to the bottom of the inner side of the box body 1, the upper end of the second base 102 is provided with a circular groove 103, and the circular groove 103 is provided with a tooth groove 411 which is meshed with the first gear 41 along the circumferential direction of the groove wall;
the lifting mechanism is connected to one side of the placing table 4;
one end of the support rod 21 is connected to the output shaft of the stepping motor 2, and the other end of the support rod 21 is connected to the lifting mechanism;
the first annular guide rail 104 is arranged at the bottom of the circular groove 103;
the second annular guide rail 105 is arranged at the bottom of the circular groove 103, and the second annular guide rail 105 and the first annular guide rail 104 are arranged at intervals;
wherein, drive through step motor 2 and place platform 4 and move in box 1 internal peripheral, drive through first gear 41 and place platform 4 and rotate, drive through elevating system and place platform 4 upper and lower circulation swing, first gear 41 lower extreme fixedly connected with and first ring rail 104 matched with first slider, elevating system lower extreme fixedly connected with and second ring rail 105 matched with second slider.
By adopting the technical scheme, the heating device and the air extractor are structurally the structures in the prior mature technology, so that the invention is not stated again, the guide rail and the sliding block are arranged to play a role of auxiliary support, after the template material A is placed on the placing table, the stepping motor is started, the placing table 4 is driven to rotate circumferentially through the supporting rod, as the first gear at the lower end of the placing table is meshed with the tooth groove, the first gear rotates, the placing table rotates, the template material A on the placing table is positioned beside the heating device while rotating, so that the template material can be rapidly dried in all directions, the local overheating is avoided, and meanwhile, the placing table is driven to circularly swing up and down through the first gear, so that the deionized water and alcohol residual liquid attached to the surface of the template material A can be rapidly shaken and thrown out, the drying effect is improved, and the template material A is prevented from being incompletely dried to influence on the preparation of the composite coating.
In an embodiment of the present invention, the elevating mechanism includes:
a second gear 5, the second gear 5 meshing with the first gear 41;
the first sleeve 6 is positioned on the upper end face of the second gear 5, and a transmission cavity 61 is formed in the first sleeve 6;
one end of the first transmission shaft 7 is in keyed connection with the middle part of the upper end of the second gear 5, and the other end of the first transmission shaft 7 penetrates through the lower end of the first sleeve 6 and extends into the transmission cavity 61 and is in keyed connection with a first bevel gear 71;
the second transmission shaft 8 is rotatably connected to one side of the outer side of the upper end of the first sleeve 6, one end of the second transmission shaft 8 extends into the transmission cavity 61 and is in key connection with a second bevel gear 81;
the rotary table 9 is fixedly arranged at the other end, away from the first sleeve 6, of the second transmission shaft 8;
the rotating frame 91, the rotating frame 9 is connected to one end of the rotating disc 9, which is far away from the second transmission shaft 8, through a connecting rod 92;
a third ring groove 62, wherein the third ring groove 62 is formed at the lower end of the first sleeve 6;
the limiting plate 20 is positioned at the left lower part of the rotating frame 91 and is parallel to the turntable 9, the limiting plate 20 is fixedly connected with the first sleeve 6 through a connecting plate, and the limiting plate 20 is provided with a long groove 21 arranged along the height direction of the limiting plate 20;
the fixture block 19 is connected in the long groove 21 in a sliding mode;
wherein, be equipped with a plurality of first balls between third annular 62 and the second gear 5, first bevel gear 71 and the meshing of second bevel gear, rotating turret 91 is the isosceles triangle pipe support, the central axis of rotating turret 91 is located the below of carousel 9 center pin extension line and mutual interval sets up, step motor 2 drives carousel 9 through gear drive and rotates, first opening 101 has been seted up to one side edge that carousel 9 center pin extension line was kept away from to rotating turret 91, second opening 102 has been seted up at one side middle part that first opening 101 was kept away from to rotating turret 91, when carousel 9 did not rotate, second opening 102 is located the top of carousel 9 center pin extension line, fixture block 19 one end extends to the rotating turret 91 inboardly, other end fixed connection is on placing platform 4.
By adopting the technical scheme, when the first gear rotates to drive the second gear to synchronously rotate, the second gear drives the first bevel gear to rotate through the first transmission shaft, the first bevel gear rotates to drive the second bevel gear to rotate, the second bevel gear rotates to drive the second transmission shaft to drive the turntable, the turntable drives the rotating frame to eccentrically rotate, when the rotating frame rotates, the clamping block is driven to enable the third sleeve to be upwards pulled and lifted, when the clamping block moves to the second opening, the clamping block slides out of the rotating frame, at the moment, the third sleeve downwards and rapidly moves under the action of gravity, when the third sleeve stops, deionized water or alcohol residual liquid on the template material A is thrown out due to inertia, when the clamping block slides out of the rotating frame, the rotating frame continuously rotates, then the first opening rotates to one side of the clamping block, and the clamping block enters the rotating frame again through the first opening to continuously circulate.
In the embodiment of the invention: the placement stage 4 includes:
a second sleeve 11, wherein the second sleeve 11 is connected to the upper end of the first gear 41;
the third sleeve 12, the third sleeve 12 is connected to the upper end of the second sleeve 11;
the first slot 13, the first slot 13 locates at the middle part of upper end of the second sleeve 11;
the second slot 14, the second slot 14 locates at the middle part of the lower end of the third sleeve 12;
the fixed end of the elastic telescopic rod 15 is fixedly arranged at the bottom of the first slot 13, and the movable end of the elastic telescopic rod 15 is fixedly arranged at the bottom of the second slot 14;
the return spring 151 is sleeved outside the elastic telescopic rod 15, the upper end of the return spring 151 is fixedly connected to the bottom of the second slot 14, and the lower end of the return spring 151 is fixedly connected to the bottom of the first slot 13;
the fixed table 16 is positioned above the third sleeve 12, a through hole 162 is formed in the middle of the fixed table 16, an elastic net layer 163 is embedded in the elastic through hole 162, and a clamping arm for clamping the template material A is hinged to the edge of the upper end of the fixed table 16;
the supporting column 161, the supporting column 161 is fixedly connected between the fixed platform 16 and the third sleeve 12;
the first ring groove 17, the first ring groove 17 offers and cooperates with the outside of lower end of the third sleeve 12;
the clamping ring 18 is clamped in the first ring groove 17, and a plurality of second balls are arranged between the clamping ring 18 and the bottom of the first ring groove 17;
one end of the clamping block 19, which is far away from the turntable 9, is welded to the outer side of the clamping ring 18, and the rotating frame 91 rotates to drive the clamping block 19 to enable the third sleeve 12 to do vertical linear circulating motion.
Through adopting above-mentioned technical scheme, through setting up elasticity telescopic link and reset spring, exert elastic force when the third sleeve falls, make the fall that the third sleeve can be faster, improve the separation effect of deionized water or alcohol residual liquid and template material A, still possess buffering shock attenuation effect through elasticity telescopic link and reset spring, make the third sleeve can not collide the second sleeve, excellent in use effect.
In the embodiment of the invention: the placing table 4 further includes:
two third slots 22 are arranged, and the two third slots 22 are oppositely arranged on two sides of the edge of the upper end of the second sleeve 11;
the positioning column 24 is integrally formed at the bottom of the third slot 23;
a plurality of magnetic blocks 25 are arranged, and each magnetic block 25 is arranged in the positioning column 24 at intervals along the height direction of the positioning column 24;
two positioning rods 26 are arranged, the two positioning rods 26 are fixedly connected to the lower end of the third sleeve 12, and a fifth slot 27 matched with the positioning column 24 is formed in the lower end of each positioning rod 26;
the second ring groove 28 is formed in the side wall of the third slot 22 along the height direction of the third slot 22, a plurality of first conductors 281 are embedded at intervals at the bottoms of the two side grooves of the second ring groove 28, and each first conductor 281 and each magnetic block 25 are arranged corresponding to each other;
two second conductors 29 are arranged, the two second conductors 29 are respectively welded to the two outer sides of the lower end of the positioning rod 26, and the outer sides of the second conductors 29 are abutted to the bottom of the second annular groove 28;
the electromagnet 30, the electromagnet 30 is embedded in the locating rod 26;
the electromagnet 30 is annular, the upper end of the electromagnet 30 and the upper ends of the second conductors 29 are located on the same horizontal plane, the height of the water surface of the lower end face of each first conductor 281 is equal to the height of the water surface of the upper end face of the adjacent magnetic block 5, wires for connecting the two second conductors 29 are arranged on two sides of the electromagnet 30, the groove wall of the fifth slot 27 and the outer side wall of the positioning column 24 are arranged at intervals, and two vent holes communicated with the two third slots 22 are formed in two sides of the lower end of the second sleeve 11.
Through adopting above-mentioned technical scheme, when the third sleeve passes through fixture block and rotating turret and moves to the highest point, the level of terminal surface equals with the level of the magnetic path up end of the top in the locating lever under the electro-magnet, first conductor circular telegram thereupon, in-process when the third sleeve drives the locating lever whereabouts, the second conductor contacts with first conductor, make first conductor, form closed circuit between second conductor and the electro-magnet, the electro-magnet attracts mutually with the magnetic path opposite polarity of its below, a decurrent acceleration has been applyed to the locating column, make the speed of third sleeve whereabouts faster, further improve the separation effect of deionized water and alcohol residual liquid material template A.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (5)

1. A preparation method of a porous zinc biological composite coating for a degradable bone scaffold is characterized by comprising the following operation steps:
a. preparing a template material A by an electrodeposition method, a seepage method and an additive manufacturing method;
b. placing the template material A in acetone and alcohol solution respectively, carrying out ultrasonic oscillation for degreasing, adopting 1-3mol/L hydrochloric acid (HCl) to etch the surface of the template material A for 15-30min, and finally adopting deionized water to wash and drying in a vacuum drying oven;
c. taking out the dried template material A, taking the template material A as an anode and a stainless steel sheet as a cathode, and placing the template material A in a zinc liquid tank for anodic oxidation for 1-60min to prepare a zinc oxide layer, wherein the distance between the two electrodes is 2-10mm;
d. c, immersing the template material A prepared in the step c into phosphate bath liquid at the temperature of 20-80 ℃ under the action of ultrasonic waves, and carrying out chemical deposition for 2-60min to prepare a zinc phosphate layer;
e. after chemical deposition, taking out the template material A, respectively cleaning in an alcohol solution and deionized water, and finally drying in a vacuum drying oven;
f. taking out the sample to obtain a finished product;
in the step b, the template material A washed by deionized water is placed in a vacuum drying oven for swinging, heating and drying;
in the step e, the template material A washed by alcohol solution and deionized water is placed in a vacuum drying oven for swinging, heating and drying;
the vacuum drying oven includes:
a box body;
the heating device is positioned on the side wall of the box body;
an air extraction device;
a first base connected to the lower end of the box body
The stepping motor is positioned in the first base, an output shaft of the stepping motor penetrates through the middle part in the box body, and the output shaft of the stepping motor is in rotary sealing connection with the box body;
the heating cavity is positioned in the box body;
the placing table is positioned in the box body, and a first gear is connected with the lower end of the placing table through a key;
the second base is connected to the bottom of the inner side of the box body, a circular groove is formed in the upper end of the second base, and a tooth groove meshed with the first gear is formed in the circular groove along the circumferential direction of the groove wall;
the lifting mechanism is connected to one side of the placing table;
one end of the supporting rod is connected to an output shaft of the stepping motor, and the other end of the supporting rod is connected to the lifting mechanism;
the first annular guide rail is arranged at the bottom of the circular groove;
the second annular guide rail is arranged at the bottom of the circular groove, and the second annular guide rail and the first annular guide rail are arranged at intervals;
the device comprises a box body, a placing table, a lifting mechanism, a first annular guide rail, a second annular guide rail, a first gear, a second gear, a first sliding block, a second sliding block and a third sliding block, wherein the placing table is driven to move circumferentially in the box body through a stepping motor, is driven to rotate through the first gear, and is driven to circularly swing up and down through the lifting mechanism;
the lifting mechanism comprises:
a second gear engaged with the first gear;
the first sleeve is positioned on the upper end face of the second gear, and a transmission cavity is formed in the first sleeve;
one end of the first transmission shaft is in keyed connection with the middle part of the upper end of the second gear, and the other end of the first transmission shaft penetrates through the lower end of the first sleeve and extends into the transmission cavity and is in keyed connection with a first bevel gear;
the second transmission shaft is rotatably connected to one side outside the upper end of the first sleeve, one end of the second transmission shaft extends into the transmission cavity and is in key connection with a second bevel gear;
the rotating disc is fixedly arranged at the other end, departing from the first sleeve, of the second transmission shaft;
the rotating frame is connected to one end, away from the second transmission shaft, of the rotating disc through a connecting rod;
the third ring groove is formed in the lower end of the first sleeve;
the limiting plate is positioned at the left lower part of the rotating frame and is parallel to the rotary table, the limiting plate is fixedly connected with the first sleeve through a connecting plate, and the limiting plate is provided with a long groove arranged along the height direction of the limiting plate;
the clamping block is connected in the strip groove in a sliding manner;
when the rotating disc does not rotate, the second opening is positioned above the extension line of the central shaft of the rotating disc, one end of the clamping block extends to the inner side of the rotating frame, and the other end of the clamping block is fixedly connected to the placing table;
the placing table comprises:
the second sleeve is connected to the upper end of the first gear;
the third sleeve is connected to the upper end of the second sleeve;
the first slot is positioned in the middle of the upper end of the second sleeve;
the second slot is positioned in the middle of the lower end of the third sleeve;
the fixed end of the elastic telescopic rod is fixedly arranged at the bottom of the first slot, and the movable end of the elastic telescopic rod is fixedly arranged at the bottom of the second slot;
the reset spring is sleeved outside the elastic telescopic rod, the upper end of the reset spring is fixedly connected to the bottom of the second slot, and the lower end of the reset spring is fixedly connected to the bottom of the first slot;
the fixing table is positioned above the third sleeve, a through hole is formed in the middle of the fixing table, an elastic net layer is embedded in the elastic through hole, and a clamping arm for clamping the template material A is hinged to the edge of the upper end of the fixing table;
the supporting column is fixedly connected between the fixed table and the third sleeve;
the first ring groove is formed in the outer side of the lower end of the third sleeve;
the clamping ring is clamped in the first annular groove, and a plurality of second balls are arranged between the clamping ring and the bottom of the first annular groove;
one end of the clamping block, which is far away from the rotary disc, is welded with the outer side of the clamping ring, and the rotating frame rotates to drive the clamping block to enable the third sleeve to do vertical linear circulating motion;
the placing table further comprises:
two third slots are arranged, and the two third slots are oppositely arranged on two sides of the edge of the upper end of the second sleeve;
the positioning column is integrally formed at the bottom of the third slot;
the magnetic blocks are arranged in the positioning columns at intervals along the height direction of the positioning columns;
the two positioning rods are fixedly connected to the lower end of the third sleeve, and a fifth slot matched with the positioning column is formed in the lower end of each positioning rod;
the second ring groove is formed in the side wall of the third slot along the height direction of the third slot, a plurality of first conductors arranged at intervals are embedded in the groove bottoms on the two sides of the second ring groove, and each first conductor and each magnetic block are arranged correspondingly;
two second conductors are arranged, the two second conductors are respectively welded with the two sides outside the lower end of the positioning rod, and the outer sides of the second conductors are abutted to the bottom of the second annular groove;
the electromagnet is embedded in the positioning rod;
the electromagnet is annular, the upper end of the electromagnet and the upper ends of the second conductors are located on the same horizontal plane, the water surface height of the lower end face of each first conductor is equal to the horizontal height of the upper end face of the adjacent magnetic block, wires for connecting the two second conductors are arranged on two sides of the electromagnet, the groove wall of the fifth slot and the outer side wall of the positioning column are arranged at intervals, and two air holes communicated with the two third slots are formed in two sides of the lower end of the second sleeve.
2. The method for preparing the porous zinc biocomposite coating for the degradable bone scaffold according to claim 1, wherein in the step a, the template material A includes but is not limited to porous pure zinc, and can also be zinc-magnesium, zinc-copper, zinc-manganese, zinc-carbon nanotube porous alloy.
3. The method for preparing the porous zinc biological composite coating for the degradable bone scaffold as claimed in claim 1, wherein in the step c, the anodization process is that the anode is anodized in a zinc bath containing an anodization plating solution at a temperature of 30 to 60 ℃ by using a direct current power supply with a voltage of 5.0 to 10.0V.
4. Degradable according to claim 3The preparation method of the porous zinc biological composite coating of the bone degradation scaffold is characterized in that in the step c, the anodic oxidation plating solution contains 0.1 to 2g/L of sodium carbonate (Na) 2 CO 3 ) And 0.1 to 1g/L of sodium bicarbonate (NaHCO) 3 ) And adjusting the pH value to 8 to 10 by using a dilute sodium hydroxide solution (NaOH).
5. The method for preparing the porous zinc biological composite coating for the degradable bone scaffold as claimed in claim 1, wherein the phosphate bath solution contains 2 to 30g/L phosphoric acid (H) in step d 3 PO 4 ) 5 to 40g/L of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 •6H 2 O) and 0.5 to 5g/L of Graphene Oxide (GO) or Carbon Nanotubes (CNTs), and adjusting the pH value to 1.5 to 3.5 by using a dilute hydrochloric acid solution.
CN202111170985.9A 2021-10-08 2021-10-08 Preparation method of porous zinc biological composite coating for degradable bone scaffold Active CN113797396B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111170985.9A CN113797396B (en) 2021-10-08 2021-10-08 Preparation method of porous zinc biological composite coating for degradable bone scaffold

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111170985.9A CN113797396B (en) 2021-10-08 2021-10-08 Preparation method of porous zinc biological composite coating for degradable bone scaffold

Publications (2)

Publication Number Publication Date
CN113797396A CN113797396A (en) 2021-12-17
CN113797396B true CN113797396B (en) 2023-03-03

Family

ID=78939317

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111170985.9A Active CN113797396B (en) 2021-10-08 2021-10-08 Preparation method of porous zinc biological composite coating for degradable bone scaffold

Country Status (1)

Country Link
CN (1) CN113797396B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114985005B (en) * 2022-07-06 2023-11-21 华东理工大学 Modified cellulose nanocrystalline, supported metal catalyst, and preparation method and application thereof
CN115501392B (en) * 2022-09-28 2024-04-19 深圳先进技术研究院 Zinc oxide/zinc phosphate nano rod composite antibacterial coating and preparation method and application thereof
CN116621574A (en) * 2023-05-19 2023-08-22 温州医科大学附属口腔医院 Preparation method of porous metal mesh toughened zinc phosphate bioceramic degradable bone implant

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012095735A (en) * 2010-10-29 2012-05-24 Kyushu Univ Phosphate coating material, apatite coating material, and method for producing them
CN105797207A (en) * 2016-04-01 2016-07-27 北京联合大学 Drug release carrier on metal substrate and preparation method thereof
CN106806938A (en) * 2015-11-27 2017-06-09 先健科技(深圳)有限公司 Available iron based alloy implanted medical device
CN108144111A (en) * 2017-12-25 2018-06-12 大连三生科技发展有限公司 A kind of planting body active surface
CN108904893A (en) * 2018-07-24 2018-11-30 南方科技大学 A kind of composite coating and its preparation method and application having both antibacterial and biocompatibility
CN109966568A (en) * 2019-04-11 2019-07-05 湘潭大学 A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof
CN113082290A (en) * 2019-12-23 2021-07-09 北京科技大学天津学院 Zinc oxide coating-hydroxyapatite coating with bioactivity and antibacterial performance, preparation method and application
CN113289071A (en) * 2021-05-18 2021-08-24 中国科学院宁波材料技术与工程研究所 Implantable zinc-based alloy surface structure and preparation method and application thereof
CN114042898A (en) * 2021-11-10 2022-02-15 温州医科大学附属口腔医院 Preparation method of biomedical degradable metal skeleton reinforced Zn-based composite material with large-area galvanic corrosion structure

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9618264B1 (en) * 2010-09-09 2017-04-11 Elberto Berdut-Teruel Permanent magnet induction heating system and magnetic dehydrator
KR20130057001A (en) * 2011-11-23 2013-05-31 아인텍(주) Dry device of food treater
JP6091060B2 (en) * 2011-12-02 2017-03-08 芝浦メカトロニクス株式会社 Spin processing device
CN107339855B (en) * 2017-08-02 2023-09-19 宜诺(天津)制药设备有限公司 Rotatable direct conduction rapid continuous heating dryer for ring-type hard belt
CN207991205U (en) * 2018-03-16 2018-10-19 邢台康柴发动机垫片制造有限公司 A kind of heating drier for before product treatment
CN108458565A (en) * 2018-04-28 2018-08-28 刘霖霞 A kind of drying device in food production
CN209901325U (en) * 2019-04-02 2020-01-07 曲靖医学高等专科学校 Chemistry experiment heating frame with adjustable
CN109907349A (en) * 2019-04-04 2019-06-21 嘉兴歆瑶商贸有限公司 Breeding feed drying and crushing integrated apparatus
CN213066936U (en) * 2020-07-17 2021-04-27 东晟源研究院(广州)有限公司 Cosmetics vacuum drying case
CN114739120A (en) * 2022-04-24 2022-07-12 湖南金凯循环科技有限公司 Waste lithium ion battery recovery processing device and method with flue gas purification function

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012095735A (en) * 2010-10-29 2012-05-24 Kyushu Univ Phosphate coating material, apatite coating material, and method for producing them
CN106806938A (en) * 2015-11-27 2017-06-09 先健科技(深圳)有限公司 Available iron based alloy implanted medical device
CN105797207A (en) * 2016-04-01 2016-07-27 北京联合大学 Drug release carrier on metal substrate and preparation method thereof
CN108144111A (en) * 2017-12-25 2018-06-12 大连三生科技发展有限公司 A kind of planting body active surface
CN108904893A (en) * 2018-07-24 2018-11-30 南方科技大学 A kind of composite coating and its preparation method and application having both antibacterial and biocompatibility
CN109966568A (en) * 2019-04-11 2019-07-05 湘潭大学 A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof
CN113082290A (en) * 2019-12-23 2021-07-09 北京科技大学天津学院 Zinc oxide coating-hydroxyapatite coating with bioactivity and antibacterial performance, preparation method and application
CN113289071A (en) * 2021-05-18 2021-08-24 中国科学院宁波材料技术与工程研究所 Implantable zinc-based alloy surface structure and preparation method and application thereof
CN114042898A (en) * 2021-11-10 2022-02-15 温州医科大学附属口腔医院 Preparation method of biomedical degradable metal skeleton reinforced Zn-based composite material with large-area galvanic corrosion structure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Enhanced corrosion resistance via phosphate conversion coating on pure Zn for medical applications;Lishu Zhang et al.;《 Corrosion Science》;20200319;第169卷;1.0介绍，2.1材料的准备，3.1 ZnP涂层的微观结构表征，4.0结论 *

Also Published As

Publication number Publication date
CN113797396A (en) 2021-12-17

Similar Documents

Publication Publication Date Title
CN113797396B (en) Preparation method of porous zinc biological composite coating for degradable bone scaffold
US8828552B2 (en) Method for producing an anti-infective coating on implants
CN107456601B (en) Zn-Cu series zinc alloy and preparation method and application thereof
CN107456610B (en) Zn-Ag series zinc alloy and preparation method and application thereof
CN111733417B (en) Method for low-temperature copper infiltration on surface of titanium or titanium alloy
CN104141124A (en) Method for improving biological activity of pure titanium surface by using dopamine to be bonded with graphene oxide
CN110029383B (en) Degradable zinc-copper foam biological material
CN104726921A (en) Titanium dioxide/strontium and fluorine-containing hydroxyapatite bioactive nano-composite coating as well as preparation method and application thereof
CN111842086B (en) Preparation method of composite coating for improving corrosion resistance and antibacterial property of magnesium alloy
CN102671241A (en) Medical magnesium alloy surface phytic acid micro-arc anodic oxide film and polylactic acid coating and process
CN105274603A (en) Compound modified coating of magnesium or magnesium alloy surface carbon-containing nano tube and preparation method of compound modified coating
CN101555616B (en) Method for preparing hydroxyapatite/titanium dioxide composite coating on nickel-titanium surface
CN113502524B (en) Preparation method of medical titanium alloy surface biological piezoelectric antibacterial coating
CN112500150A (en) Magnesium alloy/biological ceramic porous scaffold and preparation method and application thereof
CN113755926A (en) Method for preparing composite coating with high corrosion resistance, antibacterial property and photo-thermal property on surface of medical magnesium alloy
CN102181904B (en) Titanium surface activation method
TWI532883B (en) Titanium or titanium alloy having antibacterial surface and method for manufacturing the same
WO2024103629A1 (en) Biomedical magnesium alloy composite coating and preparation method therefor
CN112121227A (en) Preparation method of medical composite coating of strontium titanate/strontium hydroxyapatite on titanium metal surface
CN101773412A (en) Surface activation method of dental implant
CN112974843B (en) Surface treatment process for 3D printed implant
CN111603615B (en) Controllable degradable high-strength magnesium-based composite stent composite coating and preparation method thereof
CN108560036B (en) Surface-carried Zn2+Magnesium alloy material and preparation method and application thereof
CN107773781B (en) Preparation method of bendable fully-degradable zinc alloy nerve conduit
CN117448900A (en) Porous Ti-Cu alloy bracket with MAO treated surface and preparation method and application thereof

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