CN109079124A - A kind of medical embedded bimetallic material and preparation method thereof - Google Patents
A kind of medical embedded bimetallic material and preparation method thereof Download PDFInfo
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- CN109079124A CN109079124A CN201810865875.6A CN201810865875A CN109079124A CN 109079124 A CN109079124 A CN 109079124A CN 201810865875 A CN201810865875 A CN 201810865875A CN 109079124 A CN109079124 A CN 109079124A
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- kirsite
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- titanium alloy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D19/00—Casting in, on, or around objects which form part of the product
- B22D19/08—Casting in, on, or around objects which form part of the product for building-up linings or coverings, e.g. of anti-frictional metal
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- 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
- A61L27/58—Materials at least partially resorbable by the body
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
Abstract
The present invention provides a kind of medical embedded bimetallic materials and preparation method thereof, the material inner core being prepared into is titanium alloy, outer layer is kirsite, is connected in the form of dovetail groove between the two, and makes the two in metallurgical bonding by surrounding pouring liquid kirsite under titanium alloy solid-state high temperature.Kirsite chemical component contains by mass percentage: Mg 0.05% ~ 0.8%, Ag 0.05% ~ 0.5%, La 0.1% ~ 0.5%, Se 0.1% ~ 0.5%, Sr 0.1% ~ 0.5%, Sn 0.1% ~ 0.5%, surplus Zn.The titanium alloy of inner core has excellent mechanical property, meets its medicine function needs；What is contacted with inside of human body is the kirsite of outer layer, in degradation process, can release needed by human and absorbable element.The kirsite degradation process of the human body implant devices outer layer prepared with the material needs certain time, it can be relieved adverse reaction existing for implantation initial stage metal material and tissue combination interface, after kirsite is degradable, tissue effect in conjunction with the titanium alloy of inner layer is more preferable.
Description
Technical field
The invention belongs to medical new material technology field, in particular to a kind of medical embedded bimetallic material and its preparation side
Method.
Background technique
Metal material becomes the wide implantation material of current clinical application due to its good mechanical property and processing performance
Material mainly includes that the pure metal such as titanium, zirconium, niobium, tantalum and other noble metals, cobalt-base alloys, stainless steel, titanium alloy, shape memory close
Gold etc.；These materials all have certain mechanical property and good corrosion resistance, can keep for a long time steady after being implanted into human body
It is fixed；But some problems are also brought, such as there is adverse reaction etc. at implantation Initial human and metal bonding interface.Based on such shape
Condition, biodegradable are implanted into the problem of material becomes extensive concern.
Biodegradable is mostly used to be implanted into material, including high molecular material, bioactive ceramics material in clinical application at present
Material, metal_based material.High molecular material comprehensive mechanical property is too low, and the acidic environment for generation of degrading will increase human body and generate inflammation
Probability, the plasticity and toughness of biological active ceramic material are poor, and application range is small, the degradable implantation material of Metal Substrate become faces
Bed applies main material.
The degradable implantation material of Metal Substrate mainly includes magnesium alloy, ferrous alloy and titanium alloy.But magnesium alloy and iron-based conjunction
There are some problems in terms of degradation rate as degradable implantation material for gold, and the mechanical property of magnesium alloy is again relatively poor, and
Degradation speed is too fast, influences its biocompatibility and toughness in use etc., and the problem of ferrous alloy maximum is drop
It is excessively slow to solve speed, a series of adverse reactions can be caused.
For the chemical activity of metallic zinc between magnesium and iron, corrosion rate therebetween, can prepare degradation speed
Rate material appropriate.Zinc is one of necessary microelement of human body, and the allowance,dietary of the daily zinc of health adult is 20 ~ 40mg,
Therefore zinc has certain advantage as degradable implantation material in terms of the control of degradation rate and biological safety.Chinese patent
Application number 201410556876.4 discloses a kind of degradable kirsite of medical bio and preparation method thereof.But the power of kirsite
Performance is poor, and intensity and plasticity are not able to satisfy the requirement for being implanted into material.
Titanium alloy is widely used with its excellent mechanical property, preferable biocompatibility.Titanium alloy at present
Exist as medical embedded material following insufficient: having certain biocompatibility, but can not degrade, implantation initial stage make human body with
Metal bonding interface has adverse reaction, brings potential hazard to human body.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of medical embedded bimetallic material and preparation method thereof, have
Following advantages: 1. there is excellent mechanical property；2. titanium alloy outer layer is kirsite, not only there is good biocompatibility, and
And it is degradable, after the device implantation human body of material preparation, titanium alloy has excellent mechanical property, meets its medicine function need
It wants；It can release Zn, Mg, La, Se, Sr, Sn and Ag element in degradation process with inside of human body contact kirsite, be human body
Required and absorbable element, micro silver ion is harmless, may also function as bactericidal effect；The kirsite of implant devices outer layer
Degradation process needs certain time, can be relieved implantation initial stage metal material with tissue combination interface asking there are adverse reaction
Topic, after kirsite is degradable, tissue effect in conjunction with the titanium alloy of inner layer is more preferable.
Based on object above, the present invention provides a kind of medical embedded bimetallic materials and preparation method thereof, and feature exists
In: inner core is titanium alloy, and outer layer is kirsite, and kirsite is connect in the form of dovetail groove between the two with titanium alloy, and passes through titanium
Surrounding pouring liquid kirsite makes the two in metallurgical bonding under alloy solid-state high temperature.
A kind of medical embedded bimetallic material provided by the invention and preparation method thereof, preparation process are as follows:
1) punching block inner wall applies kirsite release agent；
2) titanium alloy rod bar (diameter 2R) carry out being machined into dovetail shaped fin, it is without the diameter at dovetail shaped fin after processing
2r,r/RIt is 0.2,αIt is 30 ° ~ 40 °,βIt is 70 ° ~ 80 °, then carries out degreasing and washing；
3) the titanium alloy bar preheating with dovetail shaped fin, 980 ~ 1050 DEG C of temperature, time 8h；
4) prepare kirsite melt: the following steps are included: 1. alloying ingredient: chemical component is by mass percentage are as follows: Mg
0.05% ~ 0.8%, Ag 0.05% ~ 0.5%, La 0.1% ~ 0.5%, Se 0.1% ~ 0.5%, Sr 0.1% ~ 0.5%, Sn 0.1% ~ 0.5%,
Surplus Zn；2. melting: alloy is warming up to 1050 DEG C, is pressed into carbon trichloride into alloy melt using graphite bell jar, indentation
Carbon trichloride is the 0.2% ~ 0.3% of alloy melt total weight, then stands 10 ~ 20min in 980 DEG C of heat preservations, it is molten to form kirsite
Body；
5) kirsite melt is cooled into 480 DEG C of heat preservation 2h；
6) titanium alloy bar with dovetail shaped fin after preheating is placed in punching block vestibule center, guarantees punching block inner wall and magnesium alloy bar
Dovetail shaped fin outer arc has fixed gapδ,δ/RIt is 0.1 ~ 0.5；
7) kirsite melt is cast into punching block, punching block water flowing is cooling in casting process；
8) titanium zinc composite bar is taken out in die sinking after being cooled to room temperature；
9) by the titanium zinc composite bar stress relief annealing of preparation, 180 ~ 260 DEG C of temperature, 2.5 ~ 4h of soaking time；
10) drawing is carried out to titanium zinc composite bar, obtains different diameters, meet different clinical use requirements.
The beneficial effects of the present invention are:
The inner core of medical embedded bimetallic material is titanium alloy, and outer layer is kirsite, and kirsite and titanium alloy are between the two with dovetail
The form of slot connects, and makes the two in metallurgical bonding by surrounding pouring liquid kirsite under titanium alloy solid-state high temperature, passes through drawing
Equal processing methods are pulled out, stick (line) material that diameter meets requirement, the titanium zinc bimetallic material knot prepared using this method are obtained
Conjunction intensity is 150MPa, atom diffusion layer is not less than 100 μm.After the device implantation human body of material preparation, titanium alloy has excellent
Good mechanical property meets its medicine function needs；With inside of human body contact kirsite can release in degradation process Zn,
Mg, La, Se, Sr, Sn and Ag element, Zn, Mg, La, Se, Sr, Sn are needed by human and absorbable element, micro silver ion
It is harmless, it may also function as bactericidal effect；The kirsite degradation process of implant devices outer layer needs certain time, can be relieved plant
Enter initial stage metal material and after tissue combination interface has that adverse reaction, kirsite are degradable, tissue
Effect is more preferable in conjunction with the titanium alloy of inner layer.
Detailed description of the invention
Fig. 1 is the end face figure of medical embedded bimetallic material；Fig. 2 be in Fig. 1 A-A to cross-sectional view；Fig. 3 is medical plant
Enter state of the bimetallic material in punching block, 1 is the titanium alloy rod bar with dovetail shaped fin, and 2 be the zinc of titanium alloy rod bar outer layer
Alloy.
Specific embodiment
Principles and features of the present invention are described with reference to embodiments, listed give an actual example is served only for explaining this hair
It is bright, not limit the scope of the invention.
Embodiment 1:
1) the MK-TG environment-friendly type kirsite release agent of punching block inner wall Tu Meiya Chemical Co., Ltd. production；
2) titanium alloy rod bar (diameter 10mm) carries out being machined into dovetail shaped fin, without the diameter at dovetail shaped fin after processing
It is 2r,r/RIt is 0.2,α=35 °,βIt is 75 °, then carries out degreasing and washing；
3) the titanium alloy bar preheating with dovetail shaped fin, 980 ~ 1050 DEG C of temperature, time 8h；
4) prepare kirsite melt: the following steps are included: 1. alloying ingredient: chemical component is by mass percentage are as follows: Mg
0.15%, Ag 0.1%, La 0.2%, Se 0.2%, Sr 0.15%, Sn 0.25%, surplus Zn；2. melting: alloy is warming up to
1050 DEG C, carbon trichloride is pressed into alloy melt using graphite bell jar, the carbon trichloride of indentation is alloy melt total weight
0.22%, 10 ~ 20min then is stood in 980 DEG C of heat preservations, forms kirsite melt；
5) kirsite melt is cooled into 480 DEG C of heat preservation 2h；
6) titanium alloy bar with dovetail shaped fin after preheating is placed in punching block vestibule center, guarantees punching block inner wall and magnesium alloy bar
Dovetail shaped fin outer arc has fixed gap 2mm；
7) kirsite melt is cast into punching block, punching block water flowing is cooling in casting process；
8) titanium zinc composite bar is taken out in die sinking after being cooled to room temperature；
9) by the titanium zinc composite bar stress relief annealing of preparation, 180 ~ 260 DEG C of temperature, 2.5 ~ 4h of soaking time；
10) drawing is carried out to titanium zinc composite bar, obtains different diameters, meet different clinical use requirements.
The titanium zinc bimetallic material bond strength for using this method to prepare is 150MPa, atom diffusion layer not less than 105 μm.
Embodiment 2:
1) the MK-TG environment-friendly type kirsite release agent of punching block inner wall Tu Meiya Chemical Co., Ltd. production.
2) titanium alloy rod bar (diameter 15mm) carries out being machined into dovetail shaped fin, and the diameter after processing is 2r,r/RFor
0.2,α=35 °,βIt is 75 °, then carries out degreasing and washing；
3) the titanium alloy bar preheating with dovetail shaped fin, 980 ~ 1050 DEG C of temperature, time 8h.
4) prepare kirsite melt: the following steps are included: 1. alloying ingredient: chemical component is by mass percentage are as follows: Mg
0.25%, Ag 0.2%, La 0.3%, Se 0.25%, Sr 0.2%, Sn 0.2%, surplus Zn；2. melting: alloy is warming up to 1050
DEG C, carbon trichloride is pressed into alloy melt using graphite bell jar, the carbon trichloride of indentation is alloy melt total weight
0.22%, 10 ~ 20min then is stood in 980 DEG C of heat preservations, forms kirsite melt；
5) kirsite melt is cooled into 480 DEG C of heat preservation 2h；
6) titanium alloy bar with dovetail shaped fin after preheating is placed in punching block vestibule center, guarantees punching block inner wall and titanium alloy bar
There is fixed gap 3mm；
7) kirsite melt is cast into punching block, punching block water flowing is cooling in casting process；
8) titanium zinc composite bar is taken out in die sinking after being cooled to room temperature；
9) by the titanium zinc composite bar stress relief annealing of preparation, 180 ~ 260 DEG C of temperature, 2.5 ~ 4h of soaking time；
10) drawing is carried out to titanium zinc composite bar, obtains different diameters, meet different clinical use requirements.
The titanium zinc bimetallic material bond strength for using this method to prepare is 110 μm for 152MPa, atom diffusion layer.
Embodiment 3:
1) the MK-TG environment-friendly type kirsite release agent of punching block inner wall Tu Meiya Chemical Co., Ltd. production；
2) titanium alloy rod bar (diameter 20mm) carries out being machined into dovetail shaped fin, without the diameter at dovetail shaped fin after processing
It is 2r,r/RIt is 0.2,α=35 °,βIt is 75 °, then carries out degreasing and washing；
3) the titanium alloy bar preheating with dovetail shaped fin, 980 ~ 1050 DEG C of temperature, time 8h；
4) prepare kirsite melt: the following steps are included: 1. alloying ingredient: chemical component is by mass percentage are as follows: Mg
0.3%, Ag 0.25%, La 0.35%, Se 0.3%, Sr 0.4%, Sn 0.4%, surplus Zn；2. melting: alloy is warming up to 1050
DEG C, carbon trichloride is pressed into alloy melt using graphite bell jar, the carbon trichloride of indentation is alloy melt total weight
0.22%, 10 ~ 20min then is stood in 980 DEG C of heat preservations, forms kirsite melt；
5) kirsite melt is cooled into 480 DEG C of heat preservation 2h；
6) titanium alloy bar with dovetail shaped fin after preheating is placed in punching block vestibule center, guarantees punching block inner wall and titanium alloy bar
There is fixed gap 5mm；
7) kirsite melt is cast into punching block, punching block water flowing is cooling in casting process；
8) titanium zinc composite bar is taken out in die sinking after being cooled to room temperature；
9) by the titanium zinc composite bar stress relief annealing of preparation, 180 ~ 260 DEG C of temperature, 2.5 ~ 4h of soaking time；
10) drawing is carried out to titanium zinc composite bar, obtains different diameters, meet different clinical use requirements.
The titanium zinc bimetallic material bond strength for using this method to prepare is 155MPa, atom diffusion layer not less than 108 μm.
Embodiment 4:
1) the MK-TG environment-friendly type kirsite release agent of punching block inner wall Tu Meiya Chemical Co., Ltd. production；
2) titanium alloy rod bar (diameter 20mm) carries out being machined into dovetail shaped fin, without the diameter at dovetail shaped fin after processing
It is 2r,r/RIt is 0.2,α=35 °,βIt is 75 °, then carries out degreasing and washing；
3) the titanium alloy bar preheating with dovetail shaped fin, 980 ~ 1050 DEG C of temperature, time 8h；
4) prepare kirsite melt: the following steps are included: 1. alloying ingredient: chemical component is by mass percentage are as follows: Mg
0.4%, Ag 0.4%, La 0.45%, Se 0.4%, Sr 0.2%, Sn 0.5%, surplus Zn；2. melting: alloy is warming up to 1050
DEG C, carbon trichloride is pressed into alloy melt using graphite bell jar, the carbon trichloride of indentation is alloy melt total weight
0.22%, 10 ~ 20min then is stood in 980 DEG C of heat preservations, forms kirsite melt；
5) kirsite melt is cooled into 480 DEG C of heat preservation 2h；
6) titanium alloy bar with dovetail shaped fin after preheating is placed in punching block vestibule center, guarantees punching block inner wall and magnesium alloy bar
Dovetail shaped fin outer arc has fixed gap 6mm；
7) kirsite melt is cast into punching block, punching block water flowing is cooling in casting process；
8) titanium zinc composite bar is taken out in die sinking after being cooled to room temperature；
9) by the titanium zinc composite bar stress relief annealing of preparation, 180 ~ 260 DEG C of temperature, 2.5 ~ 4h of soaking time；
10) drawing is carried out to titanium zinc composite bar, obtains different diameters, meet different clinical use requirements.
The titanium zinc bimetallic material bond strength for using this method to prepare is 154MPa, atom diffusion layer not less than 112 μm.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of medical embedded bimetallic material and preparation method thereof, which is characterized in that preparation method the following steps are included:
1) punching block inner wall applies kirsite release agent；
2) titanium alloy rod bar (diameter 2R) carry out being machined into dovetail shaped fin, it is without the diameter at dovetail shaped fin after processing
2r, the shape and size of dovetail shaped fin byR、r、α、β It determines, then carries out degreasing and washing；
3) titanium alloy bar preheats, and 980 ~ 1050 DEG C of temperature, time 8h；
4) kirsite melt is prepared: including alloying ingredient and melting, 1050 DEG C of smelting temperature, 10 are stood in 980 DEG C of heat preservations ~
20min forms kirsite melt；
5) kirsite melt is cooled into 480 DEG C of heat preservation 2h；
6) titanium alloy bar with dovetail shaped fin after preheating is placed in punching block vestibule center, guarantees punching block inner wall and titanium alloy bar
Dovetail shaped fin outer arc has fixed gapδ；
7) kirsite melt is cast into punching block, punching block water flowing is cooling in casting process；
8) titanium zinc composite bar is taken out in die sinking after being cooled to room temperature；
9) by the titanium zinc composite bar stress relief annealing of preparation, 180 ~ 260 DEG C of temperature, 2.5 ~ 4h of soaking time；
10) drawing is carried out to titanium zinc composite bar, obtains different diameters, meet different clinical use requirements.
2. medical embedded bimetallic material according to claim 1 and preparation method thereof, which is characterized in that the change of kirsite
It studies point by mass percentage: Mg 0.05% ~ 0.8%, Ag 0.05% ~ 0.5%, La 0.1% ~ 0.5%, Se 0.1% ~ 0.5%, Sr
0.1% ~ 0.5%, Sn 0.1% ~ 0.5%, surplus Zn.
3. medical embedded bimetallic material according to claim 1 and preparation method thereof, which is characterized in thatr/RValue is
0.2。
4. medical embedded bimetallic material according to claim 1 and preparation method thereof, which is characterized in thatαValue for 30 ° ~
40°。
5. medical embedded bimetallic material according to claim 1 and preparation method thereof, which is characterized in thatβValue for 70 ° ~
80°。
6. medical embedded bimetallic material according to claim 1 and preparation method thereof, which is characterized in thatδ/RValue is 0.1
~0.5。
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ID=64833588
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637861A (en) * | 2021-08-13 | 2021-11-12 | 湘潭大学 | Zn-Se alloy and preparation method and application thereof |
| CN113737056A (en) * | 2021-09-09 | 2021-12-03 | 湘潭大学 | Zn-Se-based alloy material and preparation method and application thereof |
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| CN113637861A (en) * | 2021-08-13 | 2021-11-12 | 湘潭大学 | Zn-Se alloy and preparation method and application thereof |
| CN113737056A (en) * | 2021-09-09 | 2021-12-03 | 湘潭大学 | Zn-Se-based alloy material and preparation method and application thereof |
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