CN109609937B - Method for preparing composite phosphating film by doping inorganic nanoparticles - Google Patents
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- 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
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- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
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- 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
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- 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
- C23C22/18—Orthophosphates containing manganese cations
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- 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
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
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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
- C23C22/22—Orthophosphates containing alkaline earth metal cations
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Abstract
The invention discloses a method for preparing a composite phosphating film by doping inorganic nanoparticles; the method comprises the steps of firstly putting 5-8 parts by mass of phosphate, 7-9 parts by mass of zinc, manganese or calcium salt, 0.6-3 parts by mass of phosphoric acid, 0.04-0.4 part by mass of boron nitride, 0.1-1 part by mass of stabilizer, 6-10 parts by mass of pH buffering agent and 80-100 parts by mass of water into a reaction kettle, adjusting the pH to 2-3 by using alkali liquor, then heating to 20-40 ℃, and mechanically stirring and discharging. And then, putting the prepared phosphating solution into a phosphating tank, raising the temperature of phosphating to 20-40 ℃, then immersing the steel test piece subjected to rust and oil removal into the phosphating solution, and washing and drying the steel test piece with water after treatment. The boron nitride is used as a nucleation adsorption site of crystals during phosphorization, is beneficial to crystal adhesion and formation of a composite phosphorization film, and is a hydrophobic nano material, so that the dense composite phosphorization film can effectively prevent moisture in air from permeating, and has excellent corrosion resistance.
Description
Technical Field
The invention relates to a phosphating film, in particular to a method for preparing a phosphating film by doping nano boron nitride; belongs to the field of material science and surface technology.
Background
After removing oil and rust, the metal surface is usually chemically treated to form a protective film on the metal surface in order to prevent rust from being rusted again. Phosphating is a commonly used surface treatment technique and refers to a process of forming a phosphate coating film which is difficult to dissolve in water on the metal surface through chemical reaction in a specific acid phosphate solution. The phosphating can be classified into six types, i.e., zinc-calcium, zinc-manganese, iron, and amorphous iron, according to the kind of the phosphating film. It should be noted that although the phosphating film is thin, because it is a non-metallic non-conductive isolation layer, it can change the metal workpiece from good conductor to bad conductor, inhibit the formation of micro-battery on the surface of the metal workpiece, and further effectively prevent the corrosion of the coating film. In view of its excellent characteristics, the fields of application of the phosphating films are very wide, such as automobile manufacturing, aerospace, marine corrosion prevention, primer coating and the like.
At present, the phosphating at home and abroad mostly uses medium-temperature and high-temperature phosphating, not only has large energy consumption, long treatment process time and more sediments, but also needs closed treatment after phosphating, has more complex process and directly influences the quality, the yield and the cost of coating production. The phosphating solution for the steel test piece has the problems of environmental pollution, unstable phosphating solution and poor quality of a phosphating film. Therefore, the traditional phosphating process is time-consuming and energy-consuming.
The Chinese invention patent CN200610045653.7 discloses a technology for promoting phosphating by using nano aluminum oxide, and although the phosphating process only needs 9-12 minutes and the prepared phosphating film has good wear resistance, the temperature is 50-90 ℃, and the energy consumption is high. Moreover, the grain of the phosphating film is not compact, and the corrosion resistance needs to be improved.
The Chinese patent application with the application number of CN201610397553.4 discloses a formula of a carbon steel tube normal-temperature phosphating solution, which can quickly perform phosphating treatment on workpieces at the temperature close to the normal temperature, but uses poisonous and harmful sodium nitrite and sodium fluoride as accelerators, has high dosage, generates large difficulty in treating three wastes, and does not meet the requirement of environmental protection.
The Chinese patent application with the publication number of CN101029386A discloses a calcium-zinc-manganese-containing ternary cationic phosphating solution for treating steel plates and galvanized plates, which has the advantages of quick film formation and good matching property with an electrophoretic coating, but has high concentration, high cost, working temperature of 40-60 ℃ and relatively high energy consumption.
The Chinese patent application with the application number of CN103469187A discloses a treatment liquid for phosphating and blackening of steel surfaces, and although the operation temperature of the treatment liquid is normal temperature and the corrosion resistance and the film quality of the treated steel surfaces are good, the phosphating process is slow, needs 30-50 minutes and is time-consuming.
Disclosure of Invention
The invention aims to provide a method for quickly preparing a phosphate film with strong corrosion resistance and high quality at normal temperature. The used phosphating solution does not contain harmful chemical substances such as sodium nitrite and the like, and is harmless to the environment.
According to the invention, a small amount of nano boron nitride is added into the phosphating solution, so that the nano boron nitride and phosphate crystals are co-deposited on the surface of steel to form the nano boron nitride composite phosphating film, the corrosion resistance, the film thickness, the film hardness and the like of the phosphating film are obviously improved, the preparation time of the phosphating film is shortened, and the phosphating treatment temperature is reduced.
The invention utilizes the characteristics of boron nitride; the boron nitride is called white graphite, has a graphite-like layered structure, is a good thermal conductor and a typical electric insulator, and has the room-temperature resistivity of 1016～1018Omega cm, resistivity of 10 even at 1000 deg.C4～106Omega cm, the breakdown strength is twice of that of aluminum oxide, so the corrosion resistance is excellent; it has excellent oxidation resistance and chemical stability, and has good moisture resistance to molten metal, slag, glass, etc. The invention utilizes boron nitride as a phosphating accelerant and a modifier, and inorganic nano-particle boron nitride is doped in phosphating solution to participate in phosphating crystallization. The method of the invention meets the market competition requirement of rapid development, improves the quality of the phosphating film, realizes the aim of preparing the phosphating film at normal temperature in a green way and rapidly saves energy, and utilizes the characteristics of nano materials such as surface effect, small-size effect and the like; the invention relates to a new method for improving the compactness and the corrosion resistance of a phosphating film.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a composite phosphating film by doping inorganic nanoparticles comprises the following steps:
1) preparing a phosphating solution: putting 5-8 parts by mass of phosphate, 7-9 parts by mass of zinc, manganese or calcium salt, 0.6-3 parts by mass of phosphoric acid, 0.04-0.4 part by mass of boron nitride, 0.1-1 part by mass of stabilizer, 6-10 parts by mass of pH buffering agent and 80-100 parts by mass of water into a reaction kettle, adjusting the pH to 2-3 by using alkali liquor, then heating to 20-40 ℃, controlling the stirring speed to 200-300 r/min, mechanically stirring for 30-60 min, and taking out of the kettle;
2) and (3) a phosphating treatment process: and (3) putting the prepared phosphating solution into a phosphating tank, raising the temperature of phosphating to 20-40 ℃, then soaking the steel test piece subjected to rust and oil removal into the phosphating solution for 5-20 minutes, and washing and drying the steel test piece by water to obtain the composite phosphating film.
To further achieve the object of the present invention, preferably, the phosphate is one or more of an acid salt, a normal salt and a hydrate thereof containing zinc ions, manganese ions and calcium ions.
Preferably, the zinc, manganese or calcium salt is one or more of nitrate, chloride and hydrate thereof.
Preferably, the nano boron nitride is one or more of hexagonal boron nitride, rhombohedral boron nitride and cubic boron nitride.
Preferably, the nano boron nitride has an average particle diameter of 50 to 100nm, and 80 wt% or more of particles are included in a range of ± 30% of the average particle diameter.
Preferably, the shape of the nano boron nitride powder is an elliptical disk or a circular disk, and the minor axis La and the major axis L arebAnd the thickness t satisfies the following formula: la is more than or equal to 80nm and less than or equal to Lb≤700nm，20nm≤t≤150nm，t≤La，0.5≤La/Lb≤1.0。
Preferably, the stabilizer is one or more of linear alkyl benzene sodium sulfonate (LAS), fatty alcohol-polyoxyethylene ether sodium sulfate (AES), alkyl Alcohol Ether Carboxylate (AEC), alkylphenol ethoxylate (APEO) and fatty acid polyoxyethylene ester (SE-10).
Preferably, the PH buffer is one or more of potassium chloride-hydrochloric acid, glycine-hydrochloric acid, monochloroacetic acid-sodium hydroxide, hexamethylenetetramine-hydrochloric acid.
Preferably, in the derusting process in the step 2), the front and back surfaces of the test piece are polished by 400-800 meshes of sand paper; in the oil removing process in the step 2), the temperature of a 10 wt% sodium hydroxide solution is raised to 20-40 ℃, then the test piece is soaked for 5-10 minutes and taken out, and the ultrasonic treatment is carried out in an acetone solution for 3-5 minutes.
Preferably, the composite phosphating film is one or more of a zinc phosphating film, a manganese phosphating film and a calcium phosphating film.
The mechanism of the invention is as follows:
when a test piece is immersed in the phosphating solution, boron nitride is firstly adsorbed to the surface of the test piece, the surface layer of the test piece which is not covered by the boron nitride is slowly dissolved, and dissolved ferrous ions, zinc ions and phosphate ions are subjected to precipitation reaction to generate micro crystals. At the moment, the nanometer boron nitride particles are used as nucleation sites of crystals to promote the crystallization of phosphate and indirectly control the grain size, so that the boron nitride and the phosphate crystals are codeposited on the surface of steel to form a composite phosphating film. However, when excessive nano boron nitride particles are deposited and cover the surface of the test piece, the dissolution process of iron on the surface of the test piece is inhibited, the dissociation balance of phosphoric acid in the phosphating solution is damaged, the concentration of phosphate ions is reduced, and the formation of phosphate crystals, namely the film formation is not facilitated.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1) the boron nitride is used as a nucleation adsorption site of crystals during phosphorization, is beneficial to crystal adhesion and formation of a composite phosphorization film, and a dense and small-sized phosphorization film layer can be seen under a scanning electron microscope; the boron nitride is a hydrophobic nano material, the dense composite phosphating film can effectively prevent the permeation of moisture in the air, and the corrosion resistance is excellent; compared with a film layer without the boron nitride particles, the corrosion resistance is obviously improved.
2) According to the invention, boron nitride is used as a phosphating accelerator, a phosphating film can be rapidly prepared at a low temperature, phosphating and phosphating can be carried out at 20-40 ℃, high temperature is not required for phosphating, the time is only 5-20 minutes, and the cost and energy are saved, and the time is also saved.
3) Boron nitride is a green additive, and the phosphating sediments in the phosphating tank after phosphating treatment are less, which indicates that the success rate of phosphating of the test piece is high.
4) The phosphating solution does not contain harmful chemical substances such as sodium nitrite and the like, does not harm human health and ecological environment in the using process and after use, is convenient to use, and can meet the industrial requirement.
5) The zinc-based phosphating film prepared by the invention has a dark appearance, the film layer is hard, the film layer is uniform and fine, and the hardness of the composite film in the embodiment 1 is changed from 162Hv before modification to 350 Hv.
6) The invention takes a small amount of green pollution-free nano boron nitride particles as the phosphating accelerant, adopts the method for quickly preparing the phosphating film at normal temperature to carry out phosphating treatment on the workpiece, has high cost performance and less phosphating sediments and has obvious advantages of mass production.
Drawings
FIG. 1 is a scanning electron microscope image of the boron nitride film obtained in example 1 before and after modification at the same scale, with a magnification of 100.
FIG. 2 is a high-power scanning electron microscope photograph of the boron nitride composite phosphide film obtained in example 1, wherein (a) is magnified 20000 times and (b) is magnified 2000 times.
FIG. 3 is a photograph showing the results of measuring the corrosion resistance of the boron nitride composite phosphide film obtained in example 1 under the condition of copper sulfate dropping, wherein (a) is a phosphide film immediately after the copper sulfate dropping and (b) is a phosphide film having a reddish brown color appearing on the dropping.
FIG. 4 is an X-ray diffraction pattern of the boron nitride film obtained in example 1 before and after modification.
Detailed Description
For better understanding of the present invention, the present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the claims of the present invention, and other examples obtained by those skilled in the art without inventive efforts shall fall within the scope of the present invention.
The invention uses GB11376-89 to evaluate the appearance of the phosphating film; the film thickness of the phosphating film is tested by using GB4956 regulations; testing the corrosion resistance of the phosphating film by using a GB6458-86 neutral salt spray experiment; the corrosion resistance of the phosphating film is tested by using a GB6807-86 copper sulfate dropping method.
In the embodiment of the invention, a scanning electron microscope (FE-SEM, SU-8200, Japan) is used for representing the appearance and appearance of the phosphating film before and after BN modification.
In the examples of the present invention, a film thickness meter (kett, LZ-990) was used to measure the change in film thickness of the phosphate film before and after BN modification.
In the examples of the present invention, the main composition of the crystals of the phosphating film layer before and after BN modification was characterized by using an X-ray diffractometer (Bruker D8ADVANCE, Germany).
In the embodiment of the invention, a turret type digital microhardness tester (WILSON 402MVD) is used for measuring the microhardness of the BN modified phosphating film.
Example 1
Weighing the following raw material components in parts by weight: 5 parts of zinc dihydrogen phosphate dihydrate, 7 parts of zinc nitrate hexahydrate, 0.6 part of phosphoric acid, hexagonal boron nitride (average particle diameter 100nm, powder shape is elliptic disk or circular disk, and short axis La and long axis LbAnd the thickness t satisfies: la is more than or equal to 80nm and less than or equal to Lb≤700nm，20nm≤t≤150nm，t≤La，0.5≤La/LbLess than or equal to 1.0), 0.1 part of linear alkyl benzene sodium sulfonate (LAS), 6 parts of potassium chloride-hydrochloric acid PH buffer solution and 100 parts of water. Then putting the components into a reaction kettle, adjusting the pH of the solution in the kettle to be 2.3 by using alkali liquor, and heating to 30 ℃. Then the stirring speed is controlled at 300 rpm, and the mixture is mechanically stirred for 30 minutes and then taken out of the kettle. And then putting the prepared phosphating solution into a phosphating tank, immersing the steel test piece with the surface treated in the phosphating tank, treating for 20 minutes, washing with water and airing to obtain the phosphating test piece.
FIG. 1 is a scanning electron microscope image of the boron nitride film obtained in example 1 before and after modification at the same scale, with a magnification of 100. It is seen from the figure that the phosphating film before modification (left figure) has loose crystals and large crystal grains, and after modification (right figure) by adding boron nitride with proper proportion, the crystals become compact and fine, and the crystals on the composite film are uniformly distributed.
FIG. 2 is a high-power scanning electron microscope image of the boron nitride composite phosphide film obtained in example 1, wherein the left image (a) is magnified 20000 times and the right image (b) is magnified 2000 times. The layered film structure of the phosphate crystals can be clearly seen from the graph (a), and the boron nitride is co-deposited on the bottom of the substrate; in the graph (b), it is evident that the connection between the crystals is tight, which indicates that the tightness of the film layer is improved after boron nitride modification.
FIG. 3 is a photograph showing the results of examining the corrosion resistance of the boron nitride composite phosphide film obtained in example 1. The left panel (a) is a phosphating film on which a copper sulfate dropping liquid is just dropped, and the right panel (b) is a phosphating film on which a reddish brown dropping liquid appears. The conclusion of the embodiment shows that the color change time of the modified phosphating film reaches 320 seconds, which exceeds 60 seconds specified by the national standard, and the corrosion resistance is obviously improved.
FIG. 4 is an X-ray diffraction pattern of the boron nitride film obtained in example 1 before and after modification. As seen from the figure: the main component of the crystal before modification is Zn2Fe(PO4)2·4H2O, main component changed to Zn after adding boron nitride3(PO4)2·4H2The O, Fe peak signal is reduced and no boron nitride peak is clearly observed. The modifier is proved to be tightly wrapped by phosphate crystals, compounded and crystallized on the surfaces of more steel test pieces, and the dissolution of iron is inhibited. Doping of nano boron nitride does not change the crystal species, but merely acts as a nucleation adsorption site to change the preferential growth orientation of the crystal.
The phosphating film obtained in the embodiment 1 has a dark appearance and a fine film layer, the thickness of the film is 18.1 micrometers according to a test method of GB4956, and the hardness of the composite film is 350Hv by using a turret type digital microhardness tester. The corrosion resistance of the phosphating film is tested according to a copper sulfate drop experiment specified in GB6807-86, and the experiment shows that the phosphating film generates discoloration within 320 seconds. According to the neutral salt spray experiment specified in GB6458-86, the phosphating film does not corrode in 20 hours, and compared with a film layer without boron nitride particles, the corrosion resistance of the embodiment is obviously improved.
Compared with the traditional phosphating process such as 40-60 ℃ process technology reported in Chinese patent CN101029386A, the invention adopts a green low-temperature rapid preparation method of the phosphating film to carry out phosphating treatment on the workpiece, can greatly simplify the phosphating process, has low phosphating temperature and can be carried out at normal temperature.
Compared with the prior art that sodium nitrite and sodium fluoride which are harmful to the environment are used as the accelerant for phosphating treatment as reported in Chinese patent CN201610397553.4, the invention adopts green and pollution-free inorganic nano-particle boron nitride as the accelerant, thereby meeting the requirement of environmental protection.
Compared with the treatment liquid technology for the phosphorization and blackening of the steel surface reported by Chinese patent application No. CN103469187A, the phosphorization speed of the invention is high, only 5-20 minutes is needed, and time is saved.
Example 2
The raw material components are taken according to the weight ratio as follows: zinc phosphate 8 parts, zinc chloride 4 parts, zinc nitrate 3 parts, phosphoric acid 2.5 parts, cubic boron nitride (average particle diameter 50nm, powder shape is elliptic disk or disc, minor axis La, major axis LbAnd the thickness t satisfies: la is more than or equal to 80nm and less than or equal to Lb≤700nm，20nm≤t≤150nm，t≤La，0.5≤La/LbLess than or equal to 1.0), 0.08 part of fatty alcohol-polyoxyethylene ether sodium sulfate (AES), 6 parts of glycine-hydrochloric acid PH buffer solution and 100 parts of water. Putting the components into a reaction kettle, adjusting the pH of the solution in the kettle to 2.7 by using an alkaline solution, and heating to 30 ℃. Then the stirring speed is controlled at 250 rpm, and the mixture is mechanically stirred for 30 minutes and then taken out of the kettle. And (3) putting the prepared phosphating solution into a phosphating tank, immersing the steel test piece with the surface treated in the phosphating solution for 15 minutes, and washing and drying the steel test piece with water to obtain the phosphating test piece.
The phosphating film obtained in the embodiment 2 has a dark appearance and a fine film layer, the film thickness is 14.3 microns according to the GB4956 test method, and the hardness of the composite film is 316Hv by using a turret type digital microhardness tester. The corrosion resistance of the phosphating film is tested according to a copper sulfate spot experiment specified in GB6807-86, and the experiment shows that the phosphating film generates discoloration within 222 seconds. According to the neutral salt spray experiment specified in GB6458-86, the phosphating film does not corrode within 15 hours.
Example 3
The raw material components are taken according to the weight ratio as follows: zinc phosphate 7 parts, zinc nitrate hexahydrate 6 parts, phosphoric acid 1 part, hexagonal boron nitride (average particle diameter 80nm, powder shape is elliptic disk or disc, minor axis La, major axis LbAnd the thickness t satisfies: la is more than or equal to 80nm and less than or equal to Lb≤700nm，20nm≤t≤150nm，t≤La，0.5≤La/LbLess than or equal to 1.0), 0.06 parts of Alkylphenol Polyoxyethylene (APEO) emulsifier, 0.2 parts of monochloroacetic acid-sodium hydroxide PH buffer solution and 100 parts of water. Putting the components into a reaction kettle, adjusting the pH of the solution in the kettle to 2.5 by using alkali liquor, and then heating to 28 ℃. Then the stirring speed is controlled at 200 rpm, and the mixture is mechanically stirred for 30 minutes and then taken out of the kettle. Putting the prepared phosphating solution into a phosphating pool, and putting the surface into a furnaceAnd (3) immersing the steel test piece subjected to surface treatment in the water, wherein the treatment time is 10 minutes, and washing and airing the steel test piece by using water to obtain the phosphating test piece.
The phosphating film obtained in the embodiment 3 is dark in appearance and fine and smooth in film layer, the film thickness is 12.4 microns according to the GB4956 test method, and the hardness of the composite film is 253Hv by using a turret type digital microhardness tester. The corrosion resistance of the phosphating film is tested according to a copper sulfate spot experiment specified in GB6807-86, and the experiment shows that the phosphating film generates discoloration within 202 seconds. According to the neutral salt spray experiment specified in GB6458-86, the phosphating film does not corrode within 12 hours.
Example 4
The raw material components are taken according to the weight ratio as follows: 5 parts of zinc dihydrogen phosphate, 9 parts of zinc nitrate, 3 parts of phosphoric acid and rhombohedral boron nitride (the average particle diameter is 90 nanometers, the powder is in the shape of an elliptical disk or a circular disk, and the minor axis La and the major axis L arebAnd the thickness t satisfies the following formula: la is more than or equal to 80nm and less than or equal to Lb≤700nm，20nm≤t≤150nm，t≤La，0.5≤La/LbLess than or equal to 1.0), 0.04 parts of alkyl Alcohol Ether Carboxylate (AEC) stabilizer, 8 parts of hexamethylenetetramine-hydrochloric acid PH buffer solution and 100 parts of water. Putting the components into a reaction kettle, adjusting the pH value of the solution in the kettle to 2.5 by using alkali liquor, then heating to 30 ℃, controlling the stirring speed to be 250 revolutions per minute, mechanically stirring for 30 minutes, and taking out of the kettle. And (3) putting the prepared phosphating solution into a phosphating tank, immersing the steel test piece with the surface treated in the phosphating tank, treating for 10 minutes, washing with water and airing to obtain the phosphating test piece.
The phosphating film obtained in the embodiment 4 has a dark appearance and a fine film layer, the film thickness is 11.8 microns according to the GB4956 test method, and the hardness of the composite film is 206Hv by using a turret type digital microhardness tester. The corrosion resistance of the phosphating film is tested according to a copper sulfate spot experiment specified in GB6807-86, and the experiment shows that the phosphating film generates discoloration within 173 seconds. According to the neutral salt spray test specified in GB6458-86, the phosphating film does not corrode within 10 hours.
It should be noted that the present invention is not limited by the above-mentioned embodiments, and various changes and modifications can be made in the present invention without departing from the spirit and scope of the present invention, and these changes and modifications fall into the protection scope of the claimed invention; the scope of the invention is defined by the following claims.
Claims (8)
1. A method for preparing a composite phosphating film by doping inorganic nanoparticles is characterized by comprising the following steps:
1) preparing a phosphating solution: putting 5-8 parts by mass of phosphate, 7-9 parts by mass of zinc, manganese or calcium salt, 0.6-3 parts by mass of phosphoric acid, 0.04-0.4 part by mass of boron nitride, 0.1-1 part by mass of stabilizer, 6-10 parts by mass of pH buffering agent and 80-100 parts by mass of water into a reaction kettle, adjusting the pH to 2-3 by using alkali liquor, then heating to 20-40 ℃, controlling the stirring speed to 200-300 r/min, mechanically stirring for 30-60 min, and taking out of the kettle;
the stabilizer is one or more of linear alkyl benzene sulfonic acid sodium, fatty alcohol-polyoxyethylene ether sodium sulfate, alkyl alcohol ether carboxylate, alkylphenol polyoxyethylene and fatty acid polyoxyethylene ester;
the nano boron nitride is one or more of hexagonal boron nitride, rhombohedral boron nitride and cubic boron nitride;
2) and (3) a phosphating treatment process: and (3) putting the prepared phosphating solution into a phosphating tank, raising the temperature of phosphating to 20-40 ℃, then soaking the steel test piece subjected to rust and oil removal into the phosphating solution for 5-20 minutes, and washing and drying the steel test piece by water to obtain the composite phosphating film.
2. The method for preparing a composite phosphating film by doping inorganic nanoparticles according to claim 1, wherein the phosphate is one or more of acid salts, normal salts and hydrates thereof containing zinc ions, manganese ions and calcium ions.
3. The method for preparing the composite phosphating film by doping the inorganic nanoparticles according to claim 1, wherein the zinc, manganese or calcium salt is one or more of nitrate, chloride and hydrate thereof.
4. The method of claim 1, wherein the boron nitride nanoparticles have an average particle size of 50-100 nm, and more than 80 wt% of the particles are within ± 30% of the average particle size.
5. The method for preparing a composite phosphating film by doping inorganic nanoparticles according to claim 1, wherein the shape of the nano boron nitride powder is an elliptical disk or a circular disk, and the short axis La, the long axis Lb and the thickness t satisfy the following formula: la is more than or equal to 80nm and less than or equal to Lb is more than or equal to 700nm, t is more than or equal to 20nm and less than or equal to 150nm, t is more than or equal to La, and La/Lb is more than or equal to 0.5 and less than or equal to 1.0.
6. The method of claim 1, wherein the pH buffer is one or more of potassium chloride-hydrochloric acid, glycine-hydrochloric acid, monochloroacetic acid-sodium hydroxide, and hexamethylenetetramine-hydrochloric acid.
7. The method for preparing the composite phosphating film by doping the inorganic nanoparticles according to claim 1, wherein in the derusting process in the step 2), the front and back surfaces of a test piece are polished by 400-800 meshes of sand paper;
in the oil removing process in the step 2), the temperature of a 10 wt% sodium hydroxide solution is raised to 20-40 ℃, then the test piece is soaked for 5-10 minutes and taken out, and the ultrasonic treatment is carried out in an acetone solution for 3-5 minutes.
8. The method for preparing a composite phosphating film by doping inorganic nanoparticles according to claim 1, wherein the composite phosphating film is one or more of a zinc phosphating film, a manganese phosphating film and a calcium phosphating film.
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