CN102392249B - Method for removing coatings on surfaces of hard alloys - Google Patents
Method for removing coatings on surfaces of hard alloys Download PDFInfo
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- CN102392249B CN102392249B CN 201110382784 CN201110382784A CN102392249B CN 102392249 B CN102392249 B CN 102392249B CN 201110382784 CN201110382784 CN 201110382784 CN 201110382784 A CN201110382784 A CN 201110382784A CN 102392249 B CN102392249 B CN 102392249B
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Abstract
The invention discloses a method for removing coatings on the surfaces of hard alloys. In the invention, alkali is used as a reactant; and under the action of alkali salt with high melting point, the melting point of the reactant is controlled and then the reaction temperature is controlled, so that the alkali in molten state only acts with the coatings on the surfaces of the hard alloys and does not act with the matrix materials of the hard alloys. By using the method provided by the invention, not only the aluminum oxide on the surfaces of the hard alloys can be removed, but the coatings such as TiC, TiN, TiA1N, A1CrSiN and the like also can be removed without damaging the matrixes of the hard alloys; and after the treatment, the outer surface structures of the hard alloy materials are compact and the contents of the elements such as wolfram (W), cobalt (Co), titanium (Ti), nickel (Ni) and the like are not decreased.
Description
Technical field
The present invention relates to a kind for the treatment of process of hard alloy piece, be specifically related to a kind for the treatment of process of coatings on surfaces of hard alloys.
Background technology
China is the big producing country of Wimet in the world, and the production of Wimet has consumed the important resources such as a large amount of tungsten (W), cobalt (Co), titanium (Ti), nickel (Ni), causes the day by day poor situation of this strategic resource.Therefore, strengthen the research of scrap hard alloy recycle, improve the rate of recovery of tungsten, cobalt, titanium, nickel in waste alloy, realize that the application of reclaimed materials in high-grade hart metal product production seems particularly important.
At present, hard alloy piece has all passed through the top coat processing basically, effectively removes as effects on surface coating not, and the top coat thing will directly be sneaked in the secondary raw material of recovery, affect later regeneration hart metal product quality.Because coating film and hard alloy substrate mutually combine tightly, cohesive force is strong, and the characteristics such as coated component complex structure, hardness be high, anti-oxidant, wear-resisting and corrosion-resistant, gives again to remove hard and close top coat and brought very large difficulty.In succession reported the method for some decoatings both at home and abroad.For example adopt vacuum treated method that TiC, TiN hard alloy coating are peeled off; Adopt hydrogen peroxide and potassium oxalate alkaline mixed solution and the vitriol oil and two kinds of methods of peeling off the TiAlN coating of potassium permanganate mixing solutions.Aluminium sesquioxide has very high thermostability and chemical stability, be difficult to dissolving, prior art generally adopts sodium carbonate-borax mixed solvent or nitric acid-sulfuric acid mixing acid to carry out pyrolytic decomposition in platinum crucible, experiment is found, after sodium carbonate-borax mixed solvent is processed, carbide surface adheres to the extremely strong material of one deck viscosity, and Wimet change of shape after pyroprocessing is large, and the cemented carbide substrate surfaces infringement is serious; Cobalt reaction in nitric acid-sulfuric acid mixing acid and hard alloy substrate causes cobalt to run off in a large number, the present rarely seen report of removal effective ways to aluminum oxide coating.Therefore, research is removed aluminium sesquioxide and other coating and is not injured the method for cemented carbide substrate, has positive industrial significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that can effectively remove coatings on surfaces of hard alloys, it not only can remove the aluminium sesquioxide of carbide surface, and can remove the coatings such as TiC, TiN, TiAlN, and do not injure hard alloy substrate, the constituent contents such as the tungsten in Wimet (W), cobalt (Co), titanium (Ti), nickel (Ni) also can not descend, and the Hardmetal materials outer surface structure after processing is fine and close.
The present invention can solve above-mentioned prior art problem by implementing following technical scheme and processing step:
(1) with the hard alloy piece surface of coating routinely cleaning clean and dry, pending;
(2) add 0.01～0.5 mass parts fusing point higher than the inorganic base metal salt solid powder of 300 ℃ in the alkali metal hydroxide pressed powder, mix;
(3) alkali metal hydroxide and inorganic base metal salt mixture are heated to 300～900 ℃ in plumbago crucible, the hard alloy piece of the coating that will clean up and dry again immerses in the above-mentioned alkali metal hydroxide and inorganic base metal salt mixture that is molten state, constant temperature keeps 5～180 minutes reaction times, and hard alloy piece is fully contacted with fused solution;
(4) take out above-mentioned hard alloy piece, to be cooled, clean and dry after, obtain the hard alloy piece that coating is removed clean.
In order to obtain better result of use, the present invention can also implement following technical measures: above-mentioned alkali metal hydroxide pressed powder is sodium hydroxide or potassium hydroxide pressed powder; Above-mentioned fusing point is one or more combination in sodium carbonate, sodium sulfate, sodium-chlor, Sodium chromate, SODIUMNITRATE, salt of wormwood, vitriolate of tartar, Repone K, potassiumchromate, saltpetre higher than the inorganic base metal salt solid powder of 300 ℃; Above-mentioned temperature of reaction is 600～800 ℃; Temperature of reaction the best is 700 ℃; The above-mentioned reaction times is 10～80 minutes; Reaction times the best is 40 minutes; It is above-mentioned that hard alloy piece and fused solution are fully contacted is by stirring rake or/and shake, vibrate plumbago crucible and realize; Above-mentioned conventional cleaning is for washing away the surface and oil contaminant that adheres to, borings etc. with acetone, then uses successively pure water, alcohol ultrasonic cleaning; Above-mentioned alcohol ultrasonic cleaning time 5-30 minute.
Compare with other methods of removing the carbide surface coating, the present invention has following advantage:
1, production cost is low.The reactant that relates in the present invention is common medicine, and conditional request is loose;
2, production technique is simple.Reaction process of the present invention is simple, need not to drop into more equipment and can satisfy processing requirement;
3, practical, adaptability is high.The present invention also is fit to the removal of other top coats of hard alloy piece except the removal that is fit to hard alloy piece aluminium sesquioxide top coat.
Description of drawings
Fig. 1 is sample power spectrum ultimate analysis figure after embodiment 8 processes.
Embodiment
Embodiment 1
Get one piece of the scrap hard alloy coated chip of trade mark IC9350, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, then after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the sodium carbonate solid of 5% mass ratio in solid sodium hydroxide, mix.
Solid mixture is heated up in plumbago crucible, to 600 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 80min time in the fused solution of 600 ℃, and need stir the assurance molten sodium hydroxide and Wimet fully reacts by stirring rake.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Get one piece of the scrap hard alloy coated chip of trade mark GC3215, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the sodium carbonate solid of 10% mass ratio in solid sodium hydroxide, mix.
Solid mixture is heated up in plumbago crucible, to 750 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 5min time in the fused solution of 750 ℃, and need to guarantee that by shaking plumbago crucible molten sodium hydroxide and Wimet fully react.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Embodiment 3
Get one piece of the scrap hard alloy coated chip of trade mark YBC252, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the sodium sulfate solid of 1% mass ratio in solid sodium hydroxide, mix.
Solid mixture is heated up in plumbago crucible, to 900 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 5min time in the fused solution of 900 ℃, and need guarantee that by stirring molten sodium hydroxide and Wimet fully react.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Get one piece of the scrap hard alloy coated chip of trade mark IC9150, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the solid sodium chloride of 50% mass ratio in solid sodium hydroxide, mix.
Solid mixture is heated up in plumbago crucible, to 300 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 180min time in the fused solution of 300 ℃, and need guarantee that by stirring molten sodium hydroxide and Wimet fully react.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Embodiment 5
Get one piece of the scrap hard alloy coated chip of trade mark GC4235, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the SODIUMNITRATE solid of 15% mass ratio in solid sodium hydroxide, mix.
Solid mixture is heated up in plumbago crucible, to 400 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 150min time in the fused solution of 400 ℃, and need guarantee that by stirring molten sodium hydroxide and Wimet fully react.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Get one piece of the scrap hard alloy coated chip of trade mark GC3215, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, then after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the solid sodium chloride of 20% mass ratio in solid sodium hydroxide, mix.
Solid mixture is heated up in plumbago crucible, to 600 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 40min time in the fused solution of 600 ℃, and need stir the assurance molten sodium hydroxide and Wimet fully reacts by stirring rake.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Embodiment 7
Get one piece of the scrap hard alloy coated chip of trade mark GC4225, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the Sodium chromate solid of 30% mass ratio in solid sodium hydroxide, mix.
Solid mixture is heated up in plumbago crucible, to 800 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 100min time in the fused solution of 800 ℃, and need guarantee that by stirring molten sodium hydroxide and Wimet fully react.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Get one piece of the scrap hard alloy coated chip of trade mark YBC152, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the sodium carbonate solid of 10% mass ratio, the solid sodium chloride of 15% mass ratio, the sodium sulfate solid of 5% mass ratio, the Sodium chromate solid of 5% mass ratio, the SODIUMNITRATE solid of 5% mass ratio in solid sodium hydroxide, mix.
Solid mixture is heated up in plumbago crucible, to 700 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 40min time in the fused solution of 700 ℃, and need guarantee that by stirring molten sodium hydroxide and Wimet fully react.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Embodiment 9
Solid sodium hydroxide is replaced with solid potassium hydroxide, and sodium carbonate replaces with salt of wormwood, and other are with embodiment 1.
Solid sodium hydroxide is replaced with solid potassium hydroxide, and sodium carbonate replaces with salt of wormwood, and other are with embodiment 2.
Embodiment 11
Solid sodium hydroxide is replaced with solid potassium hydroxide, and sodium sulfate replaces with vitriolate of tartar, and other are with embodiment 3.
Solid sodium hydroxide is replaced with solid potassium hydroxide, and sodium-chlor replaces with Repone K, and other are with embodiment 4.
Embodiment 13
Solid sodium hydroxide is replaced with solid potassium hydroxide, and SODIUMNITRATE replaces with saltpetre, and other are with embodiment 5.
Solid sodium hydroxide is replaced with solid potassium hydroxide, and sodium-chlor replaces with Repone K, and other are with embodiment 6.
Embodiment 15
Solid sodium hydroxide is replaced with solid potassium hydroxide, the SODIUMNITRATE solid that the Sodium chromate solid that the sodium sulfate solid that the solid sodium chloride that the sodium carbonate solid of 10% mass ratio replaces with potash solid, 15% mass ratio of 10% mass ratio replaces with the solid potassium chloride of 15% mass ratio, 5% mass ratio replaces with vitriolate of tartar solid, 5% mass ratio of 5% mass ratio replaces with the potassiumchromate solid of 5% mass ratio, 5% mass ratio replaces with the saltpetre solid of 5% mass ratio, and other are with embodiment 8.
Embodiment 16
Get one piece of the scrap hard alloy coated chip of trade mark YBC152, wash away the surface and oil contaminant that adheres to, borings etc. with acetone, after using successively pure water, alcohol ultrasonic cleaning, put into the drying baker oven dry.
Add the sodium carbonate solid of 5% mass ratio, the potash solid of 5% mass ratio, the solid sodium chloride of 7.5% mass ratio, the solid potassium chloride of 7.5% mass ratio, the sodium sulfate solid of 1% mass ratio, the vitriolate of tartar solid of 1% mass ratio, the Sodium chromate solid of 1% mass ratio, the potassiumchromate solid of 1% mass ratio, the SODIUMNITRATE solid of 2% mass ratio, the saltpetre solid of 2% mass ratio in the solid potassium hydroxide mixture of the solid sodium hydroxide of 50% mass ratio and 50% mass ratio, mix.
Solid mixture is heated up in plumbago crucible, to 700 ℃ of fusings, then the scrap hard alloy coated chip is immersed in temperature and is the constant temperature 40min time in the fused solution of 700 ℃, and need guarantee that by stirring molten sodium hydroxide and Wimet fully react.
Take out blade after reaction finishes, cleaning, drying obtains the carbide chip that coating is removed clean.
Embodiment 17
Following trade mark hard alloy piece sample is processed
| Coated component | The affiliated trade mark |
| Al 2O 3 - TiCN | GC4225、GC4205、GC4215、GC4235 |
| Ti (C,N) - Al 2O 3 - TiN | GC3005、GC2015、GC2025 |
| TiN - TiC - TiN | GC235 |
| Ti (C,N) - Al 2O 3 | GC3205、GC3215、S05F |
| TiAlN、TiN | GC1025 |
| TiA1N | GC1005、GC1105、GC1125 |
| PCBN | GC1115 |
| TiAlN - TiN | GC2035 |
| Ti（C,N）- TiN | GC1525 |
By embodiment 8 methods, above-mentioned trade mark hard alloy piece sample is processed, obtained the hard alloy piece blade that coating is removed clean.
Claims (8)
1. method of removing coatings on surfaces of hard alloys, its processing step is:
(1) with the hard alloy piece surface of coating routinely cleaning clean and dry, pending;
(2) add 0.01～0.5 mass parts fusing point higher than the inorganic base metal salt solid powder of 300 ℃ in the alkali metal hydroxide pressed powder, mix;
(3) alkali metal hydroxide and inorganic base metal salt mixture are heated to 300～900 ℃ in plumbago crucible, the hard alloy piece of the coating that will clean and dry again immerses in the above-mentioned alkali metal hydroxide and inorganic base metal salt mixture that is molten state, constant temperature keeps 5～180 minutes reaction times, and hard alloy piece is fully contacted with fused solution;
(4) take out above-mentioned hard alloy piece, to be cooled, clean and dry after, obtain the hard alloy piece that coating is removed clean.
2. the method for removal coatings on surfaces of hard alloys according to claim 1, is characterized in that described alkali metal hydroxide pressed powder is sodium hydroxide or potassium hydroxide pressed powder.
3. the method for removal coatings on surfaces of hard alloys according to claim 1 is characterized in that described fusing point is one or more combination in sodium carbonate, sodium sulfate, sodium-chlor, Sodium chromate, SODIUMNITRATE, salt of wormwood, vitriolate of tartar, Repone K, potassiumchromate, saltpetre higher than the inorganic base metal salt solid powder of 300 ℃.
One of according to claim 1 to 3 described removal coatings on surfaces of hard alloys method, it is characterized in that described temperature of reaction is 600～800 ℃.
5. the method for removal coatings on surfaces of hard alloys according to claim 4, is characterized in that described reaction optimum temps is 700 ℃.
One of according to claim 1 to 3 described removal coatings on surfaces of hard alloys method, it is characterized in that the described reaction times is 10～80 minutes.
7. the method for removal coatings on surfaces of hard alloys according to claim 6, is characterized in that described reaction times the best is 40 minutes.
One of according to claim 1 to 3 described removal coatings on surfaces of hard alloys method, it is characterized in that described hard alloy piece and fused solution are fully contacted is by stirring rake or/and shake, vibrate plumbago crucible and realize.
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| TWI629719B (en) * | 2015-01-15 | 2018-07-11 | 聯華電子股份有限公司 | Multi-stage cleaning method for susceptor |
| CN109576723B (en) * | 2019-01-29 | 2020-08-28 | 苏州涂冠镀膜科技有限公司 | Film stripping liquid and method for removing nitride film on surface of cobalt-based hard alloy |
| CN113666374A (en) * | 2021-08-23 | 2021-11-19 | 嘉兴鸷锐新材料科技有限公司 | Method for recovering carbide from waste Ti (C, N) -based metal ceramic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1696350A (en) * | 2005-06-17 | 2005-11-16 | 自贡科瑞德新材料有限责任公司 | Method for removing coat layer on surface of coated hard alloy |
| CN1929931A (en) * | 2004-01-30 | 2007-03-14 | 西门子公司 | Method for removing a layer |
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| CN1635180A (en) * | 2004-12-30 | 2005-07-06 | 北京航空航天大学 | Process for removing ceramic layer from thermal barrier coating |
| CN100366366C (en) * | 2005-12-29 | 2008-02-06 | 东营市恒诚精密铸造有限责任公司 | Tech. for removing sand by high temp. alkaline explosion |
| CN100497743C (en) * | 2006-03-17 | 2009-06-10 | 中国科学院金属研究所 | Chemical removing method of ion-plating TiAlN coating on stainless steel substrate |
| CN101709474B (en) * | 2009-11-26 | 2011-06-22 | 攀钢集团江油长城特殊钢有限公司 | Alkali-acid washing method for titanium alloy |
| CN101818360B (en) * | 2010-03-16 | 2011-11-30 | 西安泰金工业电化学技术有限公司 | Method for removing waste titanium anode coating |
| CN102573158B (en) * | 2012-01-05 | 2014-04-09 | 江苏舾普泰克自动化科技有限公司 | Method and device for removing electromagnetic induction type metallic surface coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1929931A (en) * | 2004-01-30 | 2007-03-14 | 西门子公司 | Method for removing a layer |
| CN1696350A (en) * | 2005-06-17 | 2005-11-16 | 自贡科瑞德新材料有限责任公司 | Method for removing coat layer on surface of coated hard alloy |
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