CN103205618B - A kind of preparation method of cochrome thin-film material - Google Patents
A kind of preparation method of cochrome thin-film material Download PDFInfo
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- CN103205618B CN103205618B CN201210010765.4A CN201210010765A CN103205618B CN 103205618 B CN103205618 B CN 103205618B CN 201210010765 A CN201210010765 A CN 201210010765A CN 103205618 B CN103205618 B CN 103205618B
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Abstract
The invention discloses a kind of cochrome thin-film material and preparation method thereof, cochrome thin-film material includes cobalt Co element, two kinds of elements of chromium Cr element；The mass percent of each element is: Co:20 ~ 30%, Cr:70 ~ 80%, and cochrome film thickness is 1 ~ 10 μm.The preparation method of above-mentioned cochrome thin-film material uses electrocasting method, is placed in electroforming solution using sulfate system as electroforming solution, metal anode and cathode, and at negative electrode deposit cobalt evanohm；Described electroforming solution specifically includes: the chromic anhybride of 220～260g/L, the cobaltous sulfate of 60～100g/L, the ammonium sulfate of 40～50 g/L.The present invention can prepare the uniform cochrome thin-film material of high stability, high corrosion-resistant, good biocompatibility, is with a wide range of applications in terms of medical product.
Description
Technical field
The present invention relates to a kind of cochrome thin-film material, this material is widely used in medical instruments field；Meanwhile, the invention still further relates to the preparation method of above-mentioned cochrome thin-film material.
Background technology
Cochrome is a kind of excellent biocompatible materials, is widely used in medical instruments field, and it is applied to transplantation treatment the earliest, uses as joint prosthesis.Have been widely used for the treatment of coronary atherosclerosis disease with cochrome for the intravascular drug FirebirdTM that matrix is prepared from, make the support with 316L stainless steel as matrix have more preferable biocompatibility and vessel support；And due to its dense structure, nickel content is low, there is good metallic luster and case hardness simultaneously, also have a wide range of applications in dental implant.More traditional noble metal dental implant, the cobalt chromium alloy porcelain tooth being prepared from this kind of material, its low production cost, preparation technology is simple, there is good corrosion resistance and high mechanical properties simultaneously so that it is implant at medicine equipment, on market, there is bigger advantage.Simultaneously as the content without Ni element or Ni element is extremely low in cochrome, can effectively solve the allergic problem of nickel metal, in implanting patient's mouth, also not have alloy metachromatism simultaneously.
Cochrome has multiple production method: such as direct electro-smelting-purifying method, cold plastic deformation, spatter film forming, twin-roller quenching method etc..But compared with above-mentioned technology of preparing, electrocasting has the advantage that deposition layer has the high density of uniqueness and low hole；The constituent of material can also be controlled by being changed the condition such as parameter, solution composition in technique；Have higher productivity ratio and good economy, easily prepare thin-film material in a large number；Equipment needed thereby investment is relatively low.Therefore electrocasting is to prepare a kind of the most promising method of thin cochrome thin-film material.
At present, the electrodeposition technology of disclosed electroforming cochrome also has a lot of weak point, and as concentration of metal ions is bigger than normal, electrolyte property is not sufficiently stable, and antioxygenic property is relatively low, and deposition layer hardness is high, poor toughness.
In view of this, be necessary in fact to design a kind of avoid nickel use, cost-effective, mitigate the medical cochrome thin-film material of the high-biocompatibility of disposal of three wastes burden.
Content of the invention
It is contemplated that at least solve one of technical problem present in prior art.To this end, it is an object of the present invention to propose a kind of cochrome thin-film material, to avoid the use of nickel, cost-effective, mitigate disposal of three wastes burden.
Another object of the present invention is to propose the preparation method of above-mentioned cochrome thin-film material, high rigidity can be prepared, the uniform alloy material of high-biocompatibility.
A kind of cochrome thin-film material of the present invention, including Co cobalt element, two kinds of elements of Cr chromium element；Wherein, the mass percent of each element is: Co:20%～30%, Cr:70%～80%.
A kind of cochrome thin-film material of the present invention, its thickness range is at 1～10 μm.
The preparation method of a kind of cochrome thin-film material of the present invention, uses electrocasting method, is placed in electroforming solution as electroforming solution, metal anode and cathode using sulfate system, and at negative electrode deposit cobalt evanohm；Described electroforming solution specifically includes: the chromium sulfate of 220～260g/L, the cobaltous sulfate of 60～100g/L, the ammonium sulfate of 40～50 g/L.
Preferably, the minus plate of described metal anode and cathode is 430 corrosion resistant plates；The anode of described metal anode and cathode uses graphite.
Preferably, described preparation method comprises the steps: cleaning step；Activation step；Cleaning step；Electroforming step；Recovery and rinsing step；Baking step.
Preferably, described electroforming solution includes the agent that walks of the stabilizer of following additive: 0.5～1ml/L, the wetting agent of 0.5～1ml/L, 1～5ml/L.
Preferably, the concrete electroforming process parameter of described preparation method is as follows: pH value is 8.0～9.0；Temperature is 60～85 DEG C；Cathode-current density value is 1～3A/dm2；Teeming speed is 9～12 μm/h.
Preferably, described preparation method is provided with the anode baffle of control uniformity.
In the preferred embodiment, can get the alloy that chromium content is 70%～80%, it is to avoid the use of nickel, cost-effective, mitigate disposal of three wastes burden.The alloy film material similar to the physical property of bone alloy-porcelain tooth material can be obtained by electroforming process；The film that present invention process prepares has high rigidity, high compactness and high-biocompatibility.Meanwhile, the selection of cathode material, is conducive to peeling off；The selection of additive, advantageously ensures that high quality of materials (plate face outward appearance)；The selection of operating procedure, advantageously ensures that good plate face outward appearance, without the defect such as pit, pin hole；Solution formula, can guarantee that higher production efficiency.
The attendant advantages of the present invention will be given in following detailed description of the invention part, and concrete advantage substantially will be embodied in following embodiment, or be recognized by the practice of the present invention.
Brief description
Above-mentioned and/or the attendant advantages of the present invention from combine the description to embodiment for the accompanying drawings below will be apparent from easy to understand, wherein:
Fig. 1 is the flow chart of the cochrome thin-film material preparation method according to one embodiment of the invention.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of same or like function from start to finish.The embodiment describing below with reference to accompanying drawing is exemplary, is only used for explaining the present invention, and is not considered as limiting the invention.
The present invention discloses a kind of cochrome thin-film material, including Co cobalt element, two kinds of elements of Cr chromium element；Wherein, the mass percent of each element is: Co:20%-30%, Cr:70%-80%.
The present invention discloses the preparation method of above-mentioned cochrome thin-film material simultaneously, uses electrocasting method, is placed in electroforming solution as electroforming solution, metal anode and cathode using sulfate system, and at negative electrode deposit cobalt evanohm.Described electroforming solution specifically includes: the chromium sulfate of 220～260g/L, the cobaltous sulfate of 60～100g/L, the ammonium sulfate of 40～50 g/L.Wherein, cobalt element and Cr element using the form of sulfate liquor as electrolyte negative electrode generation reduction reaction during electroforming.Preferably, described electroforming solution includes the agent that walks of the stabilizer of following additive: 0.5～1ml/L, the wetting agent of 0.5～1ml/L, 1～5ml/L.The concrete electroforming process parameter of described preparation method is as follows: pH value is 8.0～9.0；Temperature is 60～85 DEG C；Cathode-current density value is 1～3A/dm2；Teeming speed is 9～12 μm/h.
In one embodiment of the invention, it is preferable that the minus plate of described metal anode and cathode is 304 corrosion resistant plates；The anode of described metal anode and cathode uses graphite.
In one embodiment of the invention, described preparation method comprises the steps: cleaning step；Activation step；Cleaning step；Electroforming step；Recovery and rinsing step；Baking step.
Referring to Fig. 1, specifically, described preparation method specifically includes following steps:
Prepare required electroforming cobalt chromium solution according to above-mentioned formulation of electroforming solution, its circulation stirring is uniform, it is heated to required temperature.
Choose the thick core of 1.8mm ~ 2.0mm of bright in mirror surface, surface no marking, carry out pre-treating technology, including electrochemical deoiling, pickling, sandblasting, ultrasonic embathe.
Before electroforming, first carry out activation process, increase the adhesion between cast layer and core.Control soak time well, be allowed to both be not easy to come off, be also easily peeled.
During electroforming, subsidiary conditions include the anode baffle that can improve uniformity, are used for reducing vibrations and the stirring of pin hole, mitigate the circulation timei of cast layer edge effect and the combination of intercycle time and flow.
Adjust ratio and the content of additive, be allowed to surface quality good (free of pinholes, pit, cast layer light).
Control electroforming parameter well, including temperature, pH, current density, Co2+/Cr3+Concentration than etc. so that the cobalt chromium content of electroforming material cast layer out reaches requirement.
Additionally, described preparation method is provided with the anode baffle for controlling uniformity.
Play the effect of control uniformity row.
In the description of this specification, the description of reference term " embodiment ", " some embodiments ", " illustrative examples ", " example ", " specific example " or " some examples " etc. means to combine this embodiment or example describes specific features, structure, material or feature are contained at least one embodiment or the example of the present invention.In this manual, identical embodiment or example are not necessarily referring to the schematic representation of above-mentioned term.And, the specific features of description, structure, material or feature can combine in any one or more embodiment or example in an appropriate manner.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: can carry out multiple change, modification, replacement and modification to these embodiments in the case of without departing from the principle of the present invention and objective, the scope of the present invention is limited by claim and equivalent thereof.
Claims (9)
1. the preparation method of a cochrome thin-film material, it is characterised in that described cochrome thin-film material is made up of Co cobalt element, Cr chromium element；Wherein, the mass percent of each element is: Co: 20%～30%, Cr: 70%～80%；The preparation method of described cochrome thin-film material uses electrocasting method, is placed in electroforming solution using sulfate system as electroforming solution, metal anode and cathode, and at negative electrode deposit cobalt evanohm；Described electroforming solution specifically includes: the chromic anhybride of 220～260g/L, the cobaltous sulfate of 60～100g/L, the ammonium sulfate of 40～50 g/L.
2. the preparation method of cochrome thin-film material according to claim 1, it is characterised in that the thickness of described cochrome thin-film material is 1 ~
10
μ
m。
3. preparation method according to claim 1, it is characterised in that the anode of described metal anode and cathode uses anode graphite.
4. preparation method according to claim 1, it is characterised in that the minus plate of described metal anode and cathode is the 304th, the 306th, the one in 430 corrosion resistant plates.
5. preparation method according to claim 1, it is characterised in that described electroforming solution includes following additive: 0.5～
The stabilizer of 1mL/L, 0.5～
The wetting agent of 1mL/L, 1～
The agent that walks of 5mL/L.
6. preparation method according to claim 1, it is characterised in that described preparation method comprises the steps: cleaning step；Activation step；Cleaning step；Electroforming step；Recovery and rinsing step；Baking step.
7. preparation method according to claim 1, it is characterised in that the concrete electroforming process parameter of described preparation method is as follows:
PH value is 8.0～9.0；Temperature is 60～85 DEG C；Cathode-current density value is 1～3A/dm2；Teeming speed is 9～12 μm/h.
8. preparation method according to claim 1, it is characterised in that described preparation method is provided with the anode baffle of control uniformity.
9. anode baffle according to claim 8, it is characterised in that be provided with and be available for the perforate that solution passes through.
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| CN201210010765.4A CN103205618B (en) | 2012-01-16 | 2012-01-16 | A kind of preparation method of cochrome thin-film material |
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| CN201210010765.4A CN103205618B (en) | 2012-01-16 | 2012-01-16 | A kind of preparation method of cochrome thin-film material |
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| CN103205618A CN103205618A (en) | 2013-07-17 |
| CN103205618B true CN103205618B (en) | 2016-10-05 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953484A (en) * | 1957-07-22 | 1960-09-20 | Allen Bradley Co | Cobalt-chromium electrical resistance device |
| US3816111A (en) * | 1971-05-12 | 1974-06-11 | Sulzer Ag | Chromium-base alloy for making a chill-mold and a process of making same |
| CN1794374A (en) * | 2005-12-06 | 2006-06-28 | 钢铁研究总院 | Nanometer crystal soft magnetic alloy film material and its preparation method |
| CN102021365A (en) * | 2010-12-30 | 2011-04-20 | 许正诚 | Cobalt chromium alloy |
| CN201817561U (en) * | 2010-10-28 | 2011-05-04 | 南通华达微电子集团有限公司 | Opening shape-adjustable electroplate anode baffle |
| CN102154665A (en) * | 2011-03-21 | 2011-08-17 | 济南德锡科技有限公司 | Trivalent chromium plating solution composite, preparation method thereof and chromium plating process |
-
2012
- 2012-01-16 CN CN201210010765.4A patent/CN103205618B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953484A (en) * | 1957-07-22 | 1960-09-20 | Allen Bradley Co | Cobalt-chromium electrical resistance device |
| US3816111A (en) * | 1971-05-12 | 1974-06-11 | Sulzer Ag | Chromium-base alloy for making a chill-mold and a process of making same |
| CN1794374A (en) * | 2005-12-06 | 2006-06-28 | 钢铁研究总院 | Nanometer crystal soft magnetic alloy film material and its preparation method |
| CN201817561U (en) * | 2010-10-28 | 2011-05-04 | 南通华达微电子集团有限公司 | Opening shape-adjustable electroplate anode baffle |
| CN102021365A (en) * | 2010-12-30 | 2011-04-20 | 许正诚 | Cobalt chromium alloy |
| CN102154665A (en) * | 2011-03-21 | 2011-08-17 | 济南德锡科技有限公司 | Trivalent chromium plating solution composite, preparation method thereof and chromium plating process |
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| CN103205618A (en) | 2013-07-17 |
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