CN115138863A - Preparation method capable of improving antibacterial function of medical cobalt-based alloy - Google Patents
Preparation method capable of improving antibacterial function of medical cobalt-based alloy Download PDFInfo
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
- B22F2003/175—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/241—Chemical after-treatment on the surface
- B22F2003/242—Coating
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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Abstract
The invention discloses a preparation method capable of improving antibacterial function of a medical cobalt-based alloy, and particularly relates to the technical field of medical materials, wherein CoCrWNi alloy powder is used as a raw material, copper powder is added, a treated metal block has antibacterial performance, an SLM-CoCrWNi metal block has an obvious inhibition effect on growth of staphylococcus aureus, the antibacterial rate on the staphylococcus aureus can reach more than 98%, and bacterial adhesion can be inhibited at the same time, so that formation of a biological film is greatly reduced, the hemolytic rate of the SLM-CoCrWNi metal block is far lower than 5%, the SLM-type medical cobalt-based alloy can be used for medical science, metal forming is carried out by adopting an SLM technology, the forming mode of the cobalt-based alloy can be optimized, the metal form is better formed, and after the metal block is subjected to solid solution treatment at 1200 ℃ for 1h, the shaping, toughness and machining performance of the material are improved, and the SLM-type cobalt-based alloy can be better used for medical equipment machining.
Description
Technical Field
The invention particularly relates to the technical field of medical materials, and particularly relates to a preparation method capable of improving the antibacterial function of a medical cobalt-based alloy.
Background
Because of good mechanical property, corrosion resistance and biocompatibility, the cobalt-based alloy is widely applied to the field of medical metal materials, and has been manufactured into various medical implants for replacing and repairing parts such as bearing bones, damaged joints, oral cavity decayed teeth, mutated necrotic tissues and organs and the like in a human body. Cobalt-based alloys have been used as biomedical metallic materials for replacement of all-metal joints in the human body for over seventy years.
However, the existing cobalt-based alloy is an inert metal material, bacteria are easily adhered to the surface of the alloy and form a bacterial biofilm, which is not beneficial to the body recovery of patients, and the cost of silver is high, so the metal-based antibacterial material usually takes copper as an antibacterial element, is added into a matrix of the metal material, and adopts special antibacterial heat treatment to ensure that copper-rich phases are uniformly and dispersedly distributed from the surface to the inside of the material, thereby meeting the requirement of antibacterial performance.
Disclosure of Invention
The invention aims to provide a preparation method capable of improving the antibacterial function of a medical cobalt-based alloy, and aims to solve the problems that the existing cobalt-based alloy proposed in the background art is an inert metal material, bacteria are easily adhered to the surface of the alloy, a bacterial biofilm is formed on the surface of the alloy, and the recovery of the body of a patient is not facilitated.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method capable of improving the antibacterial function of a medical cobalt-based alloy comprises the following steps:
step 1: selecting materials;
step 2: preparing a material;
and step 3: forging;
and 4, step 4: heat treatment;
and 5: solution treatment;
and 6: and (4) electroplating silver.
Preferably, the step 1: the materials are selected, copper powder with the purity of 99.9 percent and the granularity of 15-50 mu m and CoCrWNi alloy powder are fully mixed to obtain mixed powder with the copper content of 3 wt.%.
Preferably, the step 1: the chemical components of the mixed powder are as follows: cr19.19wt.%, w15.03wt.%, ni10.36wt.%, cu3wt.%, and the balance Co.
Preferably, the step 2: and (3) preparing the material, namely sieving the mixed powder, and then preparing the SLM-CoCrWNi metal block from the qualified mixed powder through an SLM forming instrument.
Preferably, the step 3: and forging, namely peeling the metal block, cutting a dead head to remove the part with uneven components, and forging at 1250 ℃.
Preferably, the step 4: and (4) performing heat treatment, namely performing heat preservation heat treatment on the forged SLM-CoCrWNi metal block at 1000 ℃ for 1 h.
Preferably, the step 5: and (3) solution treatment, namely performing water-cooling solution treatment on the metal block subjected to heat treatment in the step (4) at 1200 ℃ for 1h, and performing aging treatment for 6h in an environment at 800 ℃.
Preferably, the step 6: and electroplating silver, wherein the anode plate adopts a silver plate with the purity of more than 99.9 percent, the thickness of the silver plate is 10mm, the cathode is a red copper plate, the size of the red copper plate is 20mm × 30mm × 3mm, and the direct current electroplating power supply is adopted for electroplating.
Preferably, the silver plating solution for silver plating in the step 6 is a double complexing agent system consisting of DMH and NA, wherein the DMH concentration is 114g/L, the NA concentration is 18g/L, the temperature is 40 ℃, and the pH range is 10.0-12.0.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, coCrWNi alloy powder is used as a raw material, copper powder is added, the treated metal block has antibacterial performance, the SLM-CoCrWNi metal block has an obvious inhibition effect on the growth of staphylococcus aureus, the antibacterial rate on the staphylococcus aureus can reach more than 98%, and bacterial adhesion can be inhibited, so that the formation of a biological film is greatly reduced, the hemolytic rate of the SLM-CoCrWNi metal block is far lower than 5%, the SLM-CoCrWNi metal block can be used as medicine, the SLM technology is adopted for metal forming, the forming mode of a cobalt-based alloy can be optimized, a metal form can be better formed, after the metal block is subjected to solution treatment at 1200 ℃ for 1h, the molding, toughness and machining performance of the material are improved, the SLM-CoCrWNi metal block can be better used for processing medical equipment, good corrosion resistance is kept, silver electroplating treatment is further enhanced, antibacterial treatment of other strains on the SLM-CoCrWNi metal block is performed, and a cyanide-free silver plating mode is adopted, a more delicate plating layer can be generated, and no harm is caused to a human body.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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.
In the embodiment of the invention, a preparation method capable of improving the antibacterial function of a medical cobalt-based alloy comprises the following steps:
step 1: selecting materials;
step 2: preparing a material;
and 3, step 3: forging;
and 4, step 4: heat treatment;
and 5: solution treatment;
step 6: and (4) electroplating silver.
Preferably, the step 1: the materials are selected, copper powder with the purity of 99.9 percent and the granularity of 15-50 mu m and CoCrWNi alloy powder are fully mixed to obtain mixed powder with the copper content of 3 wt.%.
Preferably, the step 1: the chemical components of the mixed powder are as follows: cr19.19wt.%, w15.03wt.%, ni10.36wt.%, cu3wt.%, and the balance Co.
Preferably, the step 2: and (3) preparing the material, namely sieving the mixed powder, and then preparing the SLM-CoCrWNi metal block from the qualified mixed powder through an SLM forming instrument.
Preferably, the step 3: and (3) forging, namely peeling the metal block, cutting a dead head to remove the part with uneven components, and forging at the forging temperature of 1250 ℃.
Preferably, the step 4: and (4) performing heat treatment, namely performing heat preservation heat treatment on the forged SLM-CoCrWNi metal block at 1000 ℃ for 1 h.
Preferably, the step 5: and (3) solution treatment, namely performing water-cooling solution treatment on the metal block subjected to heat treatment in the step (4) at 1200 ℃ for 1h, and performing aging treatment for 6h in an environment at 800 ℃.
Preferably, the step 6: and electroplating silver, wherein the anode plate adopts a silver plate with the purity of more than 99.9 percent, the thickness of the silver plate is 10mm, the cathode is a red copper plate, the size of the red copper plate is 20mm × 30mm × 3mm, and the direct current electroplating power supply is adopted for electroplating.
Preferably, the silver plating solution for silver plating in the step 6 is a double complexing agent system consisting of DMH and NA, wherein the DMH concentration is 114g/L, the NA concentration is 18g/L, the temperature is 40 ℃, and the pH range is 10.0-12.0.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. A preparation method capable of improving the antibacterial function of medical cobalt-based alloy is characterized by comprising the following steps: the method comprises the following steps:
step 1: selecting materials;
step 2: preparing a material;
and step 3: forging;
and 4, step 4: heat treatment;
and 5: solution treatment;
step 6: and (4) electroplating silver.
2. The preparation method capable of improving the antibacterial function of the medical cobalt-based alloy according to the claim 1, characterized by comprising the following steps: the step 1: the materials are selected, copper powder with the purity of 99.9 percent and the granularity of 15-50 mu m and CoCrWNi alloy powder are fully mixed to obtain mixed powder with the copper content of 3 wt.%.
3. The preparation method capable of improving the antibacterial function of the medical cobalt-based alloy according to claim 2, wherein the preparation method comprises the following steps: the step 1: the chemical components of the mixed powder are as follows: cr19.19wt.%, w15.03wt.%, ni10.36wt.%, cu3wt.%, and the balance Co.
4. The preparation method capable of improving the antibacterial function of the medical cobalt-based alloy according to the claim 1, characterized by comprising the following steps: the step 2: and (3) preparing the material, namely sieving the mixed powder, and then preparing the SLM-CoCrWNi metal block from the qualified mixed powder through an SLM forming instrument.
5. The preparation method capable of improving the antibacterial function of the medical cobalt-based alloy according to the claim 1, characterized by comprising the following steps: the step 3: and (3) forging, namely peeling the metal block, cutting a dead head to remove the part with uneven components, and forging at the forging temperature of 1250 ℃.
6. The preparation method capable of improving the antibacterial function of the medical cobalt-based alloy according to the claim 1, characterized by comprising the following steps: and 4, the step of: and (4) performing heat treatment, namely performing heat preservation heat treatment on the forged SLM-CoCrWNi metal block at 1000 ℃ for 1 h.
7. The preparation method capable of improving the antibacterial function of the medical cobalt-based alloy according to the claim 1, characterized by comprising the following steps: and step 5: and (3) solution treatment, namely performing water-cooling solution treatment on the metal block subjected to heat treatment in the step (4) at 1200 ℃ for 1h, and performing aging treatment for 6h in an environment at 800 ℃.
8. The preparation method capable of improving the antibacterial function of the medical cobalt-based alloy according to the claim 1, characterized by comprising the following steps: and 6: and electroplating silver, namely adopting a silver plate with the purity of more than 99.9 percent as an anode plate, the thickness of the silver plate is 10mm, adopting a red copper plate as a cathode, and adopting a direct current electroplating power supply to electroplate the silver plate, wherein the size of the red copper plate is 20mm × 30mm × 3mm.
9. The preparation method capable of improving the antibacterial function of the medical cobalt-based alloy according to claim 8, wherein the preparation method comprises the following steps: the silver plating solution for silver electroplating in the step 6 comprises a double complexing agent system consisting of DMH and NA, wherein the DMH concentration is 114g/L, the NA concentration is 18g/L, the temperature is 40 ℃, and the pH range is 10.0-12.0.
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Citations (8)
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| DE102012223239A1 (en) * | 2012-12-14 | 2014-06-18 | BEGO Bremer Goldschlägerei Wilh. Herbst GmbH & Co. KG | Noble metal-dental alloy made of e.g. cobalt, ruthenium, rhodium, palladium, osmium, iridium or platinum, chromium, molybdenum and tungsten, useful for producing metallic component, preferably a dental component as dental restoration |
| CN104651670A (en) * | 2013-11-15 | 2015-05-27 | 中国科学院金属研究所 | Antibacterial infectious forging cobalt-based alloy used for surgical implant and preparation method thereof |
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| CN111455221A (en) * | 2020-04-03 | 2020-07-28 | 钢铁研究总院 | Cobalt-based high-temperature alloy for additive manufacturing, preparation method and application thereof, and additive manufactured product |
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2021
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