CN106222645B - The method of brass surfaces chemically blackening - Google Patents

The method of brass surfaces chemically blackening Download PDF

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Publication number
CN106222645B
CN106222645B CN201610676822.0A CN201610676822A CN106222645B CN 106222645 B CN106222645 B CN 106222645B CN 201610676822 A CN201610676822 A CN 201610676822A CN 106222645 B CN106222645 B CN 106222645B
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brass
blackening
sodium
carbonate
nigrescence
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CN106222645A (en
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魏守强
刘聘
邵忠才
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Shenyang Ligong University
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Shenyang Ligong University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • C23F3/06—Heavy metals with acidic solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy metals

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The invention discloses a kind of method of brass surfaces chemically blackening, core is that brass is answered with hair blackening liquid hair, is formed on its surface the oxidation film of one layer of black.First, by brass base oil removing, polishing, activation, cleaning；Then it is put in the hair blackening liquid being made of mantoquita and ammonium salt, at room temperature, makes itself and solution reaction, taken out after brass surfaces generate the uniform and stable black film layer of color, then carry out relevant subsequent processing, prevent film surface contaminated.The advantage of the invention is that：Technological process is simple, at low cost, and prepared membranous layer corrosion resistance and binding force are strong, can be good at playing the role of decoration and corrosion-resistant.

Description

The method of brass surfaces chemically blackening
Technical field
The invention belongs to technical field of surface, more particularly to a kind of method of brass surfaces chemically blackening prepares corrosion resistant Lose and have functional protective layer.
Background technology
Ormolu is also known as brass, and intensity and the plasticity scope of application are wide, has good mechanical performance and castability Can, it is processed in material, workpiece manufacture, ornameutal handiwork etc. is widely used.But common binary brass easy oxidation discoloration, Corrosion resistance is poor in the environment of high temperature and humidity, in addition in furnishing fields due to the need of update and the outlet of product in recent years It wants, the single tone of brass is far from meeting production requirement；So being often surface-treated when in use, while playing dress Decorations and corrosion-resistant effect.
Brass surfaces blackening process generally by chemical method one layer of black of its Surface Creation or auburn oxidation film, Sulfide film or alloy layer.Current blackening method common in production has one ammoxidation processing of copper, vulcanizing treatment, persulfate Oxidation processes, thiosulfuric acid salt treatment and black nickel plating etc..But there is certain defect in each system, such as：Sulfide systems The Film color of processing is undesirable；The reaction of thiosulfuric acid salt system needs to heat and react slow；Copper ammonia complexation objects system exists Peculiar smell operation, environment is not good enough, but the obtained Film color of the method preferably and has good binding force.In recent years, someone was sub- Selenic acid-copper sulphate hair blackening liquid blacks copper piece at normal temperatures, but the disadvantage is that pre-treatment requires stringenter, the binding force of black film It is poor.
Invention content
In view of the above-mentioned problems, the present invention provides a kind of methods of brass surfaces chemically blackening.
The technical solution adopted by the present invention is that：A kind of method of brass surfaces chemically blackening, operating process include following step Suddenly
Step 1：Prepare hair blackening liquid, degreasing fluid, polishing fluid, activating solution；
Step 2：Brass is immersed in degreasing fluid and carries out oil removing, is washed later；
Step 3：It will immerse in polishing fluid and be polished through step 2 treated brass, wash later；
Step 4：It will immerse in activating solution and activate through step 3 treated brass, wash later；
Step 5：It will be immersed in hair blackening liquid through step 4 treated brass and carry out blackening process, dried up after washing, you can Black chemical conversion coating is made in brass surfaces；
Step 6：Brass after film forming is washed with water, is used in combination wet cloth or hairbrush to wipe, drying；
Step 7：The corrosion resistance of nigrescence brass is detected by salt spray test.
As a kind of perferred technical scheme：Conversion fluid group, which becomes in 1L solution, to be contained
Basic copper carbonate 30-50g
Ammonium hydrogen carbonate 80-120g
Sodium hydroxide 60-80g.
As a kind of perferred technical scheme：Black night preparation process be with water by basic copper carbonate micro dissolution, then add Enter sodium hydroxide to basic copper carbonate and become navy blue, the ammonium hydrogen carbonate of micro dissolution is added, is stirred continuously to precipitation and dissolves；Finally PH value is adjusted to 10-11 with sodium hydroxide, 2-3h is placed and obtains hair blackening liquid.
As a kind of perferred technical scheme：Oil removal process is in 60-7003-5min, the composition of degreasing fluid are reacted under the conditions of C For
Sodium hydroxide 40-50 g/L
Sodium carbonate 15-20 g/L
Sodium phosphate 40-50 g/L
Sodium metasilicate 5-8 g/L.
As a kind of perferred technical scheme：Polishing process reacts 30s at ambient temperature, and the group of polishing fluid becomes
Hydrogen peroxide 600-700 mL/L
Ethylene glycol 120-150 g/L
Sulfuric acid 30-40g/L
OP-10 1-3ml。
As a kind of perferred technical scheme：Activation process reacts 10-20s at ambient temperature, and the group of activating solution becomes Sulfuric acid 10ml/L.
As a kind of perferred technical scheme：Reaction black to react 2-3min at ambient temperature.
As a kind of perferred technical scheme：One of laking procedure can be added after film forming according to actual needs；Fixation work Sequence is to handle 1-2min at room temperature；The group of fixation liquid becomes
Benzotriazole 0.1-0.5g/L
Ethyl alcohol 20-30ml/L
Lauryl sodium sulfate 1-2g/L.
The beneficial effects of the invention are as follows：Keep technological process simple in brass surfaces plated film using chemical method, reduces cost； Prepared Film color is uniform, corrosion resistance is good, binding force is strong, can be good at playing the role of decoration and corrosion-resistant.
Specific implementation mode
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is technology description to be briefly described, it is therefore apparent that in being described below is only some embodiments of the present invention.
Embodiment 1
1) weighing 30.0000g basic copper carbonates adds water to modulate paste, adds 60.0000g sodium hydroxides with water-soluble Solution, waits for that temperature is down to room temperature, has precipitation to generate in solution at this time, and 80.0000g ammonium hydrogen carbonate is added, and is stirred continuously to having precipitated Fully dissolved adds water to be settled to 1000 mL；It is 10 to adjust pH value, places 2h；
2) 50g sodium hydroxides are weighed, 20g sodium carbonate, 50g sodium phosphates, 8g sodium metasilicate is soluble in water successively, adds water constant volume To 1000mL；
3) 700mL hydrogen peroxide is measured, 150g ethylene glycol, the 40g concentrated sulfuric acids are added later, 2mLOP-10 adds water to be settled to 1000mL；
4) the 10mL concentrated sulfuric acids are slowly added in water, are cooled to room temperature Hou Jiashui and are settled to 1000mL；
5) 0.5g benzotriazole is weighed, 2g lauryl sodium sulfate is soluble in water successively, adds 30mL ethyl alcohol, Water is added to be settled to 1000mL；
5) brass surfaces pre-treatment：To matrix 700Oil removing, duration 5min are carried out under the conditions of C；In room temperature item It is polished under part, duration 30s；Activation process, duration 20s, every two steps operation are carried out at ambient temperature Between intert one of washing step；
6) by treated before menstruation, matrix cleaning dries up, and carries out blackening process.Temperature is room temperature, and the time is 3 minutes；
7) it post-processes, the brass after nigrescence is subjected to fixation treatment at ambient temperature, duration 2min, later Washing drying；
8) corrosion resistance of nigrescence brass is detected by salt spray test, it is as a result as follows：
Salt spray test detection is carried out to the brass after nigrescence by air standard：Nigrescence brass is put into 5% salt fog cabinet, Find that nigrescence brass surfaces do not have apparent pitting corrosion phenomenon through 48 hours salt mist experiments；It is preferable to illustrate that nigrescence brass has Corrosion resistance；
9) binding force that film layer is detected according to hundred lattice testing standards of ISO2409 chooses one 60 mm * in nigrescence brass surfaces The grid of 2 mm * 2mm is drawn in the range of 60 mm with paper knife, all cutting lines must all draw permeable membrane layer to matrix surface；So Adhesive tape is attached to the specimen surface for having drawn grid afterwards, holds one end of adhesive tape, by the direction vertical with film surface at 0.5-1 seconds Inside adhesive tape is pulled open rapidly, checks the case where film layer is sticked up and removed by adhesive tape.It tests nigrescence brass surfaces and finds coloring film layer It does not occur any peeling, peels off, broken phenomenon, illustrate that prepared film layer and basal body binding force are good.
Embodiment 2
1) weighing 40.0000g basic copper carbonates adds water to modulate paste, adds 70.0000g sodium hydroxides with water-soluble Solution, waits for that temperature is down to room temperature, has precipitation to generate in solution at this time, and 95.0000g ammonium hydrogen carbonate is added, and is stirred continuously to having precipitated Fully dissolved adds water to be settled to 1000 mL；It is 10.5 to adjust pH value, places 2.5h；
2) 40g sodium hydroxides are weighed, 15g sodium carbonate, 40g sodium phosphates, 5g sodium metasilicate is soluble in water successively, adds water constant volume To 1000mL；
3) 600mL hydrogen peroxide is measured, 120g ethylene glycol, the 30g concentrated sulfuric acids are added later, 1mLOP-10 adds water to be settled to 1000mL；
4) the 10mL concentrated sulfuric acids are slowly added in water, are cooled to room temperature Hou Jiashui and are settled to 1000mL；
5) 0.1g benzotriazole is weighed, 1g lauryl sodium sulfate is soluble in water successively, adds 20mL ethyl alcohol, Water is added to be settled to 1000mL；
5) brass surfaces pre-treatment：To matrix 600Oil removing, duration 3min are carried out under the conditions of C；In room temperature item It is polished under part, duration 30s；Activation process, duration 10s, every two steps operation are carried out at ambient temperature Between intert one of washing step；
6) by treated before menstruation, matrix cleaning dries up, and carries out blackening process.Temperature is room temperature, and the time is 2 minutes；
7) it post-processes, the brass after nigrescence is subjected to fixation treatment at room temperature, duration 1min is washed later Drying；
8) corrosion resistance of nigrescence brass is detected by salt spray test, it is as a result as follows：
Salt spray test detection is carried out to the brass after nigrescence by air standard：Nigrescence brass is put into 5% salt fog cabinet, Find that nigrescence brass surfaces do not have apparent pitting corrosion phenomenon through 48 hours salt mist experiments；It is preferable to illustrate that nigrescence brass has Corrosion resistance；
9) binding force that film layer is detected according to hundred lattice testing standards of ISO2409 chooses one 60 mm * in nigrescence brass surfaces The grid of 2 mm * 2mm is drawn in the range of 60 mm with paper knife, all cutting lines must all draw permeable membrane layer to matrix surface；So Adhesive tape is attached to the specimen surface for having drawn grid afterwards, holds one end of adhesive tape, by the direction vertical with film surface at 0.5-1 seconds Inside adhesive tape is pulled open rapidly, checks the case where film layer is sticked up and removed by adhesive tape.It tests nigrescence brass surfaces and finds coloring film layer It does not occur any peeling, peels off, broken phenomenon, illustrate that prepared film layer and basal body binding force are good.
Embodiment 3
1) weighing 50.0000g basic copper carbonates adds water to modulate paste, adds 800.0000g sodium hydroxides with water-soluble Solution, waits for that temperature is down to room temperature, has precipitation to generate in solution at this time, and 120.0000g ammonium hydrogen carbonate is added, is stirred continuously to precipitation It is completely dissolved, water is added to be settled to 1000 mL；It is 11 to adjust pH value, places 3h；
2) 5045g sodium hydroxides are weighed, 18g sodium carbonate, 46g sodium phosphates, 7g sodium metasilicate is soluble in water successively, adds water fixed Hold to 1000mL；
3) 670mL hydrogen peroxide is measured, 135g ethylene glycol, the 35g concentrated sulfuric acids are added later, 3mLOP-10 adds water to be settled to 1000mL；
4) the 10mL concentrated sulfuric acids are slowly added in water, are cooled to room temperature Hou Jiashui and are settled to 1000mL；
5) 0.3g benzotriazole is weighed, 1.8g lauryl sodium sulfate is soluble in water successively, adds 27mL second Alcohol adds water to be settled to 1000mL；
5) brass surfaces pre-treatment：To matrix 650Oil removing, duration 4min are carried out under the conditions of C；In room temperature item It is polished under part, duration 30s；Activation process, duration 16s, every two steps operation are carried out at ambient temperature Between intert one of washing step；
6) by treated before menstruation, matrix cleaning dries up, and carries out blackening process.Temperature is room temperature, and the time is 2.5 minutes；
7) it post-processes, the brass after nigrescence is subjected to fixation treatment at ambient temperature, duration 1.6min, it Washing drying afterwards；
8) corrosion resistance of nigrescence brass is detected by salt spray test, it is as a result as follows：
Salt spray test detection is carried out to the brass after nigrescence by air standard：Nigrescence brass is put into 5% salt fog cabinet, Find that nigrescence brass surfaces do not have apparent pitting corrosion phenomenon through 48 hours salt mist experiments；It is preferable to illustrate that nigrescence brass has Corrosion resistance；
9) binding force that film layer is detected according to hundred lattice testing standards of ISO2409 chooses one 60 mm * in nigrescence brass surfaces The grid of 2 mm * 2mm is drawn in the range of 60 mm with paper knife, all cutting lines must all draw permeable membrane layer to matrix surface；So Adhesive tape is attached to the specimen surface for having drawn grid afterwards, holds one end of adhesive tape, by the direction vertical with film surface at 0.5-1 seconds Inside adhesive tape is pulled open rapidly, checks the case where film layer is sticked up and removed by adhesive tape.It tests nigrescence brass surfaces and finds coloring film layer It does not occur any peeling, peels off, broken phenomenon, illustrate that prepared film layer and basal body binding force are good.
It should be noted last that above example is only unrestricted to supplement explaination technical scheme of the present invention.To the greatest extent Pipe is described the invention in detail with reference to embodiment, and this field vast is it will be appreciated by the skilled person that skill to the present invention Art scheme is modified or is replaced on an equal basis, without departure from the spirit and scope of technical solution of the present invention, should all cover at this In the right of invention.

Claims (5)

1. a kind of method of brass surfaces chemically blackening, which is characterized in that specifically include following steps：
Step 1: preparing hair blackening liquid, degreasing fluid, polishing fluid, activating solution；
Oil removing is carried out Step 2: brass is immersed in degreasing fluid, except oil temperature is 60-70 DEG C, the oil removing time is 3-5min, later Washing；
It is polished 30s at room temperature Step 3: will be immersed in polishing fluid through step 2 treated brass, washes later；
Step 4: the brass after step 3 oil removal treatment is immersed in activating solution, 10-20s is activated at room temperature, is washed later；
Step 5: will be immersed in chemically blackening liquid through step 4 treated brass, black reaction to react at ambient temperature 2-3min is dried up after washing, i.e., nigrescence film layer is made in brass surfaces；
Step 6: the brass after film forming is washed with water, it is used in combination wet cloth or hairbrush to wipe, drying；
Step 7: detecting nigrescence brass by salt spray test；
The group of the chemically blackening liquid becomes：Contain basic copper carbonate 30-50g, ammonium hydrogen carbonate 80-120g, hydrogen in 1L solution Sodium oxide molybdena 60-80g；
The preparation method of the chemically blackening liquid：With water by basic copper carbonate micro dissolution, sodium hydroxide is added to basic carbonate Copper becomes navy blue, and the ammonium hydrogen carbonate of micro dissolution is added, and is stirred continuously to precipitation and dissolves；Finally pH value is adjusted with sodium hydroxide For 10-11, places 2-3h and obtain hair blackening liquid.
2. the method for brass surfaces chemically blackening as described in claim 1, which is characterized in that the composition of the degreasing fluid For：40~50 g/L of sodium hydroxide, 5~8 g/L of 15~20 g/L of sodium carbonate, 40~50 g/L of sodium phosphate and sodium metasilicate.
3. the method for brass surfaces chemically blackening as described in claim 1, which is characterized in that the group of the polishing fluid becomes： 600~700 mL/L of hydrogen peroxide, 120~150 g/L of ethylene glycol, 1~3mL/L of sulfuric acid 30~40g/L and OP-10.
4. the method for brass surfaces chemically blackening as described in claim 1, which is characterized in that the activating solution group becomes：Sulphur Sour 10ml/L.
5. the method for brass surfaces chemically blackening as described in claim 1, which is characterized in that add after step six processing It is to handle 1-2min at room temperature to add one of laking procedure, laking procedure；The group of fixation liquid becomes：Benzotriazole 0.1- 0.5g/L, ethyl alcohol 20-30ml/L, lauryl sodium sulfate 1-2g/L.
CN201610676822.0A 2016-08-17 2016-08-17 The method of brass surfaces chemically blackening Expired - Fee Related CN106222645B (en)

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CN108360000A (en) * 2018-04-17 2018-08-03 江苏江润铜业有限公司 Lian Lalian plates aqueous annealing liquid
CN109112522A (en) * 2018-08-07 2019-01-01 道晟拉链科技（太仓）有限公司 A kind of coloring process of brass teeth zipper
CN109023377A (en) * 2018-08-07 2018-12-18 道晟拉链科技（太仓）有限公司 A kind of polishing process of brass teeth zipper
CN109207980A (en) * 2018-09-28 2019-01-15 宁波永新光学股份有限公司 A kind of method that brass part surface oxidation blacks
WO2021134293A1 (en) * 2019-12-30 2021-07-08 诚瑞光学(常州)股份有限公司 Light shield component and blackening method therefor
CN112111734A (en) * 2020-06-28 2020-12-22 宁波博曼特工业有限公司 Copper product blackening process
CN112779531B (en) * 2020-12-08 2024-02-02 广东山之风环保科技有限公司 Treatment process for coloring black oxide film on metal surface

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CN102154638B (en) * 2011-03-21 2012-09-12 厦门大学 Brass part blackening solution and preparation method and application thereof
CN103352216B (en) * 2013-07-09 2016-04-13 嘉兴职业技术学院 The coloring treatment process of a kind of copper or copper alloy surface
CN104630760B (en) * 2015-01-23 2016-11-23 沈阳理工大学 A kind of brass surfaces prepares the preparation method of purple chemical composition coating

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