CN104294349B - A kind of steel surface covers the method for cold black coslettising film - Google Patents
A kind of steel surface covers the method for cold black coslettising film Download PDFInfo
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- CN104294349B CN104294349B CN201410489111.3A CN201410489111A CN104294349B CN 104294349 B CN104294349 B CN 104294349B CN 201410489111 A CN201410489111 A CN 201410489111A CN 104294349 B CN104294349 B CN 104294349B
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- phosphating
- black
- film
- antimony
- organic acid
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- 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
Abstract
A kind of steel surface covers the method for cold black coslettising film, relate to the film covering method of a kind of steel surface, nigrescent phosphatizing solution of the present invention is by organic acid antimony, the zinc oxide of 5 ~ 10g/L, the phosphoric acid of 30 ~ 60g/L, the Mazhev salt of 20 ~ 40g/L, the nickel nitrate composition of 1 ~ 3g/L, water surplus.Using catholyte method for bonderizing, steel surface is carried out normal temperature phosphating, electric current density is 0.5 ~ 3A/dm2, and the time is 5 ~ 20 minutes.The present invention is a kind of steel by black phosphating coat preparation method energy-conservation, environmentally friendly, and Phosphating Solution is stable, and phosphating process is simple and convenient to operate, and film forming speed is fast, and film layer color and luster is pitch-black, and corrosion resistance is good, it is adaptable to various steel surfaces process.
Description
Technical field
The present invention relates to the film covering method of a kind of steel surface, particularly relate to a kind of method that steel surface covers 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 has the methods such as high-temperature alkaline chemical oxidation blackout, room temperature selenides system blackout and black phosphating.The power consumption of high-temperature alkaline blackening is big, production cycle length, labor condition are poor and environmental pollution is serious.Although it is time-consuming long that room temperature selenides system blackout solves high-temperature alkaline blackout, need the problems such as heating, but the selenides in hair blackening liquid is expensive, and toxicity is bigger.Black phosphating is chemical conversion membrane preparation technology blackout being integrated in one with phosphatization, not only has the excellent properties of general phosphating coat, and phosphating coat outward appearance is black.At present, most of steel surface black phosphatings are the middle high temperature phosphorizations of manganese systems.The outward appearance of middle high temperature manganese phosphate coating and corrosion resistance are preferable, but its efficiency is low, and energy expenditure is big, and parkerizing process complex management, produce sediment many.In recent years, have been reported with the cold black coslettising technology that Sb3+ ion is main blackening agent for surface.Compared with selenides, Sb3+ ion toxicity is low, and raw material is relatively cheap to be easy to get.But Sb3+ ion easily hydrolyzes, phosphatization needs to carry out in denseer hydrochloric acid medium, and the careless slightly hydrolysis being easy for causing Sb3+ ion in Phosphating Solution process for preparation.Phosphatization in hydrochloric acid medium, inevitably brings substantial amounts of chloride ion in phosphating coat, chloride ion has important impact to the corrosion resisting property of film layer.
Summary of the invention
It is an object of the invention to provide a kind of method that steel surface covers cold black coslettising film, the phosphatization hair blackening liquid environmental friendliness of the method employing, stable performance, by electrolytic phosphating technology, steel by black phosphating coat can be quickly prepared with room temperature, by Sb3+ ion and organic acid reaction, generate stable organic acid antimony complex and add in Phosphating Solution.This Phosphating Solution is stable, it is not necessary to strong acid media phosphorization filming, and energy consumption is low, and film forming is fast, sediment is few, and technique is simple, medicine uses few, and film layer color and luster is pitch-black firmly, and corrosion resistance is good.
It is an object of the invention to be achieved through the following technical solutions:
A kind of steel surface covers method described in the method for cold black coslettising film and includes procedure below:
(1) Butter of antimony. (SbCl3) or antimony oxide (Sb2O3) are generated the antimonious complex of organic acid with organic acid reaction；
(2) antimonious for organic acid complex is dissolved in Phosphating Solution, obtains the Phosphating Solution containing organic acid antimony；
(3) phosphatization, the steel sample after will 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, forms one layer of pitch-black, fine and close phosphorization membrane at steel surface after oil sealing.
The method that described a kind of steel surface covers cold black coslettising film, described organic acid is any one in tartaric acid, citric acid, disodiumedetate.
The method that described a kind of steel surface covers cold black coslettising film, 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 nickel nitrate of 1 ~ 3g/L.
The method that described a kind of steel surface covers cold black coslettising film, described antimony ion content in Phosphating Solution is 0.5 ~ 2g/L.
The method that described a kind of steel surface covers cold black coslettising film, the electric current density of described electrolytic phosphating is 0.5 ~ 3A/dm2.
The method that described a kind of steel surface covers cold black coslettising film, the described electrolytic phosphating time is 5 ~ 20 minutes.
Advantages of the present invention with effect is:
(1) normal-temperature phosphorizing liquid prepared by the present invention does not contains supervirulent selenides, environmental friendliness；
(2) main blackening agent for surface Sb3+ ion and organic acid reaction generate the complex of organic acid antimony, it is suppressed that the hydrolysis of antimony ion, Phosphating Solution is stable, it is to avoid phosphatization in strong acid media；
(3) use electrolytic phosphating can film formation, medicine uses few, it is not necessary to add various Phosphating Accelerant and coalescents, and film forming speed is fast, and energy consumption is low, and sediment is few, and technique is simple, it 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 digital photo (corresponding embodiment 1 product) 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).
Detailed description of the invention
Illustrated embodiment below in conjunction with the accompanying drawings, the invention will be further described.
The adjustable DC source of 0 ~ 30V is selected to provide adjustable DC 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, selecting different nigrescent phosphatizing formula of liquid, galvanization carries out electrolytic phosphating, is embodied as case as follows:
Embodiment 1
(1) Butter of antimony. (SbCl3) and tartaric acid are reacted the generation antimonious complex of tartaric acid；
Preparation method: 2.3 grams of Butter of antimony., 6 grams of tartaric acid are dissolved in water, and dropping sodium hydroxide solution is clarified to reactant liquor while stirring, obtains the antimonious complex of tartaric acid.
(2) antimonious for tartaric acid complex is dissolved in Phosphating Solution, obtains the Phosphating Solution containing antimony tartrate；
The zinc oxide of preparation method: 6g/L, the phosphoric acid of 35g/L, the Mazhev salt of 30g/L, the nickel nitrate of 1g/L add in tartaric acid trivalent antimony complex solution after dissolving clarification, obtain nigrescent phosphatizing solution.
(3) phosphatization, the steel sample after will cleaning is placed in containing in the antimonious Phosphating Solution of tartaric acid, room temperature electrolytic phosphating 10 minutes；
Phosphatization electric current density is 1.5A/dm2, and phosphating coat is complete, colors black.
(4) steel sample after phosphatization carries out washing, saponification, can form one layer of pitch-black, fine and close phosphorization membrane at steel surface after oil sealing.
In order to improve corrosion resistance and the dicoration of film layer further, nigrescent phosphatizing film is carried out saponification, oil sealing process.Saponification process is soap 10 ~ 30g/L, 70 ~ 90 DEG C, 3 ~ 5min；Oil sealing technique is that standard machinery oil room temperature soaks 5min.Iron and steel test piece after phosphatization processes through washing, saponification and oil sealing, and the drop of the resistance to copper sulfate time is more than 20min.
Fig. 1 is the infrared spectrogram of the tartaric acid trivalent antimony complex of embodiment 1 preparation.At 1690 ~ 1730cm-
1 does not has absworption peak to occur, illustrates that the carboxyl in tartaric acid molecules has become salt.Antisymmetric stretching vibration absworption peak and the symmetrical stretching vibration absworption peak of carboxyl in carboxylate it is respectively at 1560cm-1 and 1340cm-1.The absworption peak occurred at 472cm-1 is Sb-O stretching vibration absworption peak, the formation of infrared spectrum explanation tartaric acid trivalent antimony complex.
The digital photograph of phosphating coat is shown in Fig. 2, it can be seen that Film color is black, covers matrix good, even film layer, densification.The wiping of exerting oneself of film layer cotton is hundreds of time, and phosphating coat does not fall ash, do not fades, and display black phosphating film is strong with matrix adhesive force.
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 close granular particles.
EDAX results such as Fig. 4 of electrolysis black phosphating film layer.Result shows, black phosphating film layer is mainly made up of chemical elements such as Zn, Mn, O, P, Sb, Ni.
Embodiment 2
(1) Butter of antimony. (SbCl3) is generated the antimonious complex of citric acid with citric acid reactions；
Preparation method: 3.8 grams of Butter of antimony., 12 grams of citric acids are dissolved in water, and dropping sodium hydroxide solution is clarified to reactant liquor while stirring, obtains the antimonious complex of citric acid.
(2) antimonious for citric acid complex is dissolved in Phosphating Solution, obtains the Phosphating Solution containing citric acid antimony；
The zinc oxide of preparation method: 8g/L, the phosphoric acid of 60g/L, the Mazhev salt of 20g/L, the nickel nitrate of 3g/L add in citric acid trivalent antimony complex solution after dissolving clarification, obtain nigrescent phosphatizing solution.
(3) phosphatization, the steel sample after will cleaning is placed in containing in the antimonious Phosphating Solution of tartaric acid, room temperature electrolytic phosphating 20 minutes；
Phosphatization electric current density is 0.5A/dm2, and phosphating coat is complete, colors black.
(4) steel sample after phosphatization carries out washing, saponification, can form one layer of pitch-black, fine and close phosphorization membrane at steel surface after oil sealing.
Steel sample after phosphatization processes through washing, saponification and oil sealing, and the drop of the resistance to copper sulfate time is more than 20min.
Embodiment 3
(1) antimony oxide (Sb2O3) and disodiumedetate are reacted the generation antimonious complex of ethylenediaminetetraacetic acid；
Preparation method: 0.95 gram of antimony oxide, 4 grams of disodiumedetates are dissolved in water, and dropping sodium hydroxide solution is clarified to reactant liquor while stirring, obtains the antimonious complex of ethylenediaminetetraacetic acid.
(2) antimonious for ethylenediaminetetraacetic acid complex is dissolved in Phosphating Solution, obtains the Phosphating Solution containing ethylenediaminetetraacetic acid antimony；
The zinc oxide of preparation method: 5g/L, the phosphoric acid of 30g/L, the Mazhev salt of 40g/L, the nickel nitrate of 2g/L add in ethylenediaminetetraacetic acid trivalent antimony complex solution after dissolving clarification, obtain nigrescent phosphatizing solution.
(3) phosphatization, the steel sample after will cleaning is placed in containing in the antimonious Phosphating Solution of ethylenediaminetetraacetic acid, room temperature electrolytic phosphating 5 minutes；
Phosphatization electric current density is 2.0A/dm2, and phosphating coat is complete, colors black.
(4) steel sample after phosphatization carries out washing, saponification, can form one layer of pitch-black, fine and close phosphorization membrane at steel surface after oil sealing.
Steel sample after phosphatization processes through washing, saponification and oil sealing, and the drop of the resistance to copper sulfate time is more than 20min.
Claims (1)
1. the method that a steel surface covers cold black coslettising film, it is characterised in that described method includes procedure below:
(1) by Butter of antimony. (SbCl3) or antimony oxide (Sb2O3) generate the antimonious complex of organic acid with organic acid reaction；
(2) antimonious for organic acid complex is dissolved in Phosphating Solution, obtains the Phosphating Solution containing organic acid antimony；
(3) phosphatization, the steel sample after will 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, forms one layer of pitch-black, fine and close phosphorization membrane at steel surface after oil sealing；
Described organic acid is any one in tartaric acid, citric acid, disodiumedetate；
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 nickel nitrate of 1 ~ 3g/L；
Described antimony ion content in Phosphating Solution is 0.5 ~ 2g/L；
The electric current density of described electrolytic phosphating is 0.5 ~ 3A/dm2；
The described electrolytic phosphating time is 5 ~ 20 minutes.
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| 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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| CN1077757A (en) * | 1992-04-13 | 1993-10-27 | 无锡市电镀总厂 | black phosphating solution and preparation method thereof |
| DK173338B1 (en) * | 1996-08-29 | 2000-07-31 | Danfoss As | Process for electrochemical phosphating of metal surfaces, especially of stainless steel, with CaZnPO4 by cold flow of metal |
| 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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