CN103938201B - A kind of high corrosion-resistance black phosphating method - Google Patents
A kind of high corrosion-resistance black phosphating method Download PDFInfo
- Publication number
- CN103938201B CN103938201B CN201410182004.6A CN201410182004A CN103938201B CN 103938201 B CN103938201 B CN 103938201B CN 201410182004 A CN201410182004 A CN 201410182004A CN 103938201 B CN103938201 B CN 103938201B
- Authority
- CN
- China
- Prior art keywords
- washing
- carry out
- normal temperature
- workpiece
- high corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a kind of high corrosion-resistance black phosphating method, comprise the following steps: first carry out skimming treatment at 0 ~ 50 DEG C, remove workpiece surface greasy dirt, wash under normal temperature after degreasing, use hydrochloric acid to carry out pickling after washing, after pickling, workpiece is washed; Blackening pretreatment is carried out under using pre-black liquor normal temperature; Middle temperature Zinc-calcium series phosphatating liquid is used to carry out bonderizing; Workpiece after washing process phosphatization.Present invention process is simple, and ferrous metal, finishing workpiece, precision instrument steel-iron components can obtain the fine and closely woven phosphatize phosphate coat of one deck ater.The fine and closely woven degree of rete is close to the rete of high temperature oxidation, and black level is higher than high temperature oxidation, and film adhesion is high, resistance to copper sulfate titration and the salt-fog test time all high than high temperature oxidation.
Description
Technical field
What the present invention relates to is a kind of phosphorization treatment process, in particular a kind of high corrosion-resistance black phosphating method.
Background technology
Phosphatization is conventional pretreatment technology, principle should belong to the process of chemical transformation film, be mainly used in steel surface phosphatization, and non-ferrous metal (as aluminium, zinc) part also can apply phosphatization.Phosphatization is the process that a kind of chemistry and electrochemical reaction form phosphate chemical conversion film, and the phosphate conversion film formed is referred to as phosphatize phosphate coat.
The object of phosphatization is mainly: provide protection to matrix metal, prevent metal to be corroded to a certain extent; For front bottoming of painting, improve sticking power and the anti-corrosion capability of paint film layer; Antifriction lubrication is played in metal cold complete processing.
Blackening pretreatment is the pretreatment technology before product phosphatization, and in the processing or use procedure of ferrous metal, accurately machined accessory, precision instrument accessory, blackening pretreatment is absolutely necessary.Traditional pre-black liquor adopts dyeing or oxidation to realize black in advance usually, and the effect of dyeing is also bad, does not reach the effect of black, easily fades in follow-up parkerizing process simultaneously; Whole pre-black-labour skill is comparatively complicated, needs to operate under the condition heated up, and the treatment time is also longer.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of high corrosion-resistance black phosphating method, the phosphatize phosphate coat that obtained black is fine and closely woven.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
(1) pre-treatment
First carry out skimming treatment at 0 ~ 50 DEG C, remove workpiece surface greasy dirt, wash under normal temperature after degreasing, use hydrochloric acid to carry out pickling to removing workpiece surface foreign material after washing, after pickling, workpiece is washed;
(2) black in advance
Carry out blackening pretreatment under using pre-black liquor normal temperature, described pre-black liquor comprises following component: Bismuth trinitrate 0.01 ~ 1g/L, and the aqueous solution of molybdate and trolamine amounts to 5 ~ 25mL/L, and mass concentration is the nitric acid 8 ~ 10mL/L of 65%, and surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
Use middle temperature Zinc-calcium series phosphatating liquid to carry out bonderizing, described middle temperature Zinc-calcium series phosphatating liquid by volume concentration, comprises zinc oxide 2 ~ 4g/L; Phosphoric acid 8 ~ 15g/L; Nitric acid 15 ~ 25g/L; Calcium carbonate 10 ~ 20g/L; Citric acid 0 ~ 1g/L;
(4) aftertreatment
Workpiece after washing process phosphatization.
As one of optimal way of the present invention, in described step (1), skimming treatment comprises pre-degreasing and degreasing.Twice degreasing can ensure the more thorough of degreasing.
As one of optimal way of the present invention, in described step (1), degreasing after washing comprises the first washing and the second washing, and the time of twice washing is 10 ~ 30s, and normal temperature is washed.It is more thorough that twice cleaning can be cleaned, and can not the tank liquor of last operation be taken in subsequent processing, avoid polluting.
As one of optimal way of the present invention, in described step (1), pickling after washing comprises the 3rd washing and the 4th washing, and the time of twice washing is 10 ~ 30s, and normal temperature is washed.It is more thorough that twice cleaning can be cleaned, and can not the tank liquor of last operation be taken in subsequent processing, avoid polluting.
As one of optimal way of the present invention, during described step (3) bonderizing, the mass ratio that concentrated solution is made into working fluid is 3 ~ 10%, and free acid is 2 ~ 4, and total acid is 30 ~ 60, and treatment temp is 60 ~ 75 DEG C, and the treatment time is 8 ~ 20min.
As one of optimal way of the present invention, in described step (4), the washing after bonderizing comprises the 5th washing and hot water wash, and described 5th washing is normal temperature washing, washing time 10 ~ 30s; Hot water wash is washing time 10 ~ 30s at 50 ~ 80 DEG C.
The present invention has the following advantages compared to existing technology: present invention process is simple, can obtain the fine and closely woven phosphatize phosphate coat of one deck ater on ferrous metal, finishing workpiece, precision instrument steel-iron components.The fine and closely woven degree of rete is close to the rete of high temperature oxidation, and black level is higher than high temperature oxidation, and film adhesion is high, resistance to copper sulfate titration and the salt-fog test time all high than high temperature oxidation.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The present embodiment comprises the following steps:
(1) pre-treatment
First skimming treatment is carried out at 25 DEG C, skimming treatment comprises pre-degreasing and degreasing, remove workpiece surface greasy dirt, the first washing and the second washing is carried out under normal temperature after degreasing, each washing time is 10 ~ 30s, and using hydrochloric acid to carry out pickling to workpiece surface after washing does not have oxide skin or other foreign material, exposes the outward appearance of metal itself, carry out the 3rd washing and the 4th washing to workpiece after pickling, each washing time is 10 ~ 30s;
(2) black in advance
Carry out blackening pretreatment under using pre-black liquor normal temperature, described pre-black liquor comprises following component: Bismuth trinitrate 0.01g/L, and the aqueous solution of molybdate and trolamine amounts to 5mL/L, and mass concentration is the nitric acid 8mL/L of 65%, and surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
Middle temperature Zinc-calcium series phosphatating liquid is used to carry out bonderizing; Described middle temperature Zinc-calcium series phosphatating liquid by volume concentration, comprises zinc oxide 2g/L; Phosphoric acid 8g/L; Nitric acid 15g/L; Calcium carbonate 10g/L; During bonderizing, the mass ratio that concentrated solution is made into working fluid is 3%, and free acid is 2 ~ 4, and total acid is 30 ~ 60, and treatment temp is 60 DEG C, and the treatment time is 8 ~ 20min;
(4) aftertreatment
Workpiece after washing process phosphatization, washing comprises the 5th washing and hot water wash, and described 5th washing is normal temperature washing, washing time 10 ~ 30s; Hot water wash is 50 DEG C, washing time 10 ~ 30s.
Embodiment 2
The present embodiment comprises the following steps:
(1) pre-treatment
First skimming treatment is carried out at 0 DEG C, skimming treatment comprises pre-degreasing and degreasing, remove workpiece surface greasy dirt, the first washing and the second washing is carried out under normal temperature after degreasing, each washing time is 10 ~ 30s, and using hydrochloric acid to carry out pickling to workpiece surface after washing does not have oxide skin or other foreign material, exposes the outward appearance of metal itself, carry out the 3rd washing and the 4th washing to workpiece after pickling, each washing time is 10 ~ 30s;
(2) black in advance
Carry out blackening pretreatment under using pre-black liquor normal temperature, described pre-black liquor comprises following component: Bismuth trinitrate 1g/L, and the aqueous solution of molybdate and trolamine amounts to 25mL/L, and mass concentration is the nitric acid 10mL/L of 65%, and surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
Middle temperature Zinc-calcium series phosphatating liquid is used to carry out bonderizing; Described middle temperature Zinc-calcium series phosphatating liquid by volume concentration, comprises zinc oxide 4g/L; Phosphatase 11 5g/L; Nitric acid 25g/L; Calcium carbonate 20g/L; Citric acid 1g/L; During bonderizing, the mass ratio that concentrated solution is made into working fluid is 10%, and free acid is 2 ~ 4, and total acid is 30 ~ 60, and treatment temp is 75 DEG C, and the treatment time is 8 ~ 20min;
(4) aftertreatment
Workpiece after washing process phosphatization, washing comprises the 5th washing and hot water wash, and described 5th washing is normal temperature washing, washing time 10 ~ 30s; Hot water wash is 50 ~ 80 DEG C, washing time 10 ~ 30s.
Embodiment 3
The present embodiment comprises the following steps:
(1) pre-treatment
First skimming treatment is carried out at 50 DEG C, skimming treatment comprises pre-degreasing and degreasing, remove workpiece surface greasy dirt, the first washing and the second washing is carried out under normal temperature after degreasing, each washing time is 10 ~ 30s, and using hydrochloric acid to carry out pickling to workpiece surface after washing does not have oxide skin or other foreign material, exposes the outward appearance of metal itself, carry out the 3rd washing and the 4th washing to workpiece after pickling, each washing time is 10 ~ 30s;
(2) black in advance
Carry out blackening pretreatment under using pre-black liquor normal temperature, described pre-black liquor comprises following component: Bismuth trinitrate 0.5g/L, and the aqueous solution of molybdate and trolamine amounts to 10mL/L, and mass concentration is the nitric acid 9mL/L of 65%, and surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
Middle temperature Zinc-calcium series phosphatating liquid is used to carry out bonderizing; Described middle temperature Zinc-calcium series phosphatating liquid by volume concentration, comprises zinc oxide 3g/L; Phosphatase 11 0g/L; Nitric acid 20g/L; Calcium carbonate 15g/L; Citric acid 0.5g/L; During bonderizing, the mass ratio that concentrated solution is made into working fluid is 8%, and free acid is 2 ~ 4, and total acid is 30 ~ 60, and treatment temp is 70 DEG C, and the treatment time is 8 ~ 20min;
(4) aftertreatment
Workpiece after washing process phosphatization, washing comprises the 5th washing and hot water wash, and described 5th washing is normal temperature washing, washing time 10 ~ 30s; Hot water wash is 50 ~ 80 DEG C, washing time 10 ~ 30s.
Relatively conventional black phosphatization, tradition blackout and process of turning blue, middle temperature black phosphating result of the present invention are as shown in the table:
Claims (6)
1. a high corrosion-resistance black phosphating method, is characterized in that, comprises the following steps:
(1) pre-treatment
First carry out skimming treatment at 0 ~ 50 DEG C, remove workpiece surface greasy dirt, wash under normal temperature after degreasing, use hydrochloric acid to carry out pickling to removing workpiece surface foreign material after washing, after pickling, workpiece is washed;
(2) black in advance
Carry out blackening pretreatment under using pre-black liquor normal temperature, described pre-black liquor comprises following component: Bismuth trinitrate 0.01 ~ 1g/L, and the aqueous solution of molybdate and trolamine amounts to 5 ~ 25mL/L, and mass concentration is the nitric acid 8 ~ 10mL/L of 65%, and surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
Use middle temperature Zinc-calcium series phosphatating liquid to carry out bonderizing, described middle temperature Zinc-calcium series phosphatating liquid by volume concentration, comprises zinc oxide 2 ~ 4g/L; Phosphoric acid 8 ~ 15g/L; Nitric acid 15 ~ 25g/L; Calcium carbonate 10 ~ 20g/L; Citric acid 0 ~ 1g/L;
(4) aftertreatment
Workpiece after washing process phosphatization.
2. a kind of high corrosion-resistance black phosphating method according to claim 1, is characterized in that, in described step (1), skimming treatment comprises pre-degreasing and degreasing.
3. a kind of high corrosion-resistance black phosphating method according to claim 1, is characterized in that, in described step (1), degreasing after washing comprises the first washing and the second washing, and the time of twice washing is 10 ~ 30s, and normal temperature is washed.
4. a kind of high corrosion-resistance black phosphating method according to claim 1, is characterized in that, in described step (1), pickling after washing comprises the 3rd washing and the 4th washing, and the time of twice washing is 10 ~ 30s, and normal temperature is washed.
5. a kind of high corrosion-resistance black phosphating method according to claim 1, it is characterized in that, during described step (3) bonderizing, the mass ratio that concentrated solution is made into working fluid is 3 ~ 10%, free acid is 2 ~ 4, total acid is 30 ~ 60, and treatment temp is 60 ~ 75 DEG C, and the treatment time is 8 ~ 20min.
6. a kind of high corrosion-resistance black phosphating method according to claim 1, is characterized in that, in described step (4), the washing after bonderizing comprises the 5th washing and hot water wash, and described 5th washing is normal temperature washing, washing time 10 ~ 30s; Hot water wash is 50 ~ 80 DEG C, washing time 10 ~ 30s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410182004.6A CN103938201B (en) | 2014-04-30 | 2014-04-30 | A kind of high corrosion-resistance black phosphating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410182004.6A CN103938201B (en) | 2014-04-30 | 2014-04-30 | A kind of high corrosion-resistance black phosphating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103938201A CN103938201A (en) | 2014-07-23 |
| CN103938201B true CN103938201B (en) | 2016-04-06 |
Family
ID=51186062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410182004.6A Active CN103938201B (en) | 2014-04-30 | 2014-04-30 | A kind of high corrosion-resistance black phosphating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103938201B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711553A (en) * | 2015-02-12 | 2015-06-17 | 安徽启明表面技术有限公司 | Environment-friendly membrane treating agent and using method thereof |
| CN104630867A (en) * | 2015-02-17 | 2015-05-20 | 蚌埠市钰诚新材料科技有限公司 | High-efficiency electrolytic phosphating solution |
| CN105441921B8 (en) * | 2015-11-29 | 2019-12-06 | 台州和兴锻造有限公司 | Metal part rust prevention process |
| CN107587127A (en) * | 2017-08-24 | 2018-01-16 | 合肥正明机械有限公司 | A kind of method for improving steel plate phosphating coat wearability |
| CN110184596A (en) * | 2019-06-20 | 2019-08-30 | 佛山市众之助新材料科技有限公司 | A method of black phosphating film is covered in metal surface |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405354A (en) * | 2002-11-08 | 2003-03-26 | 中国重型汽车集团有限公司 | Pretreating liquid for black bonderizing |
| CN101876070A (en) * | 2009-04-28 | 2010-11-03 | 北京科技桥科贸有限公司 | Hair blackening liquid |
| CN102140635A (en) * | 2011-03-12 | 2011-08-03 | 蚌埠市钰诚五金工贸有限公司 | Metal surface pre-blackening treatment method |
-
2014
- 2014-04-30 CN CN201410182004.6A patent/CN103938201B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405354A (en) * | 2002-11-08 | 2003-03-26 | 中国重型汽车集团有限公司 | Pretreating liquid for black bonderizing |
| CN101876070A (en) * | 2009-04-28 | 2010-11-03 | 北京科技桥科贸有限公司 | Hair blackening liquid |
| CN102140635A (en) * | 2011-03-12 | 2011-08-03 | 蚌埠市钰诚五金工贸有限公司 | Metal surface pre-blackening treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103938201A (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103938201B (en) | A kind of high corrosion-resistance black phosphating method | |
| CN102912338B (en) | Aluminium alloy trivalent chromium passivation solution as well as preparation method and passivation technology thereof | |
| CN105714299A (en) | Chemical polishing liquid used for metal and polishing technology | |
| CN107130233A (en) | ZK61M magnesium alloys conversion film treating agent and its conversion membrane processing method | |
| CN107345297A (en) | A kind of alkaline cleaning fluid, phosphating solution and metal surface treating method | |
| CN101851755B (en) | Magnesium alloy chromium-free fluorine-free phosphorization solution and phosphorization method | |
| CN102534591B (en) | Thick film phosphating method | |
| CN103510090B (en) | A kind of pretreatment liquid and pre-treating process improving corrosion resistance of aluminum alloy | |
| CN106148974A (en) | A kind of iron and steel derusting and phosphorating agent | |
| CN105441921B (en) | A kind of metalwork anti-corrosive technology | |
| CN108707888A (en) | A kind of aluminum alloy surface passivation process improving corrosion resistance | |
| WO2016201935A1 (en) | Method for forming golden yellow film layer on surface of aluminum alloy | |
| CN104073796A (en) | Metal plating passivation solution and preparation method thereof | |
| CN105239065A (en) | Aluminum board purifying process | |
| CN105887056A (en) | Chemical nickel plating method for surface of magnesium alloy | |
| CN103451645B (en) | A kind of adopt magnesium alloy film agent that magnesium alloy is carried out the method for surface treatment | |
| CN105442018A (en) | Conductive oxidation process for automobile aluminum alloy parts | |
| CN103710688A (en) | Weakly acidic non-phosphorus transforming agent | |
| CN104451634B (en) | Aluminum and aluminum alloy passivation solution, preparation method and using method thereof | |
| CN102234798B (en) | Magnesium alloy surface conversion film forming solution and using method thereof | |
| CN101089227A (en) | Magnesium alloy surface non-chromium chemical solution and chemical process technology | |
| CN107130236A (en) | A kind of aluminum alloy surface passivation process for improving corrosion resistance | |
| CN107338430A (en) | A kind of phosphating solution and phosphating process | |
| CN109208058B (en) | Surface treatment method for improving corrosion resistance of 17-4PH material | |
| CN101892476A (en) | Chemical oxidation treatment solution for aluminum alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Black phosphorizing method with high corrosion resistance Effective date of registration: 20190530 Granted publication date: 20160406 Pledgee: Huizhou Merchants Bank, Hefei Shuguang Road subbranch Pledgor: Anhui Qiming Surface Technology Co., Ltd. Registration number: 2019340000277 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |