CN108179411A - A kind of medium temperature black phosphating solution and its application - Google Patents
A kind of medium temperature black phosphating solution and its application Download PDFInfo
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- CN108179411A CN108179411A CN201810005138.9A CN201810005138A CN108179411A CN 108179411 A CN108179411 A CN 108179411A CN 201810005138 A CN201810005138 A CN 201810005138A CN 108179411 A CN108179411 A CN 108179411A
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- medium temperature
- temperature black
- black phosphating
- phosphating solution
- phosphating
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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
- C23C22/06—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 aqueous acidic solutions with pH less than 6
- C23C22/40—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 aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—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 aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The medium temperature black phosphating solution of the present invention is included comprising blackening agent for surface, auxiliary film former, film forming accelerating, pH buffer, complexing agent, surface active agent and water, which is combined phosphating solution with blackening liquid, simplicity operating procedure.The surface medium temperature black phosphating solution of the present invention can be used for the phosphorating treatment of the steel such as carbon steel, and easy to operate, phosphating time is short, and temperature is relatively low, and phosphatization effect is good, and corrosion resistance is excellent, is suitable for industrialization promotion.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, and in particular to a kind of black phosphating solution for carbon steel and
Its application in phosphorating treatment.
Background technology
Carbon steel black phosphating film not only has good corrosion resisting property, but also with certain decoration function.Black phosphating
Film outward appearance is in black, and good bonding strength, film is not easy to erase, with the property such as intensive grain structure and insulating properties, bright property
Energy.Since traditional high temperature black phosphatization has the following disadvantages：It is operated under hot conditions, energy expenditure is excessive, and black phosphorus
Change liquid ingredient to be lost in due to volatilization, composition transfer is fast, and black phosphating film is easier attachment precipitation, and film forming thickness is uneven.It is black
Color phosphatization gradually develops to middle low temperature direction.Medium temperature black phosphating process membranous layer corrosion resistance is similar with high temperature phosphorization film, simultaneously
Solution is relatively stablized, and faster, production efficiency higher, application is very extensive for black phosphating rate.
Due in some optical instruments, to reduce the irreflexive interference of instrument inner wall, it is desirable that film layer will be in not only black, and
And need to have good corrosion resisting property.In order to meet this requirement, people begin one's study the new process of carbon steel black phosphating, will
Melanism and phosphatization are combined, both comprehensive advantage, improve the extensive use of black phosphating.Research shows that black phosphating film has
There are the excellent properties such as decoration, anti-attrition, extinction, delustring, heat absorption, insulation.Melanism and phosphating process are combined, can by addition into
Film accelerating agent is realized, in the oxidation film of matrix surface generation, has reached protection and decoration function, has had extensive promotion and application
Value.Carbon steel black phosphating is the comprehensive Common advantages to black with phosphatization, and black phosphating film is not only excellent with general phosphating coat
It is different in nature can, and phosphatization film outward appearance darkly color has good decoration performance.
At present, black phosphating process mainly divides two types.One kind is on the basis of former phosphating solution, adds blackening agent for surface,
Carry out the black phosphating of steel.Another is will to black and phosphatization carries out step-by-step processing, i.e., first melanism phosphatization or first phosphatization again
Darkening process again.A kind of steel surface is disclosed in Chinese invention patent application CN104294349A and covers cold black coslettising film
Method, using catholyte method for bonderizing, normal temperature phosphating is carried out to steel surface.Chinese invention patent application
A kind of process of surface treatment of ferrous metal product is disclosed in 201610450588.X, needs that phosphating solution temperature first is heated to 60
It~65 DEG C, then sprays to ferrous metal product surface, complicated for operation, waste is more.
Invention content
For carbon steel when carrying out phosphatization, easily generate that blackness is inadequate, and adhesive force is poor, it is a series of that corrosion resisting property is poor etc.
Problem the present invention is intended to provide a kind of black phosphating solution can improve film properties, can realize efficient phosphatization at low ambient temperatures,
Both achieve the purpose that beauty, and can also enhance the corrosion resistance of film, and be conducive to the popularization and application of carbon steel.
Specifically, the present invention adopts the following technical scheme that：
The present invention provides a kind of medium temperature black phosphating solution, which is made of the raw material of following parts by weight：
In per 1L medium temperature black phosphating solutions containing 0~5g of blackening agent for surface, auxiliary film former 1g, 0~3g of film forming accelerating, pH buffer 0~
5g, complexing agent 2g and surface active agent 3g, surplus are water.
Blackening agent for surface of the present invention is preferably selenous acid.
Auxiliary film former of the present invention includes cobalt nitrate, phosphate dihydrogen manganese, ferric sulfate, nickel sulfate, sodium molybdate, molybdic acid
It is one or more in ammonium.
Film forming accelerating of the present invention is one in potassium permanganate, tert-butyl hydroquinone, 4- tert. butyl cyclohexanols
Kind is a variety of.
PH buffer of the present invention is zinc dihydrogen phosphate and phosphoric acid.
Surface active agent of the present invention is preferably citric acid；The complexing agent is preferably alkyl phenol polyoxyethylene ether；
The water is preferably distilled water.
The present invention also provides a kind of preparation method of medium temperature black phosphating solution, 40 DEG C of the phosphatization temperature of the preparation method, phosphorus
It is 10~20 minutes to change the time.
40 DEG C of the phosphatization temperature of currently preferred preparation method, phosphating time are 15 minutes.
It is described the present invention also provides a kind of application of medium temperature black phosphating solution in the processing of metal material medium temperature black phosphating
Metal material is preferably carbon steel material.
Compared with prior art, there are following advantages using the present invention of above-mentioned technical proposal：
(1) phosphating solution is combined by the present invention with blackening liquid, simplicity operating procedure；
(2) black phosphating solution of the invention is free of the heavy metal elements such as nitrite and chromium, and harmfulness is low, and performance is stablized,
Service life is long；
(3) phosphatization temperature of the invention is relatively low, and the time is short, easy to operate；
(4) present invention compared organic film forming accelerating and influence of the inorganic film forming accelerating to phosphatization film properties；
(5) film properties can be improved using the present invention, both achieved the purpose that beauty, can also enhance the corrosion resistance of film, be conducive to
The popularization and application of carbon steel.
Description of the drawings
Fig. 1：It is (a concentration of to the influence schematic diagram of phosphating coat open circuit potential-time graph for TBHQ content
0-2.5g/L)。
Fig. 2：The influence schematic diagram (a concentration of 0-5g/L) for being selenous acid content to phosphating coat AC impedance spectroscopy.
Fig. 3：The influence schematic diagram (a concentration of 0-4g/L) for being biphosphate Zn content to phosphating coat Tafel curve.
Fig. 4：For gained black phosphating film surface topography map, (figure a, b, c, d, e, f are 1000 times to 20000 times of amplification respectively
The surface topography map of film layer, each component concentration are respectively selenous acid 2g/L, cobalt nitrate 1g/L, phosphate dihydrogen manganese 1g/L, ferric sulfate
1g/L, nickel sulfate 1g/L, sodium molybdate 1g/L, ammonium molybdate 1g/L, tert-butyl hydroquinone 2.5g/L, zinc dihydrogen phosphate 3g/L, phosphorus
Sour 2g/L, citric acid 2g/L, alkyl phenol polyoxyethylene ether 3g/L).
Specific embodiment
Further description is made to the technical solution in the present invention below in conjunction with the drawings and specific embodiments.Except as otherwise
Outside illustrating, instrument, material, reagent used in the following example etc. can be obtained by routine business means.
Embodiment 1-3：Different film forming acceleratings test the impact effect of carbon steel black phosphating film properties.
Embodiment 1-3 components and its dosage
3 kinds of black phosphating solutions in embodiment 1-3 are used for the phosphorating treatment of carbon steel, phosphatization temperature to be 40 DEG C, during phosphatization
Between be 15min.The phosphorus characteristic to judge phosphating solution is tested according to drop, the results are shown in Table 1.
Table 1：Embodiment 1-3 testing results
| Embodiment | Drop experimental period/s |
| 1 | 46 |
| 2 | 16 |
| 3 | 28 |
As shown in Table 1, in the case where film forming accelerating content is 1g/L, C10H14O2Drop experimental period up to
76s illustrates that its corrosion resistance is preferable.
Embodiment 4-9：Various concentration film forming accelerating tests the impact effect of carbon steel black phosphating film properties.
Table 2：Embodiment 4-9 components and its dosage
6 kinds of phosphating solutions in embodiment 4-9 are used for the phosphorating treatment of carbon steel, phosphatization temperature to be 40 DEG C, and phosphating time is
15min.Judge the phosphorus characteristic of phosphating solution (corrosion resistance) according to electrochemistry experiment, the results are shown in Figure 1.
It is learnt by Fig. 1, the AC impedance curves of different tert-butyl hydroquinone concentration lower films is in high frequency region by an approximation
The curve of semicircle, is made of in low frequency range straight line, wherein, the capacitive reactance arc radius of the corresponding AC impedance curves of 2.5g/L is most
Greatly, charge transport capability is worst, and impedance value is maximum, and the corrosion resistance of film is best.Therefore, when phosphorus acid content is 2.5g/L, sample
Corrosion resistance it is more excellent.
Embodiment 10-15：Various concentration blackening agent for surface tests the impact effect of carbon steel black phosphating film properties.
Table 4：Embodiment 10-15 components and its dosage
6 kinds of phosphating solutions in embodiment 10-15 are used for the phosphorating treatment of Al-alloy parts, phosphatization temperature to be 40 DEG C, phosphatization
Time is 15min.Judge the phosphorus characteristic of phosphating solution (corrosion resistance) according to electrochemistry experiment, the results are shown in Figure 2.
In AC impedance figure, the semicircle in high-frequency range represents the transfer process of charge, low frequency model under normal conditions
The straight line enclosed represents the diffusion process of ion.As shown in Figure 2, capacitive reactance arc radius is bigger, and film layer charge transport capability is weaker, film layer
Resistance is larger.Low frequency range is straight line, and ideally, slope 1, under nonideality, slope is bigger, show solution from
The diffusional resistance of son is bigger.During a concentration of 2g/L of selenous acid, film layer resistance RpIt is up to 130.9 Ω, illustrates Charge-transfer resistance
Larger, corrosion resistance is preferable, and the effect of comprehensive charge transport capability and ion-diffusibility preferably selects a concentration of 2g/ of selenous acid
L。
Embodiment 16-20：PH buffers test the impact effect of carbon steel black phosphating film properties.
Table 4：Embodiment 16-20 components and its dosage
5 kinds of phosphating solutions in embodiment 16-20 are used for the phosphorating treatment of Al-alloy parts, phosphatization temperature to be 40 DEG C, phosphatization
Time is 15min.Judge the phosphorus characteristic of phosphating solution (corrosion resistance) according to electrochemistry experiment, the results are shown in Figure 3.
From the figure 3, it may be seen that as a concentration of 3g/L of zinc dihydrogen phosphate, most just, corrosion current is smaller for corrosion potential, accordingly
Corrosion resistance it is maximum.During a concentration of 0g/L of zinc dihydrogen phosphate, corrosion resistance is minimum.Relative to blank sample, di(2-ethylhexyl)phosphate is added
After hydrogen zinc, the corrosion resistance of film all improves a lot, and significantly reduces the extent of corrosion of film, improves the corrosion resistance of film.
Therefore, biphosphate zinc concentration is preferably 3g/L, and the corrosion resistance of black phosphating film is best at this time, is effectively protected carbon steel, corresponding
The surface topography of gained film layer is illustrated in Fig. 4, can be seen that the in irregular shape of particle from 20000 times of figure of amplification, size is not
Unified, some is in twisted shape, and some is in grains.Can be seen that black phosphating film from 1000 times and 2000 times of figure of amplification is
It is made of crystal grain of different sizes one by one, grain shape is irregular, and has and can see some apparent slight cracks, overall next
Say that film layer can be said to be uniform.
Claims (10)
1. a kind of medium temperature black phosphating solution, which is characterized in that the medium temperature black phosphating solution is made of the raw material of following parts by weight：
In per 1L medium temperature black phosphating solutions containing 0~5g of blackening agent for surface, auxiliary film former 1g, 0~3g of film forming accelerating, pH buffer 0~
5g, complexing agent 2g and surface active agent 3g, surplus are water.
2. medium temperature black phosphating solution according to claim 1, which is characterized in that the blackening agent for surface is selenous acid.
3. medium temperature black phosphating solution according to claim 1, which is characterized in that the auxiliary film former include cobalt nitrate,
It is one or more in phosphate dihydrogen manganese, ferric sulfate, nickel sulfate, sodium molybdate, ammonium molybdate.
4. medium temperature black phosphating solution according to claim 1, which is characterized in that the film forming accelerating for potassium permanganate,
It is one or more in tert-butyl hydroquinone, 4- tert. butyl cyclohexanols.
5. medium temperature black phosphating solution according to claim 1, which is characterized in that the pH buffer for zinc dihydrogen phosphate with
Phosphoric acid.
6. medium temperature black phosphating solution according to claim 1, which is characterized in that the surface active agent is citric acid；Institute
Complexing agent is stated as alkyl phenol polyoxyethylene ether；The water is distilled water.
7. according to the preparation method of claim 1-6 any one of them medium temperature black phosphating solutions, which is characterized in that the preparation side
40 DEG C of the phosphatization temperature of method, phosphating time are 10~20 minutes.
8. preparation method according to claim 7, which is characterized in that 40 DEG C of the phosphatization temperature of the preparation method, during phosphatization
Between be 15 minutes.
9. according to claim 1-6 any one of them medium temperature black phosphating solutions in the processing of metal material medium temperature black phosphating
Using.
10. application according to claim 9, which is characterized in that the metal material is carbon steel material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810005138.9A CN108179411A (en) | 2018-01-03 | 2018-01-03 | A kind of medium temperature black phosphating solution and its application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810005138.9A CN108179411A (en) | 2018-01-03 | 2018-01-03 | A kind of medium temperature black phosphating solution and its application |
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| CN108179411A true CN108179411A (en) | 2018-06-19 |
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| CN201810005138.9A Pending CN108179411A (en) | 2018-01-03 | 2018-01-03 | A kind of medium temperature black phosphating solution and its application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261837A (en) * | 2022-06-30 | 2022-11-01 | 东风商用车有限公司 | Pre-painting treatment process for steel-aluminum mixed base material |
Citations (4)
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|---|---|---|---|---|
| CN102021548A (en) * | 2010-12-18 | 2011-04-20 | 江苏德美科技有限公司 | Blackening agent used for steel and iron surface at room temperature and preparation method for blackening agent at room temperature |
| CN102953055A (en) * | 2012-11-07 | 2013-03-06 | 长沙沃尔金属表面技术有限公司 | Black phosphating liquid and use method thereof |
| CN106811742A (en) * | 2017-01-23 | 2017-06-09 | 江苏理工学院 | It is a kind of for the room temperature blackening liquid of steel and its application |
| CN106967970A (en) * | 2017-04-10 | 2017-07-21 | 武汉迪赛新材料有限公司 | Normal-temperature blackening passivating agent for steel surface |
-
2018
- 2018-01-03 CN CN201810005138.9A patent/CN108179411A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021548A (en) * | 2010-12-18 | 2011-04-20 | 江苏德美科技有限公司 | Blackening agent used for steel and iron surface at room temperature and preparation method for blackening agent at room temperature |
| CN102953055A (en) * | 2012-11-07 | 2013-03-06 | 长沙沃尔金属表面技术有限公司 | Black phosphating liquid and use method thereof |
| CN106811742A (en) * | 2017-01-23 | 2017-06-09 | 江苏理工学院 | It is a kind of for the room temperature blackening liquid of steel and its application |
| CN106967970A (en) * | 2017-04-10 | 2017-07-21 | 武汉迪赛新材料有限公司 | Normal-temperature blackening passivating agent for steel surface |
Non-Patent Citations (1)
| Title |
|---|
| 王振廷等: "《材料表面工程技术》", 30 September 2011, 哈尔滨工业大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261837A (en) * | 2022-06-30 | 2022-11-01 | 东风商用车有限公司 | Pre-painting treatment process for steel-aluminum mixed base material |
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Application publication date: 20180619 |
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