CN1686640A - Black phosphate coating treatment method of power melallugical workpiece - Google Patents
Black phosphate coating treatment method of power melallugical workpiece Download PDFInfo
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- CN1686640A CN1686640A CN 200510020633 CN200510020633A CN1686640A CN 1686640 A CN1686640 A CN 1686640A CN 200510020633 CN200510020633 CN 200510020633 CN 200510020633 A CN200510020633 A CN 200510020633A CN 1686640 A CN1686640 A CN 1686640A
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Abstract
A black phosphorizing process for the workpiece made by powder metallurgy includes such steps as washing surface, removing oil, prephosphorizing, removing film, washing with acid, regulating pH value of surface, and phosphorizing.
Description
Technical Field
The invention belongs to the field of metal surface treatment, and particularly relates to a black phosphating method for powder metallurgy metal, wherein a phosphate coating is generated on the surface of the powder metal, the color of the phosphate coating is black, and the phosphate coating is crystallized and is fine.
Background
The powder metallurgy metal technology is a precision casting technology, and is used for the production of the mechanical industry, and due to the unique casting performance, the method can reduce machining, even does not need machining, can improve the utilization rate of materials, reduce the production cost, improve the quality of products and improve the production efficiency. In the production of mechanical industry, some workpieces need to be subjected to phosphating treatment on the surfaces, and the treated phosphating layer is required to be black in color and luster, and the phosphating layer does not fall off after phosphating. The traditional black phosphating process for the surface of the powder metallurgy metal workpiece comprises the following steps: cleaning the workpiece after deoiling, pickling, cleaning again, adjusting the surface, and cleaning after phosphating. Because the main components of the powder metallurgy metal are iron, cobalt,Molybdenum Ni18Co9Mn5It is composed of hydroxyl iron powder, hydroxyl nickel powder, micro-level cobalt powder and molybdenum powder. The components of the powder metal injection piece are iron powder, nickel powder and glue, and the powder is mixed, pressed and molded and then sintered, the method ensures that the alloy elements in the components are too high, when the workpiece is phosphorized by the traditional phosphorization process, a film cannot be formed on the surface, and meanwhile, the black scale is difficult to scale by the surface residues after sintering, so the surface of the workpiece cannot be phosphorized, and even if a phosphorization layer exists, the color of the phosphorization layer is gray, the product design requirement cannot be met, and the phosphorization layer is easy to fall off after phosphorization.
Disclosure of Invention
The invention aims to provide a black phosphating method for a powder metallurgy workpiece. The phosphating agent can be used for phosphating the surface of a powder metallurgy workpiece, the color of a phosphating layer is black, the phosphating layer is fine and dense in crystallization, and the phosphating layer does not fall off after use.
The technical scheme of the invention is as follows:
treating the surface of the workpiece according to the following steps:
cleaning the surface of the powder metallurgy metal by a conventional method;
deoiling;
phosphating treatment
After being cleaned, the metal surface is subjected to black phosphating treatment according to the steps of pre-phosphating, film removal, acid cleaning, surface conditioning and rephosphorization.
The chemical composition of the phosphating solution is
65-95 g/l manganese acid phosphate
Nickel sulfate 3-5 g/l
Tartaric acid 1-3 g/L
The total acid is 90-100 points, and the free acid is 12-18 points.
The pre-phosphorization condition is that the phosphorization liquid is phosphorized for 5-7 minutes at the solution temperature of 95-100 ℃.
The membrane removing condition is that the membrane removing liquid is removed for 5 to 10 minutes at the temperature of between 95 and 100 ℃.
The chemical component of the film removing liquid is
NaOH 400-500 g/l;
KmnO420-30 g/l.
The condition of surface conditioning is to condition the surface conditioning liquid at 40-60 deg.C for 20-60 s.
The chemical components of the surface conditioning liquid are
Manganese phosphate 0.8-2 g/L;
sodium carbonate 0.8-2 g/l.
The condition of re-phosphorization is that the phosphorization liquid is placed in the solution at 95-100 deg.C for 15-25 min.
The phosphorus-free degreasing agent is used as the degreasing agent for degreasing, the operating temperature is 50-70 ℃, and the operating time is 10-15 minutes. The content of the phosphorus-free degreasing agent in the degreaser is 30-50 g/L.
The phosphorus-free degreasing agent can be a commercially available phosphorus-free degreasing agent without phosphate.
The phosphating solution is used for pre-phosphating powder parts and then is used for stripping the film by the film stripping solution, so that the loose film on the surface is completely removed, and then the phosphating is carried out for the second time, because the phosphating process has long duration and longer time for re-phosphating, the firmness of the phosphating film is promoted, and the following reaction is generated in the phosphating process
Me represents various metals.
The reason why the surface adjustment is needed before the second phosphating is that: 1. the surface of the degreased and pickled powder workpiece is provided with extremely fine micropores, manganese phosphate particles are adsorbed in the micropores through surface adjustment, a catalyst effectis realized during black phosphating, and a phosphating reaction can be accelerated; 2. the surface conditioning can enable the surface of the workpiece to generate a fine black phosphating film, can ensure that the color of the phosphating layer is black after the workpiece is subjected to black phosphating, and the phosphating layer does not fall off after the workpiece is used.
The invention can generate Me (PO) composed of multiple elements of iron, manganese, nickel and the like on the surface of a workpiece in a weak acid solution during phosphorization4)2Membrane, Me (PO)4)2The film is difficult to be cleaned in the acid washing process, and in addition, the phosphating film generated after the pre-phosphating is incomplete and incomplete, so that the film stripping after the pre-phosphating can ensure Me (PO) on the surface of the workpiece4)2Membrane removal, since the membrane removal is carried out in a strongly alkaline solution, Me (PO)4)2Membrane in strong base NaOH and strong oxidant KmnO4Is destroyed by the action of (2), then is pickled with hydrochloric acid, Me (PO)4)2The film is removed completely, the surface of the workpiece is grey white, the phosphating reaction can be completed when the workpiece is phosphated again, the film layer is uniform, the color of the phosphating layer is black after the workpiece is subjected to black phosphating, and the phosphating layer does not fall black after the workpiece is used.
The present invention will be further described with reference to the following examples.
Detailed Description
Example 1
Cleaning a powder workpiece with water, degreasing the powder workpiece for 15min at the temperature of 50-70 ℃ by using 30 g/L of phosphorus-free degreasing agent, and chemically degreasing the powder workpiece; washing with water, acid washing with HCl170 g/L at room temperature for 1-3min, washing with water, pre-phosphorizing with phosphorizing liquid containing manganese acid phosphate 65 g/L, nickel sulfate 3 g/L, tartaric acid 1 g/L, and Fe2+0.3 g/L preparation, wherein the total acid is controlled at 90-100 points, and the free acid is 12-18 points; then, washing with hot water at the temperature of 70-80 ℃, and stripping the film with strong alkaline solution and strong oxidant under the condition of NaOH 400 g/L; KmnO420 g/l, stripping the film at 95-110 deg.C for 1-3min, washing with water, acid washing at room temperature with HCl170-250 g/l1-3min, washing with water, surface conditioning with surface conditioner at 40-60 deg.C for 20-60 s, preparing surface conditioner with manganese phosphate 0.8-2 g/L and sodium carbonate 0.8-2 g/L, re-phosphating with phosphating solution 65 g/L, nickel sulfate 3 g/L, tartaric acid 1 g/L, Fe for 15-25min, and adding sodium sulfate, etc2+0.3 g/L preparation, controlling the total acid at 90-100 points, controlling the free acid at 12-18 points, then washing with hot water at 70-80 ℃, then washing with water, scalding and drying with 3-5 g/L soapy water at 90-95 ℃ for 1-3min, drying at 70-80 ℃ for 15min, cooking high-temperature oil at 105-130 ℃ for 3-5min, and cooking the high-temperature oil with 100% total loss system oil. And finishing the black phosphating process on the surface of the workpiece.
Example 2
Cleaning a powder workpiece with water, degreasing the powder workpiece for 15min at the temperature of 50-70 ℃ by using a phosphorus-free degreasing agent with the weight of 40 g/L, and chemically degreasing the powder workpiece; washing with water, acid washing with HCl170 g/L at room temperature for 1-3min,washing with water, pre-phosphorizing with phosphorizing liquid containing manganese acid phosphate 80 g/L, nickel sulfate 4 g/L, tartaric acid 2 g/L, and Fe2+2 g/L preparation, wherein the total acid is controlled at 90-100 points, and the free acid is 12-18 points; then using hot water with the temperature of 70-80 DEG CCleaning, and stripping the film by using a strong alkali solution and a strong oxidant under the condition of NaOH 450 g/L; KmnO425 g/L, stripping the film for 1-3min at the temperature of 95-110 ℃, washing with water and then acid cleaning, wherein the acid cleaning condition is that HCL is 170-250 g/L, the acid cleaning is carried out for 1-3min at room temperature, then washing with water is carried out, the surface conditioning is carried out for 20-60 s at the temperature of 40-60 ℃ after water cleaning, the surface conditioning is prepared by using manganese phosphate 0.8-2 g/L and sodium carbonate 0.8-2 g/L, the phosphating solution is used for secondary phosphating for 15-25min after surface conditioning, the phosphating solution is used for using manganese acid phosphate 80 g/L, nickel sulfate 4 g/L, tartaric acid 2 g/L, Fe2+2 g/l preparation, the total acid is controlled at 90-100 points, the free acid is 12-18 points, then the mixture is washed by hot water with the temperature of 70-80 ℃, then washed by water, dried by hot water with the temperature of 3-5 g/l soap water at 90-95 ℃ for 1-3min, dried at 70-80 ℃ for 15min, and dried in the hot waterBoiling the high-temperature oil at the temperature of 105 ℃ and 130 ℃ for 3-5min, wherein the oil for boiling the high-temperature oil adopts 100% total loss system oil. And finishing the black phosphating process on the surface of the workpiece.
Example 3
Cleaning a powder workpiece with water, degreasing the powder workpiece for 15min at the temperature of 50-70 ℃ by using a phosphorus-free degreasing agent with the weight of 50 g/L, and chemically degreasing the powder workpiece; washing with water, acid washing with HCl170 g/L at room temperature for 1-3min, washing with water, pre-phosphorizing with phosphorizing liquid containing manganese acid phosphate 95 g/L, nickel sulfate 5 g/L, tartaric acid 3 g/L, and Fe2+3.5 g/l, the total acid is controlled at 90-100 points, and the free acid is 12-18 points; then, washing with hot water at the temperature of 70-80 ℃, and stripping the film with strong alkaline solution and strong oxidant under the condition of NaOH500 g/L; KmnO430 g/L, stripping the film for 1-3min at the temperature of 95-110 ℃, washing with water and then acid cleaning, wherein the acid cleaning condition is that HCL is 170-250 g/L, the acid cleaning is carried out for 1-3min at room temperature, then washing with water is carried out, the surface conditioning is carried out for 20-60 s at the temperature of 40-60 ℃ after water cleaning, the surface conditioning is prepared by using manganese phosphate 0.8-2 g/L and sodium carbonate 0.8-2 g/L, the phosphating solution is used for secondary phosphating for 15-25min after surface conditioning, the phosphating solution is used for 95 g/L manganese acid phosphate, 5 g/L nickel sulfate, 3 g/L tartaric acid and Fe2+3.5 g/l, total acid controlled at 90-100 points, free acid at 12-18 points, followed by washing with hot water at 70-80 deg.C, then with water,scalding with 3-5 g/L soapy water at 90-95 deg.C for 1-3min, oven drying at 70-80 deg.C for 15min, boiling high temperature oil at 105 deg.C and 130 deg.C for 3-5min, and boiling the high temperature oil with 100% total loss system oil. And finishing the black phosphating process on the surface of the workpiece.
In the process, the surface regulator needs to be supplemented every day, the preparation temperature is 40-60 ℃, and 0.8-2 g/L of manganese phosphate and 0.8-2 g/L of sodium carbonate in the solution are ensured.
During phosphorization, the total acid of the solution is controlled at 90-100 points and the free acid is controlled at 12-18 points. Wherein the total acidity and free acid during phosphorization need to be measured every day by absorbing 10 ml of phosphorization liquid and measuring the total acid by using phenolphthalein as a measuring mediumIndicator, measuring free acid by using methyl orange as indicator, titrating 1 ml with 0.1 or 0.5mol/NaOH standard solution to obtain 1 'point', wherein free acid in the prepared solution is H3PO4. Total acids include free H3PO4And Me (H)2PO4)2And the sum of the acidity.
The appearance of the workpiece after phosphating treatment by the invention is checked by visual inspection to avoid the dropping of phosphate coating, and the phosphate coating is black and fine in color and luster. Soaking 0.5% of CuSO into 100 g of 46# carborundum after falling down at a height of 600mm4And performing a sand shakeout test, wherein the surface of the sample is free of copper and damage. The neutral salt spray test is carried out for more than 90 minutes according to the GB11376 standard, and the surface of the alloy has no corrosion.
Claims (10)
1. A black phosphating treatment method for a powder metallurgy workpiece is characterized in that the surface of the workpiece is treated according to the following steps:
cleaning the surface of the powder metallurgy metal by a conventional method;
deoiling;
phosphating treatment
After being cleaned, the metal surface is subjected to black phosphating treatment according to the steps of pre-phosphating,film removal, acid cleaning, surface conditioning and rephosphorization.
2. The method of black phosphating of powder metallurgical work pieces according to claim 2, characterized in that: the chemical composition of the phosphating solution is
65-95 g/l manganese acid phosphate
3-5 g/L of nickel nitrate
Tartaric acid 1-3 g/L
The total acid is 90-100 points, and the free acid is 12-18 points.
3. The method of black phosphating of powder metallurgical work pieces according to claim 1, characterized in that: the pre-phosphorization condition is that the phosphorization liquid is phosphorized for 5-7 minutes at the solution temperature of 95-100 ℃.
4. The method of black phosphating of powder metallurgical work pieces according to claim 1, characterized in that: the membrane removing condition is that the membrane removing liquid is removed for 5 to 10 minutes at the temperature of between 95 and 100 ℃.
5. The method of black phosphating of powder metallurgical work pieces according to claim 4, characterized in that: the chemical component of the film removing liquid is
NaOH 400-500 g/l;
KMnO420-30 g/l.
6. The method of black phosphating of powder metallurgical work pieces according to claim 1, characterized in that: the condition of surface conditioning is to condition the surface conditioning liquid at 40-60 deg.C for 20-60 s.
7. The method of black phosphating of powder metallurgical work pieces according to claim 6, characterized in that: the chemical components of the surface conditioning liquid are
Manganese phosphate 0.8-2 g/L;
sodium carbonate 0.8-2 g/l.
8. The method of black phosphating of powder metallurgical work pieces according to claim 1, characterized in that: the condition of re-phosphorization is that the phosphorization liquid is placed in the solution at 95-100 deg.C for 15-25 min.
9. The method of black phosphating of powder metallurgical work pieces according to claim 1, characterized in that: the phosphorus-free degreasing agent is used as the degreasing agent for degreasing, the operating temperature is 50-70 ℃, and the operating time is 10-15 minutes.
10. The method of black phosphating of powder metallurgical work pieces according to claim 1, characterized in that: the content of the phosphorus-free degreasing agent in the degreaser is 30-50 g/L.
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| CNB200510020633XA CN100509215C (en) | 2005-03-28 | 2005-03-28 | Black phosphate coating treatment method of powder melallugical workpiece |
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| CNB200510020633XA CN100509215C (en) | 2005-03-28 | 2005-03-28 | Black phosphate coating treatment method of powder melallugical workpiece |
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| CN100509215C CN100509215C (en) | 2009-07-08 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464005C (en) * | 2006-10-18 | 2009-02-25 | 重庆建设摩托车股份有限公司 | Surface treatment method for silencer internal wall |
| CN102430506A (en) * | 2011-12-15 | 2012-05-02 | 江苏腾奇电力设备科技有限公司 | Paint coating process for radiator cast |
| CN104046977A (en) * | 2013-03-12 | 2014-09-17 | 富准精密工业(深圳)有限公司 | Magnesium alloy forming method |
| CN108034938A (en) * | 2017-12-15 | 2018-05-15 | 中广核工程有限公司 | A kind of method and phosphating solution of nuclear power generating equipment bolt phosphatization |
| CN115595572A (en) * | 2022-06-10 | 2023-01-13 | 扬州保来得科技实业有限公司（Cn） | Method for improving corrosion resistance of powder metallurgy iron substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103233215B (en) * | 2013-05-10 | 2015-08-12 | 江苏永昊高强度螺栓有限公司 | Bolt surface blackening |
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2005
- 2005-03-28 CN CNB200510020633XA patent/CN100509215C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100464005C (en) * | 2006-10-18 | 2009-02-25 | 重庆建设摩托车股份有限公司 | Surface treatment method for silencer internal wall |
| CN102430506A (en) * | 2011-12-15 | 2012-05-02 | 江苏腾奇电力设备科技有限公司 | Paint coating process for radiator cast |
| CN104046977A (en) * | 2013-03-12 | 2014-09-17 | 富准精密工业(深圳)有限公司 | Magnesium alloy forming method |
| US9416454B2 (en) | 2013-03-12 | 2016-08-16 | Fu Zhun Precision Industry (Shen Zhen) Co., Ltd. | Method for conversion treating surface of magnesium alloy workpiece |
| CN104046977B (en) * | 2013-03-12 | 2017-02-22 | 富准精密工业(深圳)有限公司 | Magnesium alloy forming method |
| CN108034938A (en) * | 2017-12-15 | 2018-05-15 | 中广核工程有限公司 | A kind of method and phosphating solution of nuclear power generating equipment bolt phosphatization |
| CN115595572A (en) * | 2022-06-10 | 2023-01-13 | 扬州保来得科技实业有限公司（Cn） | Method for improving corrosion resistance of powder metallurgy iron substrate |
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| CN100509215C (en) | 2009-07-08 |
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