CN110184596A - A method of black phosphating film is covered in metal surface - Google Patents
A method of black phosphating film is covered in metal surface Download PDFInfo
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- CN110184596A CN110184596A CN201910539101.9A CN201910539101A CN110184596A CN 110184596 A CN110184596 A CN 110184596A CN 201910539101 A CN201910539101 A CN 201910539101A CN 110184596 A CN110184596 A CN 110184596A
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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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
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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
-
- 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
- C23C22/78—Pretreatment of the material to be coated
Abstract
The present invention relates to pre-treatment fields, a kind of method in metal surface covering black phosphating film are provided, for solving the problems, such as that workpiece surface color is non-uniform.A kind of method in metal surface covering black phosphating film provided by the invention, it include: that metal works are carried out ungrease treatment by S11. at 0 ~ 50 DEG C, remove workpiece surface greasy dirt, it is washed at normal temperature after degreasing, pickling is carried out with dust technology after washing, workpiece surface sundries is washed away, eluate is washed to after pickling again and is in neutrality；S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 10 ~ 20min, the extra phosphating solution of washing removal workpiece surface.By pre- black plus phosphatization treatment process, the appearance of workpiece is improved, hence it is evident that the level for improving the uniform in color that workpiece shows improves the perception of workpiece, while the corrosion resistance of workpiece also greatly improved.
Description
Technical field
The present invention relates to pre-treatment fields, and in particular to a method of black phosphating film is covered in metal surface.
Background technique
Phosphatization is common pretreatment technology, should belong to chemical conversion film process in principle, is mainly used in steel surface
Phosphatization, non-ferrous metal (such as aluminium, zinc) part can also apply phosphatization.Phosphatization is a kind of chemical and electrochemical reaction formation phosphate chemical
The process of conversion film is formed by phosphate conversion film and is referred to as phosphating coat.
The purpose of phosphatization is mainly: providing protection to parent metal, prevents metal to be corroded to a certain extent；For applying
Bottoming before painting, improves the adhesive force and anti-corrosion capability of paint film layer；Play antifriction lubrication in metal cold processing.
The color that traditional phosphating process will lead to phosphate coating is inconsistent, by causing open defect, how to make phosphating coat
Or the color of layer more consistent is a technical problem to be solved urgently.
Summary of the invention
Present invention solves the technical problem that being the non-uniform problem of workpiece surface color, provide a kind of in metal surface covering
The method of black phosphating film.
In order to solve the above technical problem, the present invention provides technical solution are as follows:
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 0 ~ 50 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing,
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 10 ~ 20min, washing removal workpiece
The extra phosphating solution on surface.
After pickling, make workpiece surface that black be presented by blackening pretreatment, workpiece can be made using phosphorating treatment
The color on surface is more consistent.
By pre- black plus phosphatization treatment process, the appearance of workpiece is improved, hence it is evident that it is equal to improve the color that workpiece shows
Even level improves the perception of workpiece, while the corrosion resistance of workpiece also greatly improved.
Preferably, the pre- black liquor includes: 0.5 ~ 0.8g/L of bismuth nitrate, 0.5 ~ 2g/L of sodium molybdate, 5 ~ 20g/ of triethanolamine
L, 11 ~ 15ml/L of nitric acid of mass concentration 55%, surplus is water.Pre- black liquor can make workpiece surface that black be presented, and improve work
The appearance of part.
Preferably, the phosphating solution includes: 7 ~ 10g/L of zinc dihydrogen phosphate, 8 ~ 12g/L of zinc nitrate, phosphatase 11 ~ 4g/L, and 35%
Graphene oxide 0.5 ~ 0.8g/L of 5 ~ 8g/L, APEO, surplus is water.The phosphating solution that joined graphene oxide can make
Phosphating coat is more closely knit, while also the color of phosphatization film surface can be promoted more uniform.
Preferably, the phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, zinc nitrate, phosphoric acid, graphene oxide,
APEO, water are added in reaction kettle, and adjusting pH is 2 ~ 4, is warming up to 25 DEG C, stirs evenly, and both obtain phosphating solution.The preparation work of phosphating solution
Skill is simple, can quickly produce in batches.
Preferably, the graphene oxide is modified graphene oxide.Modified graphene oxide can be further
The compactness for improving phosphating coat, prevents workpiece to be corroded.
Preferably, the modified graphene oxide the preparation method comprises the following steps:
Graphite oxide is dissolved in deionized water, graphite oxide solution 2 ~ 3g/L of concentration is made, 2 ~ 3h is ultrasonically treated, obtains oxygen
The solution of graphite alkene；
2h is mixed in the solution of nano-titanium dioxide and graphene oxide, the concentration of nano-titanium dioxide is in mixed liquor
1.5~2.5g/L；
Gained suspension is poured into reaction kettle bushing and is sealed, the hydro-thermal reaction 10h at 150 ~ 200 DEG C；Suspension after reaction
It is centrifuged, is washed with deionized water, obtain modified graphene oxide after dry, grinding.Pass through nano-titanium dioxide modified oxidation stone
Black alkene can effectively improve the compactness of phosphating coat, and workpiece is further prevented to be corroded.
Preferably, the graphite oxide the preparation method comprises the following steps: by the concentrated sulfuric acid, graphite powder, potassium permanganate and sodium nitrate mix
Uniformly, it is added in reactor tank, after reacting 8h at 10 ~ 15 DEG C, continues after reacting 10h at 35 ~ 40 DEG C, continue 100 ~
12h is reacted at 110 DEG C, and hydrogen peroxide and deionized water is added, obtains acidic oxidation graphite；The concentrated sulfuric acid: graphite powder: permanganic acid
Potassium: sodium nitrate: 30% hydrogen peroxide: deionized water=45:1:7:11:25:200；
Acidic oxidation graphite is washed 3 ~ 5 times by concentrated hydrochloric acid, then the vacuum drying at 60 DEG C, both obtains graphite oxide.Oxidation
Graphite is the basic material for preparing graphene, is optimized by the preparation method of graphite oxide, can further be improved
The performance of phosphating coat.
Preferably, the nano-titanium dioxide the preparation method comprises the following steps: zinc acetate, butyl titanate is taken to be dissolved in dehydrated alcohol,
It stirs evenly, obtains mixed solution, the zinc acetate: butyl titanate: dehydrated alcohol=1:1.9:7.9；By mixed solution in 70 DEG C
Lower water bath method, is then dried, and after drying under excess oxygen, is warming up to 600 DEG C of roasting 2h with 10 DEG C/min, is obtained compound
Powder；It is dry after ball milling 2h after the same stearic acid of composite granule, hydroxylmethyl cellulose rope, hexamethylene are mixed, both obtain nanometer titanium dioxide
Titanium, the composite granule: stearic acid: hydroxymethyl cellulose: hexamethylene=1:0.5:0.05:5.The doping of nano-titanium dioxide can
To improve the performance of graphene oxide, and then improve the performance of the phosphating coat of workpiece surface.
Preferably, the pre- black liquor includes: bismuth nitrate 0.6g/L, sodium molybdate 1g/L, triethanolamine 15g/L, mass concentration
55% nitric acid 12ml/L, surplus are water.
Preferably, the phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, 35% oxidation stone
Black alkene 7g/L, APEO 0.6g/L, surplus are water.
Compared with prior art, the device have the advantages that are as follows: by the treatment process of pre- black plus phosphatization, improve
The appearance of workpiece, hence it is evident that the level for improving the uniform in color that workpiece shows improves the perception of workpiece, while also greatly improving
The corrosion resistance of workpiece.
Specific embodiment
It the following examples are further illustrations of the invention, is not limitation of the present invention.
Embodiment 1
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 35 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 15min, washing removal workpiece surface
Extra phosphating solution.The pre- black liquor includes: bismuth nitrate 0.6g/L, sodium molybdate 1g/L, triethanolamine 15g/L, mass concentration 55%
Nitric acid 12ml/L, surplus is water.The phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, and 35%
Graphene oxide 7g/L, APEO 0.6g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, nitre
Sour zinc, phosphoric acid, graphene oxide, APEO, water are added in reaction kettle, and adjusting pH is 2 ~ 4, are warming up to 25 DEG C, stir evenly, both
Phosphating solution.The graphene oxide is modified graphene oxide.The modified graphene oxide the preparation method comprises the following steps:
Graphite oxide is dissolved in deionized water, graphite oxide solution concentration 2.5g/L is made, 2.5h is ultrasonically treated, obtains oxygen
The solution of graphite alkene；
2h is mixed in the solution of nano-titanium dioxide and graphene oxide, the concentration of nano-titanium dioxide is in mixed liquor
2g/L；
Gained suspension is poured into reaction kettle bushing and is sealed, the hydro-thermal reaction 10h at 180 DEG C；Suspension after reaction is spent
Ionized water centrifugation, washing obtain modified graphene oxide after dry, grinding.The graphite oxide the preparation method comprises the following steps: by dense sulphur
Acid, graphite powder, potassium permanganate and sodium nitrate are uniformly mixed, and are added in reactor tank, after reacting 8h at 12 DEG C, are continued at 37 DEG C
After lower reaction 10h, 12h is reacted in continuation at 105 DEG C, and hydrogen peroxide and deionized water is added, obtains acidic oxidation graphite；It is described dense
Sulfuric acid: graphite powder: potassium permanganate: sodium nitrate: 30% hydrogen peroxide: deionized water=45:1:7:11:25:200；
Acidic oxidation graphite is washed 3 ~ 5 times by concentrated hydrochloric acid, then the vacuum drying at 60 DEG C, both obtains graphite oxide.It is described
Nano-titanium dioxide the preparation method comprises the following steps: zinc acetate, butyl titanate is taken to be dissolved in dehydrated alcohol, stir evenly, obtain mixing molten
Liquid, the zinc acetate: butyl titanate: dehydrated alcohol=1:1.9:7.9；By mixed solution at 70 DEG C water bath method, then do
It is dry, after drying under excess oxygen, 600 DEG C of roasting 2h are warming up to 10 DEG C/min, obtain composite granule；Composite granule is same
It is dry after ball milling 2h after stearic acid, hydroxylmethyl cellulose rope, hexamethylene mixing, nano-titanium dioxide is both obtained, the composite granule: hard
Resin acid: hydroxymethyl cellulose: hexamethylene=1:0.5:0.05:5.
After pickling, make workpiece surface that black be presented by blackening pretreatment, workpiece can be made using phosphorating treatment
The color on surface is more consistent.
By pre- black plus phosphatization treatment process, the appearance of workpiece is improved, hence it is evident that it is equal to improve the color that workpiece shows
Even level improves the perception of workpiece, while the corrosion resistance of workpiece also greatly improved.Pre- black liquor can make workpiece table
Black is presented in face, improves the appearance of workpiece.The phosphating solution that joined graphene oxide can make phosphating coat more closely knit, together
When also the color of phosphatization film surface can be promoted more uniform.The preparation process of phosphating solution is simple, can quickly produce in batches.Change
The graphene oxide of property can further improve the compactness of phosphating coat, and workpiece is prevented to be corroded.Pass through nanometer titanium dioxide
Titanium modified graphene oxide can effectively improve the compactness of phosphating coat, and workpiece is further prevented to be corroded.Graphite oxide is system
The basic material of standby graphene, is optimized by the preparation method of graphite oxide, can further improve phosphating coat
Performance.The performance of graphene oxide can be improved in the doping of nano-titanium dioxide, and then improves the property of the phosphating coat of workpiece surface
Energy.
Embodiment 2
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 25 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 10 ~ 20min, washing removal workpiece
The extra phosphating solution on surface.The pre- black liquor includes: bismuth nitrate 0.5g/L, sodium molybdate 0.5g/L, triethanolamine 5g/L, and quality is dense
The nitric acid 11ml/L of degree 55%, surplus is water.The phosphating solution includes: zinc dihydrogen phosphate 7g/L, zinc nitrate 8g/L, phosphatase 11 g/L,
35% graphene oxide 5g/L, APEO 0.5g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate,
Zinc nitrate, phosphoric acid, graphene oxide, APEO, water are added in reaction kettle, and adjusting pH is 2, are warming up to 25 DEG C, stir evenly, both
Phosphating solution.The graphene oxide is modified graphene oxide.The modified graphene oxide the preparation method comprises the following steps:
Graphite oxide is dissolved in deionized water, graphite oxide solution concentration 2g/L is made, is ultrasonically treated 2h, obtains oxidation stone
The solution of black alkene；
2h is mixed in the solution of nano-titanium dioxide and graphene oxide, the concentration of nano-titanium dioxide is in mixed liquor
1.5g/L；
Gained suspension is poured into reaction kettle bushing and is sealed, the hydro-thermal reaction 10h at 150 DEG C；Suspension after reaction is spent
Ionized water centrifugation, washing obtain modified graphene oxide after dry, grinding.The graphite oxide the preparation method comprises the following steps: by dense sulphur
Acid, graphite powder, potassium permanganate and sodium nitrate are uniformly mixed, and are added in reactor tank, after reacting 8h at 10 DEG C, are continued at 35 DEG C
After lower reaction 10h, 12h is reacted in continuation at 100 DEG C, and hydrogen peroxide and deionized water is added, obtains acidic oxidation graphite；It is described dense
Sulfuric acid: graphite powder: potassium permanganate: sodium nitrate: 30% hydrogen peroxide: deionized water=45:1:7:11:25:200；
Acidic oxidation graphite is washed 3 times by concentrated hydrochloric acid, then the vacuum drying at 60 DEG C, both obtains graphite oxide.It is described to receive
Rice titanium dioxide the preparation method comprises the following steps: zinc acetate, butyl titanate is taken to be dissolved in dehydrated alcohol, stir evenly, obtain mixed solution,
The zinc acetate: butyl titanate: dehydrated alcohol=1:1.9:7.9；By mixed solution at 70 DEG C water bath method, then dry, do
After dry under excess oxygen, 600 DEG C of roasting 2h are warming up to 10 DEG C/min, obtain composite granule；By composite granule with stearic
It is dry after ball milling 2h after acid, the mixing of hydroxylmethyl cellulose rope, hexamethylene, nano-titanium dioxide is both obtained, the composite granule: stearic
Acid: hydroxymethyl cellulose: hexamethylene=1:0.5:0.05:5.
Embodiment 3
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 50 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 20min, washing removal workpiece surface
Extra phosphating solution.The pre- black liquor includes: bismuth nitrate 0.8g/L, sodium molybdate 2g/L, triethanolamine 20g/L, mass concentration 55%
Nitric acid 15ml/L, surplus is water.The phosphating solution includes: zinc dihydrogen phosphate 10g/L, zinc nitrate 12g/L, phosphatase 24 g/L, and 35%
Graphene oxide 8g/L, APEO 0.8g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, nitre
Sour zinc, phosphoric acid, graphene oxide, APEO, water are added in reaction kettle, and adjusting pH is 4, is warming up to 25 DEG C, stirs evenly, and both obtain phosphorus
Change liquid.The graphene oxide is modified graphene oxide.The modified graphene oxide the preparation method comprises the following steps:
Graphite oxide is dissolved in deionized water, graphite oxide solution concentration 3g/L is made, is ultrasonically treated 3h, obtains oxidation stone
The solution of black alkene；
2h is mixed in the solution of nano-titanium dioxide and graphene oxide, the concentration of nano-titanium dioxide is in mixed liquor
2.5g/L；
Gained suspension is poured into reaction kettle bushing and is sealed, the hydro-thermal reaction 10h at 200 DEG C；Suspension after reaction is spent
Ionized water centrifugation, washing obtain modified graphene oxide after dry, grinding.The graphite oxide the preparation method comprises the following steps: by dense sulphur
Acid, graphite powder, potassium permanganate and sodium nitrate are uniformly mixed, and are added in reactor tank, after reacting 8h at 15 DEG C, are continued at 40 DEG C
After lower reaction 10h, 12h is reacted in continuation at 110 DEG C, and hydrogen peroxide and deionized water is added, obtains acidic oxidation graphite；It is described dense
Sulfuric acid: graphite powder: potassium permanganate: sodium nitrate: 30% hydrogen peroxide: deionized water=45:1:7:11:25:200；
Acidic oxidation graphite is washed 5 times by concentrated hydrochloric acid, then the vacuum drying at 60 DEG C, both obtains graphite oxide.It is described to receive
Rice titanium dioxide the preparation method comprises the following steps: zinc acetate, butyl titanate is taken to be dissolved in dehydrated alcohol, stir evenly, obtain mixed solution,
The zinc acetate: butyl titanate: dehydrated alcohol=1:1.9:7.9；By mixed solution at 70 DEG C water bath method, then dry, do
After dry under excess oxygen, 600 DEG C of roasting 2h are warming up to 10 DEG C/min, obtain composite granule；By composite granule with stearic
It is dry after ball milling 2h after acid, the mixing of hydroxylmethyl cellulose rope, hexamethylene, nano-titanium dioxide is both obtained, the composite granule: stearic
Acid: hydroxymethyl cellulose: hexamethylene=1:0.5:0.05:5.
Embodiment 4
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 35 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 15min, washing removal workpiece surface
Extra phosphating solution.The pre- black liquor includes: bismuth nitrate 0.6g/L, sodium molybdate 1g/L, triethanolamine 15g/L, mass concentration 55%
Nitric acid 12ml/L, surplus is water.The phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, and 35%
Graphene oxide 7g/L, APEO 0.6g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, nitre
Sour zinc, phosphoric acid, graphene oxide, APEO, water are added in reaction kettle, and adjusting pH is 2 ~ 4, are warming up to 25 DEG C, stir evenly, both
Phosphating solution.
Embodiment 5
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 35 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 15min, washing removal workpiece surface
Extra phosphating solution.The pre- black liquor includes: bismuth nitrate 0.6g/L, sodium molybdate 1g/L, triethanolamine 15g/L, mass concentration 55%
Nitric acid 12ml/L, surplus is water.The phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, and 35%
Graphene oxide 7g/L, APEO 0.6g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, nitre
Sour zinc, phosphoric acid, graphene oxide, APEO, water are added in reaction kettle, and adjusting pH is 2 ~ 4, are warming up to 25 DEG C, stir evenly, both
Phosphating solution.The graphene oxide is modified graphene oxide.
Embodiment 6
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 35 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 15min, washing removal workpiece surface
Extra phosphating solution.The pre- black liquor includes: bismuth nitrate 0.6g/L, sodium molybdate 1g/L, triethanolamine 15g/L, mass concentration 55%
Nitric acid 12ml/L, surplus is water.The phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, and 35%
Graphene oxide 7g/L, APEO 0.6g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, nitre
Sour zinc, phosphoric acid, graphene oxide, APEO, water are added in reaction kettle, and adjusting pH is 2 ~ 4, are warming up to 25 DEG C, stir evenly, both
Phosphating solution.The graphene oxide is modified graphene oxide.The modified graphene oxide the preparation method comprises the following steps:
Graphite oxide is dissolved in deionized water, graphite oxide solution concentration 2.5g/L is made, 2.5h is ultrasonically treated, obtains oxygen
The solution of graphite alkene；
2h is mixed in the solution of nano-titanium dioxide and graphene oxide, the concentration of nano-titanium dioxide is in mixed liquor
2g/L；
Gained suspension is poured into reaction kettle bushing and is sealed, the hydro-thermal reaction 10h at 180 DEG C；Suspension after reaction is spent
Ionized water centrifugation, washing obtain modified graphene oxide after dry, grinding.The graphite oxide is commercially available graphite oxide.
Embodiment 7
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 35 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 15min, washing removal workpiece surface
Extra phosphating solution.The pre- black liquor includes: bismuth nitrate 0.6g/L, sodium molybdate 1g/L, triethanolamine 15g/L, mass concentration 55%
Nitric acid 12ml/L, surplus is water.The phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, and 35%
Graphene oxide 7g/L, APEO 0.6g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, nitre
Sour zinc, phosphoric acid, graphene oxide, APEO, water are added in reaction kettle, and adjusting pH is 2 ~ 4, are warming up to 25 DEG C, stir evenly, both
Phosphating solution.The graphene oxide is modified graphene oxide.The modified graphene oxide the preparation method comprises the following steps:
Graphite oxide is dissolved in deionized water, graphite oxide solution concentration 2.5g/L is made, 2.5h is ultrasonically treated, obtains oxygen
The solution of graphite alkene；
2h is mixed in the solution of nano-titanium dioxide and graphene oxide, the concentration of nano-titanium dioxide is in mixed liquor
2g/L；
Gained suspension is poured into reaction kettle bushing and is sealed, the hydro-thermal reaction 10h at 180 DEG C；Suspension after reaction is spent
Ionized water centrifugation, washing obtain modified graphene oxide after dry, grinding.The graphite oxide the preparation method comprises the following steps: by dense sulphur
Acid, graphite powder, potassium permanganate and sodium nitrate are uniformly mixed, and are added in reactor tank, after reacting 8h at 12 DEG C, are continued at 37 DEG C
After lower reaction 10h, 12h is reacted in continuation at 105 DEG C, and hydrogen peroxide and deionized water is added, obtains acidic oxidation graphite；It is described dense
Sulfuric acid: graphite powder: potassium permanganate: sodium nitrate: 30% hydrogen peroxide: deionized water=45:1:7:11:25:200；
Acidic oxidation graphite is washed 3 ~ 5 times by concentrated hydrochloric acid, then the vacuum drying at 60 DEG C, both obtains graphite oxide.It is described
Nano-titanium dioxide is commercial Anatase titanium dioxide.
Comparative example 1
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 35 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 15min, washing removal workpiece surface
Extra phosphating solution.The pre- black liquor includes: bismuth nitrate 0.6g/L, sodium molybdate 1g/L, triethanolamine 15g/L, mass concentration 55%
Nitric acid 12ml/L, surplus is water.The phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, and 35%
Graphene oxide 7g/L, APEO 0.6g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, nitre
Sour zinc, phosphoric acid, APEO, water are added in reaction kettle, and adjusting pH is 2 ~ 4, is warming up to 25 DEG C, stirs evenly, and both obtain phosphating solution.
Comparative example 2
A method of black phosphating film is covered in metal surface, comprising:
S11. metal works are subjected at 35 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing, water
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 15min, washing removal workpiece surface
Extra phosphating solution.The phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, 35% graphite oxide
Alkene 7g/L, APEO 0.6g/L, surplus is water.The phosphating solution the preparation method comprises the following steps: by zinc dihydrogen phosphate, zinc nitrate, phosphoric acid,
APEO, water are added in reaction kettle, and adjusting pH is 2 ~ 4, is warming up to 25 DEG C, stirs evenly, and both obtain phosphating solution.Remaining is the same as embodiment 1.
Experimental example
By steel samples according in embodiment 1 ~ 7 and comparative example 1 ~ 2 method for bonderizing carry out phosphatization, to the phosphating coat after phosphatization into
Performing check, the results are shown in Table 1.
1 phosphating coat performance indicator of table
Sodium chloride corrosion experiment (h) is that statistics workpiece the time of rust staining occurs when being immersed in immersion in 5% sodium chloride solution in table 1.
As known from Table 1, the phosphatization film properties of embodiment 1 ~ 3 are better than the phosphating coat that the method for bonderizing in embodiment 4 ~ 7 is formed,
Corrosion resistant ability is stronger.The formula of phosphating solution in embodiment 1 is by optimization, and corresponding anticorrosion effect is better than embodiment 2
With 3.
Graphene oxide in embodiment 4, non-modified, the anticorrosion effect of corresponding method for bonderizing is markedly less than embodiment 1；It is real
The method of modifying for applying the graphene oxide in example 5 is different with embodiment 1 ~ 3, and the performance of phosphating coat is also weaker than embodiment 1 ~ 3；It is real
Apply graphite oxide in example 6 the preparation method is the same as that of Example 1 it is ~ 3 different, in embodiment 7 nano-titanium dioxide with embodiment 1 ~ 3 not
Together, and its effect is weaker than embodiment 1 ~ 3, show the application method for bonderizing must be use by modified nano-silica
Change modified graphene oxide made of titanium and the graphite oxide of modification, and combines what certain processing method was just able to achieve.
Phosphating solution is free of graphene oxide in comparative example 1, is free of blackening pretreatment in comparative example 2 in parkerizing method,
The phosphating coat of formation is almost without etch-proof ability, it can be seen that the method for bonderizing of the application must used by being modified
Nano-titanium dioxide and modification graphite oxide made of modified graphene oxide, and phase could be generated in conjunction with blackening pretreatment
When corrosion resistant effect.
Above-listed detailed description is illustrating for possible embodiments of the present invention, and above embodiments are not to limit this
The scope of the patents of invention, all equivalence enforcements or change without departing from carried out by the present invention, is intended to be limited solely by the scope of the patents of this case.
Claims (10)
1. a kind of method in metal surface covering black phosphating film characterized by comprising
S11. metal works are subjected at 0 ~ 50 DEG C ungrease treatment, remove workpiece surface greasy dirt, is washed at normal temperature after degreasing,
Pickling is carried out with dust technology after washing, washes away workpiece surface sundries, eluate is washed to after pickling again and is in neutrality；
S12. blackening pretreatment is carried out to the metal works after washing using pre- black liquor, obtains the workpiece that surface is black；
S13. phosphating solution is used to carry out phosphorating treatment to surface for the workpiece of black, after handling 10 ~ 20min, washing removal workpiece
The extra phosphating solution on surface.
2. a kind of method in metal surface covering black phosphating film according to claim 1, which is characterized in that described pre-
Black liquor includes: 0.5 ~ 0.8g/L of bismuth nitrate, 0.5 ~ 2g/L of sodium molybdate, 5 ~ 20g/L of triethanolamine, and the nitric acid 11 of mass concentration 55% ~
15ml/L, surplus are water.
3. a kind of method in metal surface covering black phosphating film according to claim 1, which is characterized in that the phosphorus
Changing liquid includes: 7 ~ 10g/L of zinc dihydrogen phosphate, 8 ~ 12g/L of zinc nitrate, phosphatase 11 ~ 4g/L, 35% 5 ~ 8g/L of graphene oxide,
0.5 ~ 0.8g/L of APEO, surplus are water.
4. a kind of method in metal surface covering black phosphating film according to claim 3, which is characterized in that the phosphorus
Change liquid the preparation method comprises the following steps: by zinc dihydrogen phosphate, zinc nitrate, phosphoric acid, graphene oxide, APEO, water be added reaction kettle in, adjust
PH is 2 ~ 4, is warming up to 25 DEG C, stirs evenly, and both obtains phosphating solution.
5. a kind of method in metal surface covering black phosphating film according to claim 4, which is characterized in that the oxygen
Graphite alkene is modified graphene oxide.
6. a kind of method in metal surface covering black phosphating film according to claim 5, which is characterized in that described to change
Property graphene oxide the preparation method comprises the following steps:
Graphite oxide is dissolved in deionized water, graphite oxide solution 2 ~ 3g/L of concentration is made, 2 ~ 3h is ultrasonically treated, obtains oxygen
The solution of graphite alkene；
2h is mixed in the solution of nano-titanium dioxide and graphene oxide, the concentration of nano-titanium dioxide is in mixed liquor
1.5~2.5g/L；
Gained suspension is poured into reaction kettle bushing and is sealed, the hydro-thermal reaction 10h at 150 ~ 200 DEG C；Suspension after reaction
It is centrifuged, is washed with deionized water, obtain modified graphene oxide after dry, grinding.
7. a kind of method in metal surface covering black phosphating film according to claim 6, which is characterized in that the oxygen
Graphite the preparation method comprises the following steps: the concentrated sulfuric acid, graphite powder, potassium permanganate and sodium nitrate are uniformly mixed, be added in reactor tank,
After reacting 8h at 10 ~ 15 DEG C, continue after reacting 10h at 35 ~ 40 DEG C, 12h is reacted in continuation at 100 ~ 110 DEG C, and dioxygen is added
Water and deionized water obtain acidic oxidation graphite；The concentrated sulfuric acid: graphite powder: potassium permanganate: sodium nitrate: 30% hydrogen peroxide:
Deionized water=45:1:7:11:25:200；
Acidic oxidation graphite is washed 3 ~ 5 times by concentrated hydrochloric acid, then the vacuum drying at 60 DEG C, both obtains graphite oxide.
8. a kind of method in metal surface covering black phosphating film according to claim 6, which is characterized in that described to receive
Rice titanium dioxide the preparation method comprises the following steps: zinc acetate, butyl titanate is taken to be dissolved in dehydrated alcohol, stir evenly, obtain mixed solution,
The zinc acetate: butyl titanate: dehydrated alcohol=1:1.9:7.9；By mixed solution at 70 DEG C water bath method, then dry, do
After dry under excess oxygen, 600 DEG C of roasting 2h are warming up to 10 DEG C/min, obtain composite granule；By composite granule with stearic
It is dry after ball milling 2h after acid, the mixing of hydroxylmethyl cellulose rope, hexamethylene, nano-titanium dioxide is both obtained, the composite granule: stearic
Acid: hydroxymethyl cellulose: hexamethylene=1:0.5:0.05:5.
9. a kind of method in metal surface covering black phosphating film according to claim 1, which is characterized in that described pre-
Black liquor includes: bismuth nitrate 0.6g/L, sodium molybdate 1g/L, triethanolamine 15g/L, the nitric acid 12ml/L of mass concentration 55%, and surplus is
Water.
10. a kind of method in metal surface covering black phosphating film according to claim 1, which is characterized in that described
Phosphating solution includes: zinc dihydrogen phosphate 9g/L, zinc nitrate 10g/L, phosphoric acid 3g/L, 35% graphene oxide 7g/L, APEO 0.6g/
L, surplus are water.
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