CN103938201A - Black phosphorizing method with high corrosion resistance - Google Patents
Black phosphorizing method with high corrosion resistance Download PDFInfo
- Publication number
- CN103938201A CN103938201A CN201410182004.6A CN201410182004A CN103938201A CN 103938201 A CN103938201 A CN 103938201A CN 201410182004 A CN201410182004 A CN 201410182004A CN 103938201 A CN103938201 A CN 103938201A
- Authority
- CN
- China
- Prior art keywords
- washing
- black
- degreasing
- normal temperature
- 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.)
- Granted
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a black phosphorizing method with high corrosion resistance. The method comprises the following steps: firstly, degreasing at 0-50 DEG C, eliminating oil contamination on the surface of a workpiece, washing at normal temperature after degreasing, pickling by hydrochloric acid after washing, and washing the pickled workpiece; pre-blackening by a pre-blackening liquid at normal temperature; phosphorizing by an intermediate-temperature zinc-calcium phosphorizing liquid; and washing the phosphorized workpiece. The method disclosed by the invention is simple in process, and a pure black compact phosphorizing membrane can be obtained on black metals, finish machining workpieces and iron parts of precise instruments. Compaction of the membrane is approximate to a high-temperature oxidized membrane, the black degree is approximate to high-temperature oxidization, the adhesive force of the membrane is high, and the anti-copper sulfate titration and salt spray test times are longer than time of high-temperature oxidization.
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, should belong to the processing of chemical transformation film in principle, is mainly used in steel surface phosphatization, and non-ferrous metal (as aluminium, zinc) part also can be applied phosphatization.Phosphatization is the process that a kind of chemistry and electrochemical reaction form phosphate chemical conversion film, and the phosphate conversion film forming is referred to as phosphatize phosphate coat.
The object of phosphatization is mainly: provide protection to matrix metal, prevent that to a certain extent metal is corroded; The front bottoming that is used for painting, improves sticking power and the anti-corrosion capability of paint film layer; In metal cold complete processing, play antifriction lubrication.
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.It is black in advance that traditional pre-black liquor adopts dyeing or oxidation to realize conventionally, and the effect of dyeing is also bad, do not reach the effect of black, easily fades in follow-up parkerizing process simultaneously; Whole pre-black-labour skill is comparatively complicated, need under the condition heating up, operate, 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, a kind of high corrosion-resistance black phosphating method is provided, make the phosphatize phosphate coat that 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, after degreasing, under normal temperature, wash, after washing, use hydrochloric acid to carry out pickling to removing workpiece surface foreign material, after pickling, workpiece is washed;
(2) black in advance
Use under pre-black liquor normal temperature and carry out blackening pretreatment, by volume concentration of 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, nitric acid 8～10mL/L that mass concentration is 65%, surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
In use, warm Zinc-calcium series phosphatating liquid carries out bonderizing, and by volume concentration of described middle temperature Zinc-calcium series phosphatating liquid, 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
The workpiece after phosphatization is processed in washing.
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, normal temperature washing.It is more thorough that twice cleaning can be cleaned, and the tank liquor of last operation can not taken in subsequent processing, avoids 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, normal temperature washing.It is more thorough that twice cleaning can be cleaned, and the tank liquor of last operation can not taken in subsequent processing, avoids polluting.
As one of optimal way of the present invention, when 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 the 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: technique of the present invention is simple, can on 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 approaches the rete of high temperature oxidation, and black level is higher than high temperature oxidation, and film adhesion is high, and resistance to copper sulfate titration and salt-fog test time are all high than high temperature oxidation.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented under taking technical solution of the present invention as prerequisite, provided 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 carry out skimming treatment at 25 DEG C, skimming treatment comprises pre-degreasing and degreasing, remove workpiece surface greasy dirt, after degreasing, under normal temperature, carry out the first washing and the second washing, each washing time is 10～30s, and after washing, using hydrochloric acid to carry out pickling to workpiece surface does not have oxide skin or other foreign material, exposes the outward appearance of metal itself, after pickling, workpiece is carried out to the 3rd washing and the 4th washing, each washing time is 10～30s;
(2) black in advance
Use under pre-black liquor normal temperature and carry out blackening pretreatment, by volume concentration of described pre-black liquor, comprises following component: Bismuth trinitrate 0.01g/L, and the aqueous solution of molybdate and trolamine amounts to 5mL/L, the nitric acid 8mL/L that mass concentration is 65%, surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
In use, warm Zinc-calcium series phosphatating liquid carries out bonderizing; By volume concentration of described middle temperature Zinc-calcium series phosphatating liquid, comprises zinc oxide 2g/L; Phosphoric acid 8g/L; Nitric acid 15g/L; Calcium carbonate 10g/L; When 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
The workpiece after phosphatization is processed in washing, and washing comprises the 5th washing and hot water wash, and described the 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 carry out skimming treatment at 0 DEG C, skimming treatment comprises pre-degreasing and degreasing, remove workpiece surface greasy dirt, after degreasing, under normal temperature, carry out the first washing and the second washing, each washing time is 10～30s, and after washing, using hydrochloric acid to carry out pickling to workpiece surface does not have oxide skin or other foreign material, exposes the outward appearance of metal itself, after pickling, workpiece is carried out to the 3rd washing and the 4th washing, each washing time is 10～30s;
(2) black in advance
Use under pre-black liquor normal temperature and carry out blackening pretreatment, by volume concentration of described pre-black liquor, comprises following component: Bismuth trinitrate 1g/L, and the aqueous solution of molybdate and trolamine amounts to 25mL/L, the nitric acid 10mL/L that mass concentration is 65%, surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
In use, warm Zinc-calcium series phosphatating liquid carries out bonderizing; By volume concentration of described middle temperature Zinc-calcium series phosphatating liquid, comprises zinc oxide 4g/L; Phosphatase 11 5g/L; Nitric acid 25g/L; Calcium carbonate 20g/L; Citric acid 1g/L; When 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
The workpiece after phosphatization is processed in washing, and washing comprises the 5th washing and hot water wash, and described the 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 carry out skimming treatment at 50 DEG C, skimming treatment comprises pre-degreasing and degreasing, remove workpiece surface greasy dirt, after degreasing, under normal temperature, carry out the first washing and the second washing, each washing time is 10～30s, and after washing, using hydrochloric acid to carry out pickling to workpiece surface does not have oxide skin or other foreign material, exposes the outward appearance of metal itself, after pickling, workpiece is carried out to the 3rd washing and the 4th washing, each washing time is 10～30s;
(2) black in advance
Use under pre-black liquor normal temperature and carry out blackening pretreatment, by volume concentration of described pre-black liquor, comprises following component: Bismuth trinitrate 0.5g/L, and the aqueous solution of molybdate and trolamine amounts to 10mL/L, the nitric acid 9mL/L that mass concentration is 65%, surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
In use, warm Zinc-calcium series phosphatating liquid carries out bonderizing; By volume concentration of described middle temperature Zinc-calcium series phosphatating liquid, comprises zinc oxide 3g/L; Phosphatase 11 0g/L; Nitric acid 20g/L; Calcium carbonate 15g/L; Citric acid 0.5g/L; When 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
The workpiece after phosphatization is processed in washing, and washing comprises the 5th washing and hot water wash, and described the 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 the processing of turning blue, middle temperature black phosphating result of the present invention are as shown in the table:
| ? | Conventional black phosphatization | Tradition blackout and the processing of turning blue | Middle temperature black phosphating |
| Treatment temp | More than 90 DEG C | 120～140℃ | 60～70℃ |
| Treatment time | 15～30min | 10～30min | 8～20min |
| Outward appearance | Grey black～black partially | Black blueing | Ater |
| Thickness | More than 20um | Below 10um | 8～15um |
| Rete degree of roughness | More coarse | Fine and close | Fine and close |
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, after degreasing, under normal temperature, wash, after washing, use hydrochloric acid to carry out pickling to removing workpiece surface foreign material, after pickling, workpiece is washed;
(2) black in advance
Use under pre-black liquor normal temperature and carry out blackening pretreatment, by volume concentration of 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, nitric acid 8～10mL/L that mass concentration is 65%, surplus is water; In the aqueous solution of described molybdate and trolamine, by mass, molybdate: trolamine: water=1:8:11;
(3) phosphatization
In use, warm Zinc-calcium series phosphatating liquid carries out bonderizing, and by volume concentration of described middle temperature Zinc-calcium series phosphatating liquid, 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
The workpiece after phosphatization is processed in washing.
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, normal temperature washing.
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, normal temperature washing.
5. a kind of high corrosion-resistance black phosphating method according to claim 1, it is characterized in that, when 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 the 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 true CN103938201A (en) | 2014-07-23 |
| CN103938201B 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) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105441921A (en) * | 2015-11-29 | 2016-03-30 | 郑臣钏 | Metal part anti-rust technology |
| 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 |
Cited By (7)
| 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 |
| CN105441921A (en) * | 2015-11-29 | 2016-03-30 | 郑臣钏 | Metal part anti-rust technology |
| CN105441921B (en) * | 2015-11-29 | 2019-09-10 | 郑臣钏 | A kind of metalwork anti-corrosive technology |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103938201B (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103938201B (en) | A kind of high corrosion-resistance black phosphating method | |
| CN102534591B (en) | Thick film phosphating method | |
| CN109136902A (en) | A kind of corrosion-resistant post-treatment process of stainless steel tube | |
| CN101851755B (en) | Magnesium alloy chromium-free fluorine-free phosphorization solution and phosphorization method | |
| CN105714299A (en) | Chemical polishing liquid used for metal and polishing technology | |
| CN105441921B (en) | A kind of metalwork anti-corrosive technology | |
| CN106148974A (en) | A kind of iron and steel derusting and phosphorating agent | |
| CN107130233A (en) | ZK61M magnesium alloys conversion film treating agent and its conversion membrane processing method | |
| CN101892479A (en) | Aluminum alloy surface phosphatizing fluid and phosphatizing method | |
| CN105088218A (en) | Metal surface coating technology | |
| CN108707888A (en) | A kind of aluminum alloy surface passivation process improving corrosion resistance | |
| CN103938251A (en) | Aluminum alloy hub surface anodic oxidation treatment process | |
| CN108998781A (en) | A kind of car body coating front surface zirconium treatment technique | |
| CN105442018A (en) | Conductive oxidation process for automobile aluminum alloy parts | |
| CN103710688A (en) | Weakly acidic non-phosphorus transforming agent | |
| 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 | |
| CN102560459A (en) | Phosphorizing liquid for phosphorization of thick film | |
| CN107338430A (en) | A kind of phosphating solution and phosphating process | |
| CN102605364B (en) | Intermediate-temperature low-sediment and low-emission thick membrane phosphorizing liquid and phosphorizing method thereof | |
| CN107419246A (en) | One kind improves environment-friendly type hinge basic unit composite film coating technique | |
| CN105220140B (en) | A kind of corrosion-resistant protective layer of steel piece decorative surface and its preparation method and application | |
| CN104294266B (en) | Environment-friendly highly efficient brass passivation process | |
| CN105441927A (en) | Chromate-free passivant for cold-roll steel sheet and galvanized steel sheet roller coating before coating and preparing method | |
| 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 | ||
| 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 |