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 PDF

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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
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steel surface
phosphating
film
black
coslettising
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CN201410489111.3A
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CN104294349B (en
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李锋
王桂燕
孙弘
李枚枚
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Shenyang University
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Shenyang University
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/36Phosphatising

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

A kind of steel surface covers the method for cold black coslettising film
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.
CN201410489111.3A 2014-09-23 2014-09-23 A kind of steel surface covers the method for cold black coslettising film Expired - Fee Related CN104294349B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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

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CN102061503A (en) * 2010-11-19 2011-05-18 江苏巨力钢绳有限公司 Electrolytic phosphating method for steel wires
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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

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Cited By (4)

* Cited by examiner, † Cited by third party
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

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