CN108060413A - A kind of steel surface vitrified agent and preparation method thereof - Google Patents
A kind of steel surface vitrified agent and preparation method thereof Download PDFInfo
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- CN108060413A CN108060413A CN201711319417.4A CN201711319417A CN108060413A CN 108060413 A CN108060413 A CN 108060413A CN 201711319417 A CN201711319417 A CN 201711319417A CN 108060413 A CN108060413 A CN 108060413A
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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
- C23C22/34—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 fluorides or complex fluorides
Abstract
The invention discloses a kind of steel surface vitrified agent and preparation method thereof, which is that the raw material of following mass percent is included based on 100% by the gross mass of the vitrified agent：Film forming agent 5~10%, chelating agent 4~8%, inorganic acid 2~4%, the water of organic acid 0.1~0.2% and surplus.The present invention is combined using film forming agent, chelating agent, inorganic acid and organic acid, obtained vitrified agent Environmentally-friephosphorus-free phosphorus-free, without elements such as zinc, nickel, manganese, chromium, without NO3-N and NO2-N use of arranging in pairs or groups, is not polluted the environment and water source；And the vitrified agent room temperature can just use, and need not heat, the energy saving energy；It is applied to simplify technique in vitrification technique without table tune, and operates facility, and by chemical key connection between vitrification film and steel surface which forms in steel surface, adhesive force is extremely strong, and its impact resistance, salt spray corrosion resistance are strong.
Description
Technical field
The present invention relates to metal conditioner technical field, in particular to a kind of steel surface vitrified agent and its
Preparation method.
Background technology
Steel surface is easy to be corroded in an atmosphere without processing, often gets rusty, seriously affects the use of steel
Service life.Steel surface gets rusty in order to prevent, industrially generally takes and carries out phosphorating treatment to steel surface, reaches anti-corrosion function,
Some is painted or is dusted again also after phosphorating treatment processing, further improves corrosion resistance.It is incorporated in household electrical appliances, family extensively
It occupies, auto parts, Hardware fitting etc..
Steel surface processing at present is substantially with bonderite, forms one layer of phosphating coat in steel surface, main component is
Phosphatic crystalline solid, the even and fine cause of phosphate crystal, there is relatively good adhesive force.
Although phosphorating treatment film forming is strong, adhesive force and corrosion resistance are all relatively good, still there are many shortcoming, especially
It is：
1st, bonderite contains substantial amounts of phosphate, causes body eutrophication, can cause the undue growth of plant, so as to lead
The phenomenon that cause Dissolved Oxygen in Water amount declines, water quality deterioration, fish and other biological mortality.
2nd, general bonderite needs to match sodium nitrite use, and sodium nitrite is a kind of noxious material, the blood with human body
Lactoferrin is oxidized to ferrihemoglobin, loses blood and carries oxygen function, causes tissue anoxic, to human injury very
Greatly.
3rd, phosphating process is complicated, and having to pass through table before phosphatization mediates reason.
The content of the invention
In view of this, a kind of steel surface vitrified agent provided by the invention and preparation method thereof, preferably overcomes above-mentioned
Problem and defect existing in the prior art, the present invention are combined using film forming agent, chelating agent, inorganic acid and organic acid, obtained
Vitrified agent Environmentally-friephosphorus-free phosphorus-free, without elements such as zinc, nickel, manganese, chromium, without arranging in pairs or groups, NO3-N and NO2-N uses, and does not pollute the environment
And water source；And the vitrified agent room temperature can just use, and need not heat, the energy saving energy；It is applied in vitrification technique without table tune,
Technique is simplified, and operates facility, passes through chemical bond between vitrification film and metallic substrates which forms in steel surface
Connection, adhesive force is extremely strong, and its impact resistance, salt spray corrosion resistance are strong.
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：Film forming agent 5~10%, chelating agent 4~8%, inorganic acid 2~4%, the water of organic acid 0.1~0.2% and surplus.
Further, it is that the raw material of following mass percent is included based on 100% by the gross mass of the vitrified agent：Film forming
Agent 6~8%, chelating agent 5~7%, inorganic acid 3~4%, the water of organic acid 0.1~0.15% and surplus.
Further, the film forming agent is ammonium fluozirconate and/or ammonium titanium fluoride.
Further, the chelating agent is four sodium of nitrilotriacetic acid trisodium and/or iminodisuccinic acid.
Further, the inorganic acid is fluosilicic acid or fluoboric acid.
Further, the organic acid is one kind in fumaric acid, gluconic acid and ascorbic acid.
Further, the water is deionized water.
The present invention also provides a kind of preparation method of steel surface vitrified agent, the steel surface vitrified agent is above-mentioned
Steel surface vitrified agent, the preparation method comprise the following steps：
Film forming agent, chelating agent, inorganic acid, organic acid and water are uniformly mixed.
Further, the preparation method includes：First film forming agent and chelating agent are added in organic acid and are stirred, then according to
Secondary addition inorganic acid and water are uniformly mixed.
Further, the mixing speed is 100~150r/min.
Compared with prior art, a kind of advantageous effect of steel surface vitrified agent of the invention and preparation method thereof is：
The present invention is combined using film forming agent, chelating agent, inorganic acid and organic acid, obtained vitrified agent Environmentally-friephosphorus-free phosphorus-free, nothing
The elements such as zinc, nickel, manganese, chromium, nitrate-free and nitrite, do not pollute the environment and water source；And the vitrified agent room temperature is with regard to that can make
With need not heat, the energy saving energy；It is applied in vitrification technique, without table tune, simplify technique, and operate facility, the pottery
By chemical key connection between vitrification film and steel surface that agent is formed in steel surface, adhesive force is extremely strong, and impact resistance, resistance to
Salt air corrosion performance is strong.
For the above objects, features and advantages of the present invention is enable to be clearer and more comprehensible, preferred embodiment cited below particularly is made detailed
It is described as follows.
Specific embodiment
It is of the invention for the ease of understanding, it elaborates with reference to the mode of embodiment to technical scheme,
Many details are elaborated in the following description in order to fully understand the present invention.
But the invention can be embodied in many other ways as described herein, those skilled in the art can be with
Similar improvement is done without violating the connotation of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of fields of the present invention
The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
Term as used herein：
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.It is wanted for example, composition, step, method, product or device comprising listed elements are not necessarily limited to those
Element, but can include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Conjunction " by ... form " exclude any element do not pointed out, step or component.If be used in claim,
This phrase will make claim be closed, it is made not include the material in addition to the material of those descriptions, but relative
Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after
When, only it is limited to the element described in the clause；Other elements be not excluded the claim as a whole it
Outside.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1~5 ", described scope should be interpreted as including scope " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise scope intention includes its end
Value and all integers and fraction in the range.
"and/or" is used to represent that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B).
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：
Film forming agent 5~10% such as 5%, 6%, 7%, 8%, 9% or 10%；
Chelating agent 4~8% such as 4%, 5%, 6%, 7% or 8%；
Inorganic acid 2~4% such as 2%, 2.5%, 3%, 3.5% or 4%；
Organic acid 0.1~0.2% such as 0.1%, 0.12%, 0.15%, 0.18% or 0.2%；
With the water of surplus.
Preferably, it is that the raw material of following mass percent is included based on 100% by the gross mass of the vitrified agent：Film forming agent 6
~8%, the water of chelating agent 5~7%, inorganic acid 3~4%, organic acid 0.1~0.15% and surplus.
The present invention is combined using film forming agent, chelating agent, inorganic acid and organic acid, obtained vitrified agent Environmentally-friephosphorus-free phosphorus-free, nothing
The elements such as zinc, nickel, manganese, chromium, without arranging in pairs or groups, NO3-N and NO2-N uses, and does not pollute the environment and water source；And the vitrified agent
Room temperature can just use, and need not heat, the energy saving energy；It is applied in vitrification technique, it is only necessary to control vitrification point and pH value i.e.
Can, vitrification point is measured with EDTA methods, and then needs to survey total acidity, free acidity in existing phosphating process, and uses accelerating agent etc.；
In addition, carrying out vitrification processing without table tune in steel surface, technique is simplified, and operates facility.
In addition, by chemical key connection between vitrification film and steel surface that the vitrified agent is formed in steel surface, with painting
Material is also by chemical key connection, therefore the adhesive force of the vitrification film is extremely strong, and shock resistance, corrosion resistance are strong, reach 0 grade；
When the vitrification film thickness is 20~30nm, positive anti-force has extremely strong shock resistance up to 50KG, and should
Vitrification film makes its corrosion resistance extremely strong, surmounts the phosphatization obtained in steel surface progress phosphorating treatment completely with high compactness
The impact resistance of film and salt spray corrosion resistance.
Preferably, the film forming agent is ammonium fluozirconate and/or ammonium titanium fluoride.
Preferably, the chelating agent is four sodium of nitrilotriacetic acid trisodium and/or iminodisuccinic acid.
Preferably, the inorganic acid is fluosilicic acid or fluoboric acid.
Preferably, the organic acid is one kind in fumaric acid, gluconic acid and ascorbic acid.
Preferably, the water is deionized water.
The present invention also provides a kind of preparation method of steel surface vitrified agent, the steel surface vitrified agent is above-mentioned
Steel surface vitrified agent, the preparation method comprise the following steps：
Film forming agent, chelating agent, inorganic acid, organic acid and water are uniformly mixed.
Further, the preparation method includes：First film forming agent and chelating agent are added in organic acid and are stirred, then according to
Secondary addition inorganic acid and water are uniformly mixed.
Further, the mixing speed for 100~150r/min such as 100r/min, 110r/min, 120r/min,
130r/min, 140r/min or 150r/min etc..
For the ease of understanding the present invention, the technical solution further illustrated the present invention with reference to embodiment.Applicant
Statement, the present invention are illustrated by the following examples detailed process equipment and the technological process of the present invention, but not office of the invention
It is limited to following detailed process equipments and technological process, that is, does not mean that the present invention should rely on above-mentioned detailed process equipment and technique stream
Cheng Caineng is implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to each original of product of the present invention
The equivalence replacement of material and the addition of auxiliary element, the selection of concrete mode etc. all fall within protection scope of the present invention and open model
Within enclosing.
Embodiment 1
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：5% ammonium fluozirconate, 4% iminodisuccinic acid, four sodium, 2% fluosilicic acid, the water of 0.1% fumaric acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 100r/min stirrings, ammonium fluozirconate and four sodium of iminodisuccinic acid are first mixed 20 points
Then clock adds in fluosilicic acid, stirring after five minutes, adds fumaric acid, and stirring after five minutes, adds the deionized water of surplus to mix
It is even.
Embodiment 2
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：7% ammonium fluozirconate, 5% iminodisuccinic acid, four sodium, 2% fluosilicic acid, the water of 0.1% fumaric acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 120r/min stirrings, ammonium fluozirconate and four sodium of iminodisuccinic acid are first mixed 20 points
Then clock adds in fluosilicic acid, after stirring 8 minutes, add fumaric acid, stirring after five minutes, adds the deionized water of surplus to mix
It is even.
Embodiment 3
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：6% ammonium fluozirconate, 6% iminodisuccinic acid, four sodium, 3% fluosilicic acid, the water of 0.15% fumaric acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 130r/min stirrings, ammonium fluozirconate and four sodium of iminodisuccinic acid are first mixed 20 points
Then clock adds in fluosilicic acid, stirring after ten minutes, adds fumaric acid, and stirring after five minutes, adds the deionized water of surplus to mix
Uniformly.
Embodiment 4
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：8% ammonium titanium fluoride, 7% nitrilotriacetic acid trisodium, 2.5% fluoboric acid, the water of 0.12% gluconic acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 140r/min stirrings, first ammonium titanium fluoride and nitrilotriacetic acid trisodium are mixed 20 minutes,
Then fluoboric acid is added in, stirring after ten minutes, adds gluconic acid, and stirring after five minutes, adds the deionized water of surplus to mix
It is even.
Embodiment 5
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：9% ammonium titanium fluoride, 7% nitrilotriacetic acid trisodium, 3.5% fluoboric acid, the water of 0.18% gluconic acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 150r/min stirrings, first ammonium titanium fluoride and nitrilotriacetic acid trisodium are mixed 20 minutes,
Then fluoboric acid is added in, stirring after five minutes, adds gluconic acid, and stirring after five minutes, adds the deionized water of surplus to mix
It is even.
Embodiment 6
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：10% ammonium titanium fluoride, 8% nitrilotriacetic acid trisodium, 4% fluosilicic acid, the water of 0.2% fumaric acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 120r/min stirrings, first ammonium fluozirconate and nitrilotriacetic acid trisodium are mixed 20 minutes,
Then ammonium titanium fluoride is added in, stirring after five minutes, adds fumaric acid, and stirring after five minutes, adds the deionized water of surplus to mix
It is even.
Comparative example 1
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：6% ammonium fluozirconate, 6% iminodisuccinic acid, four sodium, the water of 0.15% fumaric acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 130r/min stirrings, ammonium fluozirconate, four sodium of iminodisuccinic acid and fumaric acid are mixed
20 minutes, then plus the deionized water of surplus was uniformly mixed.
Comparative example 2
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：6% ammonium fluozirconate, 6% iminodisuccinic acid, four sodium, the water of 3% fluosilicic acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 130r/min stirrings, ammonium fluozirconate, four sodium of iminodisuccinic acid and fumaric acid are mixed
20 minutes, then plus the deionized water of surplus was uniformly mixed.
Comparative example 3
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：6% ammonium fluozirconate, 3% fluosilicic acid, the water of 0.15% fumaric acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 130r/min stirrings, ammonium fluozirconate, four sodium of iminodisuccinic acid and fumaric acid are mixed
20 minutes, then plus the deionized water of surplus was uniformly mixed.
Comparative example 4
A kind of steel surface vitrified agent is based on 100% by the gross mass of the vitrified agent, includes following mass percent
Raw material：6% iminodisuccinic acid, four sodium, 3% fluosilicic acid, the water of 0.15% fumaric acid and surplus.
The preparation method of the steel surface vitrified agent includes：
(1) each raw material is weighed by above-mentioned mass percent.
(2) under rotating speed 130r/min stirrings, ammonium fluozirconate, four sodium of iminodisuccinic acid and fumaric acid are mixed
20 minutes, then plus the deionized water of surplus was uniformly mixed.
The phosphorus content of the vitrified agent prepared respectively to above-described embodiment 1~6 and comparative example 1~4 and to it in identical steel
The adhesive force for the vitrification film that iron matrix surface is formed, anti-impact resistance, salt spray corrosion resistance are detected, testing result such as table 1
It is shown.
Wherein, impact resistance：It is measured according to 1732 standards of GB/T；
Adhesive force：It is measured according to GB/T 9286-1998 standards；
Salt fog resistance：It is measured according to 10125 standards of GB/T.
Table 1
| Sample | Phosphorus content | Adhesive force | Shock-testing | Salt spray test |
| Embodiment 1 | 0mg | 0 grade | 0 grade | Bubble-free, nothing come off |
| Embodiment 2 | 0mg | 0 grade | 0 grade | Bubble-free, nothing come off |
| Embodiment 3 | 0mg | 0 grade | 0 grade | Bubble-free, nothing come off |
| Embodiment 4 | 0mg | 0 grade | 0 grade | Bubble-free, nothing come off |
| Embodiment 5 | 0mg | 0 grade | 0 grade | Bubble-free, nothing come off |
| Embodiment 6 | 0mg | 0 grade | 0 grade | Bubble-free, nothing come off |
| Comparative example 1 | 0mg | 1 grade | 1 grade | There are bubble, partial exfoliation |
| Comparative example 2 | 0mg | 2 grades | 2 grades | There are bubble, partial exfoliation |
| Comparative example 3 | 0mg | 1 grade | 2 grades | There are bubble, partial exfoliation |
| Comparative example 4 | 0mg | 2 grades | 1 grade | There are bubble, partial exfoliation |
From above-mentioned table 1, the vitrified agent that the embodiment of the present invention 1~6 is prepared is not phosphorous, and applied to vitrification skill
In, it is extremely strong in the vitrification film and the adhesive force at steel-based bottom of the formation of steel substrate surface, and its impact resistance and salt spray resistance are rotten
Lose function admirable.
And the steel surface vitrified agent that comparative example 1~4 is prepared is applied in vitrification skill, in steel substrate surface shape
Into vitrification film and the adhesive force at steel-based bottom it is poor, and its impact resistance and salt spray corrosion resistance are poor.
In conclusion the present invention is combined using film forming agent, chelating agent, inorganic acid and organic acid, obtained vitrified agent ring
Protect without phosphorus, the NO3-N and NO2-N that need not arrange in pairs or groups uses, and does not pollute the environment and water source；And the vitrified agent room temperature is with regard to that can make
With need not heat, the energy saving energy；It is applied in vitrification technique, without table tune, simplify technique, and operate facility, the pottery
By chemical key connection between vitrification film and steel surface that agent is formed in steel surface, adhesive force is extremely strong, and its impact resistance,
Salt spray corrosion resistance is strong.
The preferred embodiment of the present invention is above are only, is not intended to limit the invention, for those skilled in the art
For member, inventive formulation and preparation process can have various modifications and variations.Within the spirit and principles of the invention, institute
Any modification, equivalent substitution, improvement and etc. of work, should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of steel surface vitrified agent, it is characterised in that：It is based on 100% by the gross mass of the vitrified agent, includes following matter
Measure the raw material of percentage：Film forming agent 5~10%, chelating agent 4~8%, inorganic acid 2~4%, organic acid 0.1~0.2% and surplus
Water.
2. steel surface vitrified agent according to claim 1, it is characterised in that：Gross mass by the vitrified agent is
100% meter includes the raw material of following mass percent：It is film forming agent 6~8%, chelating agent 5~7%, inorganic acid 3~4%, organic
The water of acid 0.1~0.15% and surplus.
3. steel surface vitrified agent according to claim 1 or 2, it is characterised in that：The film forming agent for ammonium fluozirconate and/
Or ammonium titanium fluoride.
4. steel surface vitrified agent according to claim 1 or 2, it is characterised in that：The chelating agent is nitrilo- three
Four sodium of acetic acid trisodium and/or iminodisuccinic acid.
5. steel surface vitrified agent according to claim 1 or 2, it is characterised in that：The inorganic acid for fluosilicic acid or
Fluoboric acid.
6. steel surface vitrified agent according to claim 1 or 2, it is characterised in that：The organic acid is fumaric acid, Portugal
One kind in grape saccharic acid and ascorbic acid.
7. steel surface vitrified agent according to claim 1 or 2, it is characterised in that：The water is deionized water.
8. a kind of preparation method of steel surface vitrified agent, it is characterised in that：The steel surface vitrified agent for claim 1~
7 any one of them steel surface vitrified agents, the preparation method comprise the following steps：
Film forming agent, chelating agent, inorganic acid, organic acid and water are uniformly mixed.
9. the preparation method of steel surface vitrified agent according to claim 8, it is characterised in that：The preparation method bag
It includes：First film forming agent and chelating agent are added in organic acid and are stirred, inorganic acid is sequentially added and water is uniformly mixed.
10. the preparation method of steel surface vitrified agent according to claim 9, it is characterised in that：The mixing speed is
100~150r/min.
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| CN109082658A (en) * | 2018-09-27 | 2018-12-25 | 浙江工业大学之江学院 | A kind of Environmentally-friephosphorus-free phosphorus-free passivation of metal surfaces liquid and preparation method thereof |
| CN111074255A (en) * | 2019-12-05 | 2020-04-28 | 刘广付 | Metal surface pretreatment agent and preparation method and application thereof |
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