CN104294349A - Method for coating normal-temperature black phosphating film on steel surface - Google Patents
Method for coating normal-temperature black phosphating film on steel surface Download PDFInfo
- Publication number
- CN104294349A CN104294349A CN201410489111.3A CN201410489111A CN104294349A CN 104294349 A CN104294349 A CN 104294349A CN 201410489111 A CN201410489111 A CN 201410489111A CN 104294349 A CN104294349 A CN 104294349A
- Authority
- CN
- China
- Prior art keywords
- steel surface
- phosphating
- film
- black
- coslettising
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to a method for coating a film on a steel surface, particularly a method for coating a normal-temperature black phosphating film on a steel surface. The black phosphating solution is composed of organic acid antimony, 5-10 g/L zinc oxide, 30-60 g/L phosphoric acid, 20-40 g/L manganese dihydrogen phosphate, 1-3 g/L nickel nitrate and the balance of water. A cathode electrolysis phosphating process is adopted to perform normal-temperature phosphating on the steel surface, wherein the current density is 0.5-3 A/dm<2>, and the time is 5-20 minutes. The method has the advantages of energy saving, environment friendliness, stable phosphating solution, simple phosphating technique, high film-forming speed, black color of the film layer, and favorable corrosion resistance, and is convenient to operate and suitable for various steel surface treatment.
Description
Technical field
The present invention relates to a kind of film covering method of steel surface, particularly relate to a kind of steel surface and cover the method for cold black coslettising film.
Background technology
Steel surface black-emitting technology is widely used in surfacecti proteon and the decoration in the fields such as aviation, electronics, instrument, military project.Steel blackening mainly contains the methods such as high-temperature alkaline chemical oxidation blackout, normal temperature selenide system blackout and black phosphating.The power consumption of high-temperature alkaline blackening is large, the production cycle is long, labor condition is poor and environmental pollution is serious.Although normal temperature selenide system blackout solves high-temperature alkaline and to turn black length consuming time, need the problems such as heating, the selenide costliness in hair blackening liquid, and toxicity is larger.Black phosphating is chemical conversion membrane preparation technology blackout and phosphatization are integrated in one, and not only have the excellent properties of general phosphatize phosphate coat, and phosphatize phosphate coat outward appearance is black.At present, most of steel surface black phosphating is the middle high temperature phosphorization of manganese system.Outward appearance and the solidity to corrosion of middle high temperature manganese phosphate coating are better, but its efficiency is low, and energy expenditure is large, and parkerizing process complex management, produce sediment many.In recent years, the cold black coslettising technology being main blackening agent for surface with Sb3+ ion has been reported.Compared with selenide, Sb3+ ion toxicity is low, and raw material is relatively cheap to be easy to get.But Sb3+ ion is very easily hydrolyzed, phosphatization needs to carry out in denseer hydrochloric acid medium, and the careless slightly hydrolysis just easily causing Sb3+ ion in Phosphating Solution process for preparation.Phosphatization in hydrochloric acid medium, inevitably brings a large amount of chlorions in phosphatize phosphate coat, and the corrosion resisting property of chlorion on rete has important impact.
Summary of the invention
The method of the cold black coslettising film that the object of the present invention is to provide a kind of steel surface to cover, the phosphatization hair blackening liquid environmental friendliness that the method adopts, stable performance, by electrolytic phosphating technology, steel by black phosphatize phosphate coat can be prepared fast by normal temperature, by Sb3+ ion and organic acid reaction, generate stable organic acid antimony complex and add in Phosphating Solution.This Phosphating Solution is stablized, and do not need strong acid media phosphorization filming, energy consumption is low, and film forming is fast, sediment is few, and technique is simple, medicine uses few, and rete color and luster is firmly pitch-black, and solidity to corrosion is good.
The object of the invention is to be achieved through the following technical solutions:
Described in a kind of method that steel surface covers cold black coslettising film, method comprises following process:
(1) butter of antimony (SbCl3) or antimonous oxide (Sb2O3) are generated the antimonious complex compound of organic acid with organic acid reaction;
(2) by antimonious for organic acid complex dissolves in Phosphating Solution, obtain the Phosphating Solution containing organic acid antimony;
(3) phosphatization, the steel sample be about to after cleaning is placed in the Phosphating Solution containing organic acid antimony, room temperature electrolytic phosphating 5-20 minute;
(4) steel sample after phosphatization carries out washing, saponification, form pitch-black, the fine and close phosphorization membrane of one deck at steel surface after oil sealing.
Described a kind of steel surface covers the method for cold black coslettising film, and described organic acid is any one in tartrate, citric acid, disodium ethylene diamine tetraacetate.
Described a kind of steel surface covers the method for cold black coslettising film, and described Phosphating Solution is made up of the zinc oxide of 5 ~ 10g/L, the phosphoric acid of 30 ~ 60g/L, the Mazhev salt of 20 ~ 40g/L, the nickelous nitrate of 1 ~ 3g/L.
Described a kind of steel surface covers the method for cold black coslettising film, and the content of described antimony ion in Phosphating Solution is 0.5 ~ 2g/L.
Described a kind of steel surface covers the method for cold black coslettising film, and the current density of described electrolytic phosphating is 0.5 ~ 3A/dm2.
Described a kind of steel surface covers the method for cold black coslettising film, and the described electrolytic phosphating time is 5 ~ 20 minutes.
Advantage of the present invention and effect are:
(1) normal-temperature phosphorizing liquid that prepared by the present invention does not contain supervirulent selenide, environmental friendliness;
(2) main blackening agent for surface Sb3+ ion and organic acid reaction generate the complex compound of organic acid antimony, inhibit the hydrolysis of antimony ion, and Phosphating Solution is stablized, and avoids phosphatization in strong acid media;
(3) adopt electrolytic phosphating can film formation, medicine uses few, does not need to add various Phosphating Accelerant and film coalescence aid, and film forming speed is fast, and energy consumption is low, and sediment is few, and technique is simple, is easy to control.The phosphorization membrane of preparation is complete, and color is black, excellent corrosion-proof performance.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram (corresponding embodiment 1 product) of antimony tartrate;
Fig. 2 is the photo (corresponding embodiment 1 product) of the number of black phosphating film;
Fig. 3 is the stereoscan photograph (corresponding embodiment 1 product) of black phosphating film;
Fig. 4 is that black phosphating film EDS can spectrogram (corresponding embodiment 1 product).
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the invention will be further described.
The direct supply selecting 0 ~ 30V adjustable provides adjustable galvanic current.Positive pole selects graphite flake, and iron and steel test piece is as negative electrode.Iron and steel test piece after alkali cleaning oil removing, acid pickling and rust removing, washing, select different nigrescent phosphatizing liquid formula, galvanization carries out electrolytic phosphating, and concrete case study on implementation is as follows:
Embodiment 1
(1) butter of antimony (SbCl3) and tartrate are reacted generate the antimonious complex compound of tartrate;
Preparation method: 2.3 grams of butter of antimony, 6 grams of tartrate are dissolved in water, and drip sodium hydroxide solution while stirring and clarify to reaction solution, obtain the antimonious complex compound of tartrate.
(2) by antimonious for tartrate complex dissolves in Phosphating Solution, obtain the Phosphating Solution containing antimony tartrate;
The Mazhev salt of the zinc oxide of preparation method: 6g/L, the phosphoric acid of 35g/L, 30g/L, the nickelous nitrate of 1g/L add in tartrate trivalent antimony complex solution after dissolving clarification, obtain nigrescent phosphatizing solution.
(3) phosphatization, the steel sample be about to after cleaning is placed in containing the antimonious Phosphating Solution of tartrate, room temperature electrolytic phosphating 10 minutes;
Phosphatization current density is 1.5A/dm2, and phosphatize phosphate coat is complete, colors black.
(4) steel sample after phosphatization carries out washing, saponification, can form pitch-black, the fine and close phosphorization membrane of one deck at steel surface after oil sealing.
In order to improve the solidity to corrosion of rete and ornamental further, saponification, oil sealing process are carried out to nigrescent phosphatizing film.Saponification process is soap 10 ~ 30g/L, 70 ~ 90 DEG C, 3 ~ 5min; Oil sealing technique is standard machinery oil normal temperature leaching 5min.Iron and steel test piece after phosphatization is through washing, saponification and oil sealing process, and the drop of the resistance to copper sulfate time is greater than 20min.
Fig. 1 is the infrared spectrogram of tartrate trivalent antimony complex compound prepared by embodiment 1.Do not have absorption peak to occur at 1690 ~ 1730cm-1, the carboxyl all salify in tartaric acid molecules is described.1560cm-1 and 1340cm-1 place is respectively antisymmetric stretching vibration absorption peak and the symmetrical stretching vibration absorption peak of carboxyl in carboxylate salt.The absorption peak occurred at 472cm-1 place is Sb-O stretching vibration absorption peak, and infrared spectrum illustrates the formation of tartrate trivalent antimony complex compound.
The digital photograph of phosphatize phosphate coat is shown in Fig. 2, can find out, Film color is black, covers matrix good, even film layer, densification.The wiping of exerting oneself of rete cotton is hundreds of time, and phosphatize phosphate coat does not fall ash, do not fade, display black phosphating film and matrix adhesive force strong.
Fig. 3 is the scanning electron microscope (SEM) photograph of electrolytic phosphating film, and as seen from the figure, prepared black phosphating film is for piling up granular particles closely.
The EDAX results of electrolysis black phosphating rete is as Fig. 4.Result shows, black phosphating rete is primarily of chemical element compositions such as Zn, Mn, O, P, Sb, Ni.
Embodiment 2
(1) butter of antimony (SbCl3) and citric acid reactions are generated the antimonious complex compound of citric acid;
Preparation method: 3.8 grams of butter of antimony, 12 grams of citric acids are dissolved in water, and drip sodium hydroxide solution while stirring and clarify to reaction solution, obtain the antimonious complex compound of citric acid.
(2) by antimonious for citric acid complex dissolves in Phosphating Solution, obtain the Phosphating Solution containing citric acid antimony;
The Mazhev salt of the zinc oxide of preparation method: 8g/L, the phosphoric acid of 60g/L, 20g/L, the nickelous nitrate of 3g/L add in citric acid trivalent antimony complex solution after dissolving clarification, obtain nigrescent phosphatizing solution.
(3) phosphatization, the steel sample be about to after cleaning is placed in containing the antimonious Phosphating Solution of tartrate, room temperature electrolytic phosphating 20 minutes;
Phosphatization current density is 0.5A/dm2, and phosphatize phosphate coat is complete, colors black.
(4) steel sample after phosphatization carries out washing, saponification, can form pitch-black, the fine and close phosphorization membrane of one deck at steel surface after oil sealing.
Steel sample after phosphatization is through washing, saponification and oil sealing process, and the drop of the resistance to copper sulfate time is greater than 20min.
Embodiment 3
(1) antimonous oxide (Sb2O3) and disodium ethylene diamine tetraacetate are reacted generate the antimonious complex compound of ethylenediamine tetraacetic acid (EDTA);
Preparation method: 0.95 gram of antimonous oxide, 4 grams of disodium ethylene diamine tetraacetate are dissolved in water, and drip sodium hydroxide solution while stirring and clarify to reaction solution, obtain the antimonious complex compound of ethylenediamine tetraacetic acid (EDTA).
(2) by antimonious for ethylenediamine tetraacetic acid (EDTA) complex dissolves in Phosphating Solution, obtain the Phosphating Solution containing ethylenediamine tetraacetic acid (EDTA) antimony;
The Mazhev salt of the zinc oxide of preparation method: 5g/L, the phosphoric acid of 30g/L, 40g/L, the nickelous nitrate of 2g/L add in ethylenediamine tetraacetic acid (EDTA) trivalent antimony complex solution after dissolving clarification, obtain nigrescent phosphatizing solution.
(3) phosphatization, the steel sample be about to after cleaning is placed in containing the antimonious Phosphating Solution of ethylenediamine tetraacetic acid (EDTA), room temperature electrolytic phosphating 5 minutes;
Phosphatization current density is 2.0A/dm2, and phosphatize phosphate coat is complete, colors black.
(4) steel sample after phosphatization carries out washing, saponification, can form pitch-black, the fine and close phosphorization membrane of one deck at steel surface after oil sealing.
Steel sample after phosphatization is through washing, saponification and oil sealing process, and the drop of the resistance to copper sulfate time is greater than 20min.
Claims (6)
1. steel surface covers a method for cold black coslettising film, and it is characterized in that, described method comprises following process:
(1) butter of antimony (SbCl3) or antimonous oxide (Sb2O3) are generated the antimonious complex compound of organic acid with organic acid reaction;
(2) by antimonious for organic acid complex dissolves in Phosphating Solution, obtain the Phosphating Solution containing organic acid antimony;
(3) phosphatization, the steel sample be about to after cleaning is placed in the Phosphating Solution containing organic acid antimony, room temperature electrolytic phosphating 5-20 minute;
(4) steel sample after phosphatization carries out washing, saponification, form pitch-black, the fine and close phosphorization membrane of one deck at steel surface after oil sealing.
2. a kind of steel surface according to claim 1 covers the method for cold black coslettising film, it is characterized in that, described organic acid is any one in tartrate, citric acid, disodium ethylene diamine tetraacetate.
3. a kind of steel surface according to claim 1 covers the method for cold black coslettising film, it is characterized in that, described Phosphating Solution is made up of the zinc oxide of 5 ~ 10g/L, the phosphoric acid of 30 ~ 60g/L, the Mazhev salt of 20 ~ 40g/L, the nickelous nitrate of 1 ~ 3g/L.
4. a kind of steel surface according to claim 1 covers the method for cold black coslettising film, it is characterized in that, the content of described antimony ion in Phosphating Solution is 0.5 ~ 2g/L.
5. a kind of steel surface according to claim 1 covers the method for cold black coslettising film, it is characterized in that, the current density of described electrolytic phosphating is 0.5 ~ 3A/dm2.
6. a kind of steel surface according to claim 1 covers the method for cold black coslettising film, it is characterized in that, the described electrolytic phosphating time is 5 ~ 20 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410489111.3A CN104294349B (en) | 2014-09-23 | 2014-09-23 | A kind of steel surface covers the method for cold black coslettising film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410489111.3A CN104294349B (en) | 2014-09-23 | 2014-09-23 | A kind of steel surface covers the method for cold black coslettising film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104294349A true CN104294349A (en) | 2015-01-21 |
| CN104294349B CN104294349B (en) | 2016-11-23 |
Family
ID=52314290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410489111.3A Expired - Fee Related CN104294349B (en) | 2014-09-23 | 2014-09-23 | A kind of steel surface covers the method for cold black coslettising film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104294349B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109898123A (en) * | 2019-03-11 | 2019-06-18 | 山东凤阳佰乐舒家居有限公司 | A kind of steel wire drawing electrolytic phosphating liquid and preparation method thereof |
| CN110863229A (en) * | 2019-12-09 | 2020-03-06 | 嘉兴东恒机械设备有限公司 | Novel metal material acid-free electrolytic phosphating process |
| CN111197163A (en) * | 2018-11-20 | 2020-05-26 | 天津市银丰钢绞线股份有限公司 | Pretreatment process of steel strand |
| CN113073371A (en) * | 2021-03-22 | 2021-07-06 | 领润(南京)绿色化学有限公司 | Clean anode plate friendly electrolytic phosphating solution and phosphating process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077757A (en) * | 1992-04-13 | 1993-10-27 | 无锡市电镀总厂 | black phosphating solution and preparation method thereof |
| US6346186B1 (en) * | 1996-08-29 | 2002-02-12 | Danfoss A/S | Method for electrochemical phosphating of metal surfaces |
| CN102061503A (en) * | 2010-11-19 | 2011-05-18 | 江苏巨力钢绳有限公司 | Electrolytic phosphating method for steel wires |
| CN102212864A (en) * | 2011-06-10 | 2011-10-12 | 沈阳理工大学 | Method for modifying electrolysis phosphorization membrane |
-
2014
- 2014-09-23 CN CN201410489111.3A patent/CN104294349B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077757A (en) * | 1992-04-13 | 1993-10-27 | 无锡市电镀总厂 | black phosphating solution and preparation method thereof |
| US6346186B1 (en) * | 1996-08-29 | 2002-02-12 | Danfoss A/S | Method for electrochemical phosphating of metal surfaces |
| CN102061503A (en) * | 2010-11-19 | 2011-05-18 | 江苏巨力钢绳有限公司 | Electrolytic phosphating method for steel wires |
| CN102212864A (en) * | 2011-06-10 | 2011-10-12 | 沈阳理工大学 | Method for modifying electrolysis phosphorization membrane |
Non-Patent Citations (3)
| Title |
|---|
| 张允诚等: "《电镀手册》", 31 January 2007, 国防工业出版社 * |
| 秦国治等: "《防腐蚀技术及应用实例》", 30 April 2002, 化学工业出版社 * |
| 胡国辉等: "《金属磷化工艺技术》", 31 January 2009, 国防工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111197163A (en) * | 2018-11-20 | 2020-05-26 | 天津市银丰钢绞线股份有限公司 | Pretreatment process of steel strand |
| CN109898123A (en) * | 2019-03-11 | 2019-06-18 | 山东凤阳佰乐舒家居有限公司 | A kind of steel wire drawing electrolytic phosphating liquid and preparation method thereof |
| CN110863229A (en) * | 2019-12-09 | 2020-03-06 | 嘉兴东恒机械设备有限公司 | Novel metal material acid-free electrolytic phosphating process |
| CN113073371A (en) * | 2021-03-22 | 2021-07-06 | 领润(南京)绿色化学有限公司 | Clean anode plate friendly electrolytic phosphating solution and phosphating process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104294349B (en) | 2016-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103184446B (en) | Forming solution for environment-friendly non-phosphate ceramic film and preparation method and application thereof | |
| CN100464007C (en) | Process for preparing neodymium-iron-boron permanent magnetic material surface gradient function coating layer | |
| CN103695871B (en) | The rust inhibition anion intercalation hydrotalcite film that a kind of Mg alloy surface hydrothermal deposition legal system is standby | |
| CN104294349B (en) | A kind of steel surface covers the method for cold black coslettising film | |
| CN102747356B (en) | Normal temperature calcium-manganese phosphorizing liquid | |
| CN102586769A (en) | Nonphosphorus metal surface treatment agent and use method thereof | |
| CN107012453B (en) | A kind of method that green low temperature quickly prepares phosphating coat | |
| CN102653643A (en) | Zinc-based composite coating for improving corrosion resistance of neodymium-iron-boron magnet | |
| CN102839403A (en) | Method for electroplating aluminum in ionic liquid | |
| CN101476146A (en) | Method for preparing black ceramic membrane by magnesium alloy differential arc oxidation | |
| CN103265661B (en) | Coating and conductive resin of film zinc coat | |
| CN105350049A (en) | Preparing method for graphene oxide composite coating on surface of magnesium alloy | |
| CN103060865A (en) | Zinc alloy composite electroplating method for protecting at metal surface | |
| CN108998781A (en) | A kind of car body coating front surface zirconium treatment technique | |
| CN104250763A (en) | Phosphating process as cathode electrophoresis coating pretreatment | |
| CN102747360A (en) | Chromium-free passivation method for galvanized steel sheet by using molybdate/polyphosphate composite system | |
| CN104342683A (en) | Magnesium alloy work-piece surface anti-corrosion conversion film treatment process | |
| CN103087627A (en) | Metal aluminum alloy silane surface treating agent and preparation method thereof | |
| CN103160822B (en) | Fluorine-free phosphating process of AZ91 magnesium alloy | |
| CN201908133U (en) | Iridescent passivation galvanized composite layer of hinge | |
| CN104109849A (en) | Stable high-adhesive aluminum alloy surface conditioning agent | |
| CN101831685A (en) | Electrophoretic coating method for surface of magnesium alloy part | |
| CN109280913A (en) | Green galvanized chromium-free sky blue passivator | |
| CN105543919B (en) | The method that Mg alloy surface forms plating conductive coating by physical vapour deposition (PVD) | |
| CN104099592A (en) | Surface treating agent for smooth foamless 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161123 Termination date: 20170923 |