CN112391618A - Environment-friendly phosphating solution containing graphene oxide and preparation method thereof - Google Patents
Environment-friendly phosphating solution containing graphene oxide and preparation method thereof Download PDFInfo
- Publication number
- CN112391618A CN112391618A CN201910737342.4A CN201910737342A CN112391618A CN 112391618 A CN112391618 A CN 112391618A CN 201910737342 A CN201910737342 A CN 201910737342A CN 112391618 A CN112391618 A CN 112391618A
- Authority
- CN
- China
- Prior art keywords
- parts
- acid
- graphene oxide
- stirring
- phosphating solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention relates to an environment-friendly phosphating solution containing graphene oxide, which is prepared from the following raw materials in parts by weight: 15-35 parts of phosphoric acid, 5-15 parts of zinc oxide, 5-16 parts of nitric acid (68%), 6-15 parts of calcium nitrate, 0.01-0.1 part of graphene oxide, 0.2-1 part of isopropanol, 0.01-0.1 part of additive, 0.5-5 parts of composite complexing agent and the balance of water. Wherein the additive is one of rare earth metal compound lanthanum nitrate and cerium nitrate, and the composite complexing agent is two or more of citric acid, tartaric acid, gluconic acid, sulfosalicylic acid, hydroxyethylidene diphosphonic acid (HEDP), phenanthroline and phytic acid. The phosphating solution adopts graphene oxide and rare earth compound to be compounded as an oxidant and an accelerant, does not use the traditional nitrite accelerant, has environment-friendly raw materials, and does not release harmful gas in the using process; the film forming speed is high in the phosphating process, the zinc-calcium film is tightly combined, and the corrosion resistance is strong; less tank liquid sediment after phosphorization and the like.
Description
Technical Field
The invention relates to an environment-friendly phosphating solution, and particularly relates to an environment-friendly phosphating solution containing graphene oxide.
Background
Before cold working, the carbon steel material needs to be subjected to surface treatment, and then the drawing and cold heading processing processes can be carried out. The most important treatment method of the surface treatment at present is phosphating.
The phosphorization is to generate a layer of compact phosphorization film on the surface of the cleaned steel, the layer of phosphorization film is compact in crystallization, fine and smooth in film and good in binding force, and a phosphorization saponification film with strong adhesiveness and good lubricity is formed with the subsequent lubrication process. In the subsequent processing process, the phosphorus soap film layer can ensure that the wire is subjected to drawing or cold heading processing for many times, and meanwhile, the die is protected from being damaged, so that great production cost is saved for customers.
Therefore, phosphating is an important step in the metal cold processing process, but phosphating solutions in the current market have different quality, can generate a large amount of harmful gas in the using process to cause a plurality of environmental pollution problems, and can generate a large amount of sediments after being used to be additionally disposed.
At present, a lot of patents related to phosphating exist, and a Chinese patent CN 103668148B discloses a medium-temperature zinc-calcium series high-corrosion-resistance phosphating solution and a preparation method thereof, wherein the phosphating solution is prepared from the following raw materials in percentage by mass: 15-20 parts of phosphoric acid, 4-7 parts of zinc oxide, 5-10 parts of zinc nitrate, 15-20 parts of calcium chloride, 0.5-1 part of sodium citrate and the balance of water. The phosphating solution disclosed by the invention is wide in applicable temperature range and extremely strong in corrosion resistance, but has the defect that the formula needs to be additionally added with a large amount of nitrite accelerator to promote the generation of phosphating in the phosphating process, and a large amount of harmful gas is generated in the phosphating process, so that the phosphating solution belongs to the environmentally-friendly phosphating solution.
Chinese patent CN 103757620A discloses a medium-low carbon steel wire rod drawing phosphating solution which comprises the following raw materials: 11-23g/L of zinc dihydrogen phosphate; 16-26g/L of zinc nitrate; 4-6g/L of composite accelerator; 3-8g/L of tartaric acid; the balance of water. The composite accelerator is a mixture of sodium chlorate, sodium nitrite and potassium permanganate. The invention has the advantages that the formed phosphating film has compact and continuous film layer crystallization, can be firmly adsorbed on the metal surface and the like, and is suitable for high-speed drawing. The defects are that the composite accelerator is a mixture of sodium chlorate, sodium nitrite and potassium permanganate, the corrosion resistance of the phosphated wire rod is reduced due to the existence of chlorate, the nitrite accelerator can release harmful gas in the production process, and excessive addition of the nitrite accelerator also easily causes the increase of sediments after phosphation.
At present, the most commonly used accelerators of the phosphating solution are nitrite and chlorate, the chlorate can reduce the corrosion resistance of a phosphating film layer, and harmful gas released by the nitrite in the phosphating process influences the health of workshop workers and is harmful to the environment. With the stricter environmental protection requirements in various places, the research and development of a phosphating solution containing an environmental protection accelerator is urgent.
Disclosure of Invention
The invention provides an environment-friendly phosphating solution containing graphene oxide and a preparation method thereof, aiming at solving the problems of no environment-friendly accelerator, low corrosion resistance of a phosphating film layer and more sediments after phosphating in the prior phosphating solution.
The specific technical scheme is as follows:
the environment-friendly phosphating solution containing graphene oxide comprises, by weight, 100 parts of 15-35 parts of phosphoric acid, 5-15 parts of zinc oxide, 5-16 parts of nitric acid (68%), 6-15 parts of calcium nitrate, 0.01-0.1 part of graphene oxide, 0.2-1 part of isopropanol, 0.01-0.1 part of an additive, 0.5-5 parts of a composite complexing agent and the balance of water.
Preferably, the oxidant is graphene oxide, and the graphene oxide is of a nano monolayer structure.
Preferably, the additive is a promoter, and is one of cerium nitrate and lanthanum nitrate in a rare earth compound.
Preferably, the complex complexing agent is two or more of citric acid, tartaric acid, gluconic acid, sulfosalicylic acid, hydroxyethylidene diphosphonic acid (HEDP), phenanthroline and phytic acid.
Preferably, the specific components comprise, by 100 parts, 30 parts of phosphoric acid, 15 parts of zinc oxide, 15 parts of nitric acid (68%), 6 parts of calcium nitrate, 0.1 part of graphene oxide, 1 part of isopropanol, 0.1 part of cerium nitrate, 0.2 part of composite complexing agent citric acid, 0.3 part of hydroxyethylidene diphosphonic acid (HEDP) and 32.3 parts of water.
Preferably, the weight ratio of the environment-friendly phosphating solution containing graphene oxide is 1.4-1.6, grooving is performed by 6-10%, the total acid is controlled to be 17-40pt, the free acid is controlled to be 4-8pt, and the acid ratio is controlled to be 4.5-7.
The preparation method of the environment-friendly phosphating solution containing graphene oxide comprises the following steps:
(1) group A raw materials: putting a proper amount of water into a stainless steel container, adding a proper amount of zinc oxide, stirring the zinc oxide into paste, slowly adding a proper amount of phosphoric acid, putting the mixture into a stirrer, stirring for 10-20min, adding a proper amount of nitric acid, continuously stirring for 10-30min, continuously adding calcium nitrate, and stirring for 20-40min to obtain a colorless transparent solution;
(2) b group of raw materials: taking a stainless steel container again, adding a proper amount of graphene oxide, adding a proper amount of phosphoric acid, water and isopropanol, and performing ultrasonic treatment for 30min-2.5h to fully disperse the graphene oxide in the solution, wherein the solution is brown;
(3) adding the group B raw materials into the group A raw materials, mixing and stirring for 20-30min, continuously adding the additive, stirring for 5-15min, adding a proper amount of the composite complexing agent, mixing and stirring for 10min, supplementing water, stirring for 30min-1h, packaging and warehousing after being detected to be qualified.
The technical scheme of the application has the following beneficial effects at least:
1. the technical scheme comprises that the environment-friendly phosphating solution containing graphene oxide comprises, by 100 parts, 15-35 parts of phosphoric acid, 5-15 parts of zinc oxide, 5-16 parts of nitric acid (68%), 6-15 parts of calcium nitrate, 0.01-0.1 part of graphene oxide, 0.2-1 part of isopropanol, 0.01-0.1 part of additive, 0.5-5 parts of composite complexing agent and the balance of water.
2. The method comprises the technical scheme that the additive is one of rare earth compound cerium nitrate or lanthanum nitrate, and the technical effects of rapid phosphorization and strong corrosion resistance of a film layer after phosphorization can be achieved through good oxygen carrying and depolarization capabilities of rare earth metal.
3. The technical scheme of adding calcium nitrate is adopted in the application, the zinc-calcium phosphating film layer is generated, the film layer is changed from a needle-shaped structure of a zinc system to a block-shaped structure of the zinc-calcium system, and the technical effects of increasing the bonding force between film layers and being more beneficial to wire drawing can be achieved.
4. The technical scheme that the composite complexing agent is two or more of citric acid, tartaric acid, gluconic acid, sulfosalicylic acid, hydroxyethylidene diphosphonic acid (HEDP), phenanthroline and phytic acid is adopted in the application, so that the aim of meeting the requirementProviding a certain free acid and complexing metal ions (mainly Fe)2+And Fe3+) And the technical effect of reducing the sediment after phosphorization.
Detailed Description
The invention provides an environment-friendly phosphating solution containing graphene oxide, which mainly comprises phosphoric acid, zinc oxide, nitric acid (68%), calcium nitrate, graphene oxide, isopropanol, rare earth compounds, a composite complexing agent, water and the like, replaces the conventional medium-high temperature phosphating solution, is used for phosphating carbon steel wires, achieves the environment-friendly raw materials and has no harmful gas release in the use process; the film forming speed is high in the phosphating process, the zinc-calcium film is tightly combined, and the corrosion resistance is strong; less tank liquid sediment after phosphorization and the like.
The technical scheme of the invention is described in detail by combining the following embodiments:
the environment-friendly phosphating solution containing graphene oxide comprises, by weight, 100 parts of 15-35 parts of phosphoric acid, 5-15 parts of zinc oxide, 5-16 parts of nitric acid (68%), 6-15 parts of calcium nitrate, 0.01-0.1 part of graphene oxide, 0.2-1 part of isopropanol, 0.01-0.1 part of an additive, 0.5-5 parts of a composite complexing agent and the balance of water.
The invention contains rich nitrate ions, on one hand, nitrate can play a role of an accelerant under the medium-high temperature condition to promote the phosphating reaction; on the other hand, nitrate radical can oxidize redundant Fe in the phosphating solution2+To Fe3+Preventing Fe in the phosphating solution2+The quality of the phosphating film layer is affected by excessive dosage.
The zinc-calcium phosphating solution disclosed by the invention adopts zinc-calcium phosphating, calcium nitrate can provide enough calcium ions for film formation, and the zinc-calcium film has the advantages of fine crystal grains, compact crystallization and better binding force.
The oxidant is compounded by graphene oxide and additive rare earth compound cerium nitrate or lanthanum nitrate, and the graphene oxide has the function of slowing down the occurrence of corrosion reaction on the surface of the wire rod and has the function of dehydrogenation. The graphene oxide has a large specific surface area and a reticular framework structure, so that the graphene oxide can be well adsorbed on the surface of a wire rod, the corrosion reaction of the wire rod is slowed down, and Fe is reduced2+Is released. Graphene oxide also containsHas rich oxygen ions, can be quickly combined with hydrogen on the surface of the wire rod, plays a good role in dehydrogenation and greatly accelerates the progress of the phosphating reaction.
The additive is one of rare earth compound cerium nitrate or lanthanum nitrate, the lanthanum nitrate or the cerium nitrate is an accelerant with good oxygen carrying capacity and cathode depolarization, and the lanthanum nitrate or the lanthanum nitrate does not participate in film formation in the reaction, so that the lanthanum nitrate or the cerium nitrate is not basically consumed. The rare earth metal has larger ionic radius, so the rare earth metal is easily adsorbed on the surface of the wire rod, and an effective nucleation active region is formed in the anode region and the cathode region, thereby being beneficial to the formation and refinement of phosphate crystal grains and the growth and film formation of crystal nuclei. In the whole phosphating process, the rare earth nitrate plays the roles of a surface conditioner and an accelerant, so that the phosphating process is accelerated, and the corrosion resistance of a phosphating film is improved.
The isopropanol used as a solvent can not only disperse the graphene oxide, but also make the phosphating film layer smoother and finer.
The complex complexing agent is two or more of citric acid, tartaric acid, gluconic acid, sulfosalicylic acid, hydroxyethylidene diphosphonic acid (HEDP), phenanthroline and phytic acid. After being compounded, the components can provide partial free acid for the phosphating solution, reduce the consumption of the phosphating solution to a certain extent and have the function of complexing Fe2+And Fe3+The function of (1). The bath solution has more Fe2+Affecting the film layer, by Fe2+Oxidized to Fe3+Form sediment with phosphate radical, so that a proper complexing agent is added to complex Fe2+And Fe3+Can ensure Fe in the bath solution2+Maintaining proper amount of Fe3+But also is basically complexed, so that the sediment is greatly reduced.
The preparation method of the environment-friendly phosphating solution containing the graphene oxide comprises the following steps:
(1) group A raw materials: putting a proper amount of water into a stainless steel container, adding a proper amount of zinc oxide, stirring the zinc oxide into paste, slowly adding a proper amount of phosphoric acid, putting the mixture into a stirrer, stirring for 10-20min, adding a proper amount of nitric acid, continuously stirring for 10-30min, continuously adding calcium nitrate, and stirring for 20-40min to obtain a colorless transparent solution;
(2) b group of raw materials: taking a stainless steel container again, adding a proper amount of graphene oxide, adding a proper amount of phosphoric acid, water and isopropanol, and performing ultrasonic treatment for 30min-2.5h to fully disperse the graphene oxide in the solution, wherein the solution is brown;
(3) adding the group B raw materials into the group A raw materials, mixing and stirring for 20-30min, continuously adding the additive, stirring for 5-15min, adding a proper amount of the composite complexing agent, mixing and stirring for 10min, supplementing water, stirring for 30min-1h, packaging and warehousing after being detected to be qualified.
One of the purposes of the invention is to overcome the defects that the existing phosphating solution releases a large amount of harmful gases in the process of using a nitrite accelerator, which affects the health of workers in a workshop and harms the environment, and the environment-friendly graphene oxide and rare earth accelerator are used for helping to promote the phosphating reaction, so that the phosphating efficiency can be greatly improved, and no waste gas is discharged.
The phosphating solution uses rare earth compounds as an accelerant, so that the generated zinc-calcium film is fine, compact, thick and strong in corrosion resistance, can meet the requirements of various drawing and cold heading production processes, and greatly reduces the damage of a die in subsequent production of customers.
The invention also aims to greatly reduce the generation of phosphorization sediments by the phosphorization liquid, thereby saving a large amount of waste residues for customers.
In order to make the technical solution of the present invention better understood by those skilled in the art, the following detailed description is given by way of specific examples, but it should be understood that these examples are only illustrative and not restrictive, and unless otherwise specified, the raw materials involved in the present invention are all commercially available, and except for industrial grade, medical grade and food grade raw materials, and the water added in the formulation is tap water meeting the water quality requirement.
Example 1
Based on 100 parts of phosphating solution, 30 parts of phosphoric acid, 15 parts of zinc oxide, 15 parts of nitric acid (68%), 6 parts of calcium nitrate, 0.1 part of graphene oxide, 1 part of isopropanol, 0.1 part of cerium nitrate, 0.2 part of composite complexing agent citric acid, 0.3 part of hydroxyethylidene diphosphonic acid (HEDP) and 32.3 parts of water are selected.
The preparation method comprises the following steps: (1) group A raw materials: adding 15 parts of zinc oxide into 15 parts of water in a stainless steel container, stirring the zinc oxide into paste, slowly adding 20 parts of phosphoric acid, stirring in a stirrer for 15min, adding 15 parts of nitric acid, continuously stirring for 30min, continuously adding 6 parts of calcium nitrate, and stirring for 30min to obtain a colorless transparent solution;
(2) b group of raw materials: and (3) taking a stainless steel container again, adding 0.1 part of graphene oxide, adding a proper amount of phosphoric acid 10 parts, isopropanol 1 part and water 10 parts, and performing ultrasonic treatment for 2.5 hours to fully disperse the graphene oxide in the solution, wherein the solution is brown.
(3) Adding the raw materials of group B into the raw materials of group A, mixing and stirring for 30min, continuously adding 0.1 part of additive cerium nitrate, stirring for 20min, adding 0.2 part of composite complexing agent citric acid and 0.3 part of hydroxyethylidene diphosphonic acid (HEDP), mixing and stirring for 20min, supplementing 7.3 parts of water, stirring for 30min, packaging and warehousing after being detected to be qualified.
Controlling parameters in the phosphating process: grooving with the concentration of 6 percent, adding water for dilution, controlling the heating temperature to be 65-75 ℃, controlling the parameters to be 26-30pt of total acid, 4-5pt of free acid, controlling the acid ratio to be 4.5-7, and controlling the phosphating time to be 5-12 min. The weight of the phosphatized wire rod film reaches 8-15g/cm2The film layer is compact and uniform.
Example 2
The phosphating solution is prepared from 100 parts of phosphating solution, 15 parts of phosphoric acid, 5 parts of zinc oxide, 5 parts of nitric acid (68%), 15 parts of calcium nitrate, 0.06 part of graphene oxide, 0.6 part of isopropanol, 0.01 part of lanthanum nitrate, 1 part of composite complexing agent citric acid, 2 parts of sulfosalicylic acid and 56.33 parts of water.
The preparation method comprises the following steps: (1) group A raw materials: adding 15 parts of water into a stainless steel container, adding 5 parts of zinc oxide, stirring the zinc oxide into paste, slowly adding 10 parts of phosphoric acid, stirring in a stirrer for 10min, adding 5 parts of nitric acid, continuously stirring for 30min, continuously adding 15 parts of calcium nitrate, and stirring for 25min to obtain a colorless transparent solution;
(2) b group of raw materials: taking a stainless steel container again, adding 0.06 part of graphene oxide, adding a proper amount of phosphoric acid 5 parts, isopropanol 0.6 part and water 10 parts, and performing ultrasonic treatment for 1.5 hours to fully disperse the graphene oxide in the solution, wherein the solution is brown;
(3) adding the raw material B into the raw material A, mixing and stirring for 30min, continuously adding 0.01 part of additive lanthanum nitrate, stirring for 10min, adding 1 part of composite complexing agent citric acid and 2 parts of sulfosalicylic acid, mixing and stirring for 10min, supplementing 31.33 parts of water, stirring for 40min, packaging and warehousing after being detected to be qualified.
Controlling parameters in the phosphating process: grooving with the concentration of 8 percent, adding water for dilution, controlling the heating temperature to be 65-75 ℃, controlling the parameters to be 17-22pt of total acid, 4-5pt of free acid, controlling the acid ratio to be 4.5-7, and controlling the phosphating time to be 5-12 min. The weight of the phosphatized wire rod film reaches 8-15g/cm2The film layer is compact and uniform.
Example 3
Based on 100 parts of phosphating solution, 15 parts of phosphoric acid, 10 parts of zinc oxide, 15 parts of nitric acid (68%), 12 parts of calcium nitrate, 0.02 part of graphene oxide, 0.2 part of isopropanol, 0.01 part of cerium nitrate, 0.2 part of composite complexing agent citric acid, 0.3 part of tartaric acid and 52.27 parts of water are selected.
The preparation method comprises the following steps: (1) group A raw materials: adding 15 parts of water into a stainless steel container, adding 10 parts of zinc oxide, stirring the zinc oxide into paste, slowly adding 10 parts of phosphoric acid, stirring in a stirrer for 20min, adding 15 parts of nitric acid, continuously stirring for 30min, continuously adding 12 parts of calcium nitrate, and stirring for 20min to obtain a colorless transparent solution;
(2) b group of raw materials: taking a stainless steel container again, adding 0.02 part of graphene oxide, adding a proper amount of phosphoric acid 5 parts, isopropanol 0.2 part and water 10 parts, and performing ultrasonic treatment for 1 hour to fully disperse the graphene oxide in the solution, wherein the solution is brown;
(3) adding the group B raw materials into the group A raw materials, mixing and stirring for 30min, continuously adding 0.01 part of additive cerium nitrate, stirring for 10min, adding 0.2 part of composite complexing agent citric acid and 0.3 part of tartaric acid, mixing and stirring for 10min, supplementing 22.27 parts of water, stirring for 30min, packaging and warehousing after the raw materials are detected to be qualified.
Controlling parameters in the phosphating process: grooving with the concentration of 10 percent, adding water for dilution, controlling the heating temperature to be 65-75 ℃, controlling the parameters to be 24-28pt of total acid, 5-6pt of free acid, controlling the acid ratio to be 4.5-7, and controlling the phosphating time to be 5-12 min. The weight of the phosphatized wire rod film reaches 8-15g/cm2The film layer is compact and uniform.
Example 4
Calculated by 100 parts of phosphating solution, 25 parts of phosphoric acid, 10 parts of zinc oxide, 8 parts of nitric acid (68%), 6 parts of calcium nitrate, 0.08 part of graphene oxide, 0.8 part of isopropanol, 0.1 part of lanthanum nitrate, 1 part of composite complexing agent hydroxyethylidene diphosphonic acid (HEDP), 1 part of phytic acid and 48.02 parts of water are selected.
The preparation method comprises the following steps: (1) group A raw materials: adding 10 parts of zinc oxide into 20 parts of water in a stainless steel container, stirring the zinc oxide into paste, slowly adding 15 parts of phosphoric acid, stirring in a stirrer for 10min, adding 8 parts of nitric acid, continuously stirring for 30min, continuously adding 6 parts of calcium nitrate, and stirring for 25min to obtain a colorless transparent solution;
(2) b group of raw materials: taking a stainless steel container again, adding 0.08 part of graphene oxide, adding a proper amount of phosphoric acid 10 parts, 0.8 part of isopropanol and 10 parts of water, and performing ultrasonic treatment for 2 hours to fully disperse the graphene oxide in the solution, wherein the solution is brown;
(3) adding the raw materials of group B into the raw materials of group A, mixing and stirring for 30min, continuously adding 0.1 part of additive lanthanum nitrate, stirring for 20min, adding 1 part of composite complexing agent hydroxyethylidene diphosphonic acid (HEDP) and 1 part of phytic acid, mixing and stirring for 10min, supplementing 18.02 parts of water, stirring for 1h, packaging and warehousing after the raw materials are detected to be qualified.
Controlling parameters in the phosphating process: grooving with the concentration of 8 percent, adding water for dilution, controlling the heating temperature to be 65-75 ℃, controlling the parameters to be 25-29pt of total acid, 4-5pt of free acid, controlling the acid ratio to be 4.5-7, and controlling the phosphating time to be 5-12 min. The weight of the phosphatized wire rod film reaches 8-15g/cm2The film layer is compact and uniform.
Example 5
The phosphating solution is prepared from 100 parts of phosphoric acid 30 parts, zinc oxide 12 parts, nitric acid (68%) 10 parts, calcium nitrate 6 parts, graphene oxide 0.05 part, isopropanol 0.6 part, cerium nitrate 0.05 part, composite complexing agent phenanthroline 0.1 part, gluconic acid 0.4 part and water 40.8 part.
The preparation method comprises the following steps: (1) group A raw materials: adding 12 parts of zinc oxide into 20 parts of water in a stainless steel container, stirring the zinc oxide into paste, slowly adding 20 parts of phosphoric acid, stirring in a stirrer for 10min, adding 10 parts of nitric acid, continuously stirring for 20min, continuously adding 6 parts of calcium nitrate, and stirring for 20min to obtain a colorless transparent solution;
(2) b group of raw materials: taking a stainless steel container again, adding 0.05 part of graphene oxide, adding a proper amount of phosphoric acid 10 parts, isopropanol 0.6 part and water 10 parts, and performing ultrasonic treatment for 1.5 hours to fully disperse the graphene oxide in the solution, wherein the solution is brown;
(3) adding the raw materials of group B into the raw materials of group A, mixing and stirring for 30min, continuously adding 0.05 part of additive cerium nitrate, stirring for 20min, then adding 0.1 part of composite complexing agent phenanthroline and 0.4 part of gluconic acid, mixing and stirring for 10min, supplementing 10.8 parts of water, stirring for 50min, packaging and warehousing after being detected to be qualified.
Controlling parameters in the phosphating process: grooving with the concentration of 8 percent, adding water for dilution, controlling the heating temperature to be 65-75 ℃, controlling the parameters to be 34-40pt of total acid, 6-8pt of free acid, controlling the acid ratio to be 4.5-7, and controlling the phosphating time to be 5-12 min. The weight of the phosphatized wire rod film reaches 8-15g/cm2The film layer is compact and uniform.
Example 6
Calculated by 100 parts of phosphating solution, 15 parts of phosphoric acid, 8 parts of zinc oxide, 12 parts of nitric acid (68%), 8 parts of calcium nitrate, 0.02 part of graphene oxide, 0.4 part of isopropanol, 0.05 part of lanthanum nitrate, 4.5 parts of composite complexing agent tartaric acid, 0.5 part of phytic acid and 51.53 parts of water are selected.
The preparation method comprises the following steps: (1) group A raw materials: adding 8 parts of zinc oxide into 20 parts of water in a stainless steel container, stirring the zinc oxide into paste, slowly adding 10 parts of phosphoric acid, stirring in a stirrer for 20min, adding 12 parts of nitric acid, continuously stirring for 15min, continuously adding 8 parts of calcium nitrate, and stirring for 20min to obtain a colorless transparent solution;
(2) b group of raw materials: and (3) taking a stainless steel container again, adding 0.02 part of graphene oxide, adding a proper amount of phosphoric acid 5 parts, isopropanol 0.04 part and water 10 parts, and performing ultrasonic treatment for 1.5 hours to fully disperse the graphene oxide in the solution, wherein the solution is dark brown.
(3) Adding the raw materials of group B into the raw materials of group A, mixing and stirring for 30min, continuously adding 0.05 part of additive lanthanum nitrate, stirring for 20min, adding 4.5 parts of composite complexing agent citric acid and 0.5 part of phytic acid, mixing and stirring for 20min, supplementing 21.53 parts of water, stirring for 40min, packaging and warehousing after being detected to be qualified.
Controlling parameters in the phosphating process: grooving with the concentration of 8 percent, adding water for dilution, controlling the heating temperature to be 65-75 ℃, controlling the parameters to be 22-25pt of total acid, 5-6pt of free acid, controlling the acid ratio to be 4.5-7, and controlling the phosphating time to be 5-12 min. The weight of the phosphatized wire rod film reaches 8-15g/cm2The film layer is compact and uniform.
Example 7
Calculated by 100 parts of phosphating solution, 35 parts of phosphoric acid, 15 parts of zinc oxide, 16 parts of nitric acid (68%), 6 parts of calcium nitrate, 0.01 part of graphene oxide, 0.5 part of isopropanol, 0.01 part of cerium nitrate, 1 part of sulfosalicylic acid serving as a composite complexing agent, 1 part of gluconic acid and 25.48 parts of water are selected.
The preparation method comprises the following steps: (1) group A raw materials: adding 15 parts of zinc oxide into 15 parts of water in a stainless steel container, stirring the zinc oxide into paste, slowly adding 25 parts of phosphoric acid, stirring in a stirrer for 10min, adding 16 parts of nitric acid, continuously stirring for 15min, continuously adding 6 parts of calcium nitrate, and stirring for 20min to obtain a colorless transparent solution;
b group of raw materials: and (3) taking a stainless steel container again, adding 0.01 part of graphene oxide, adding a proper amount of phosphoric acid 10 parts, isopropanol 0.5 part and water 10 parts, and performing ultrasonic treatment for 1 hour to fully disperse the graphene oxide in the solution, wherein the solution is brown.
(3) Adding the raw material B into the raw material A, mixing and stirring for 30min, continuously adding 0.01 part of additive cerium nitrate, stirring for 20min, adding 1 part of composite complexing agent sulfosalicylic acid and 1 part of gluconic acid, mixing and stirring for 20min, supplementing 0.48 part of water, stirring for 1h, packaging and warehousing after being detected to be qualified.
Controlling parameters in the phosphating process: grooving with the concentration of 6 percent, adding water for dilution, controlling the heating temperature to be 65-75 ℃, controlling the parameters to be 30-34pt of total acid, 6-8pt of free acid, controlling the acid ratio to be 4.5-7, and carrying out phosphating for 5-12 min. The weight of the phosphatized wire rod film reaches 8-15g/cm2The film layer is compact and uniform.
Example 8
Calculated by 100 parts of phosphating solution, 35 parts of phosphoric acid, 15 parts of zinc oxide, 10 parts of nitric acid (68%), 10 parts of calcium nitrate, 0.1 part of graphene oxide, 1 part of isopropanol, 0.01 part of cerium nitrate, 1 part of composite complexing agent citric acid, 0.5 part of hydroxy ethylidene diphosphonic acid (HEDP), 0.5 part of gluconic acid and 26.89 parts of water are selected.
The preparation method comprises the following steps: (1) group A raw materials: adding 15 parts of zinc oxide into 15 parts of water in a stainless steel container, stirring the zinc oxide into paste, slowly adding 25 parts of phosphoric acid, stirring in a stirrer for 10min, adding 10 parts of nitric acid, continuously stirring for 20min, continuously adding 10 parts of calcium nitrate, and stirring for 30min to obtain a colorless transparent solution;
(2) b group of raw materials: and (3) taking a stainless steel container again, adding 0.1 part of graphene oxide, adding a proper amount of phosphoric acid 10 parts, isopropanol 1 part and water 10 parts, and performing ultrasonic treatment for 2 hours to fully disperse the graphene oxide in the solution, wherein the solution is brown.
(3) Adding the raw material B into the raw material A, mixing and stirring for 30min, continuously adding 0.01 part of additive cerium nitrate, stirring for 20min, then adding 1 part of composite complexing agent citric acid, 0.5 part of hydroxyethylidene diphosphonic acid (HEDP) and 0.5 part of gluconic acid, mixing and stirring for 10min, supplementing 1.89 parts of water, and stirring for 30min until the solution is brown.
Controlling parameters in the phosphating process: grooving with the concentration of 6 percent, adding water for dilution, controlling the heating temperature to be 65-75 ℃, controlling parameters to be total acid 28-32pt, free acid 5-7pt, acid ratio to be 4.5-7, and phosphating time: 5-12 min. The weight of the phosphatized wire rod film reaches 8-15g/cm2The film layer is compact and uniform.
The formulations of examples 1-8 of the present invention are shown in Table 1 (calculated on 100Kg of an environmentally friendly phosphating solution containing graphene oxide).
TABLE 1 formulations of examples 1-8
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| Phosphoric acid | 30 | 15 | 15 | 25 | 30 | 15 | 35 | 35 |
| Zinc oxide | 15 | 5 | 10 | 10 | 12 | 8 | 15 | 15 |
| Nitric acid | 15 | 5 | 15 | 8 | 10 | 12 | 16 | 10 |
| Calcium nitrate | 6 | 15 | 12 | 6 | 6 | 8 | 6 | 10 |
| Graphene oxide | 0.1 | 0.06 | 0.02 | 0.08 | 0.05 | 0.02 | 0.01 | 0.1 |
| Isopropanol (I-propanol) | 1 | 0.6 | 0.2 | 0.8 | 0.6 | 0.4 | 0.5 | 1 |
| Cerium nitrate | 0.1 | / | 0.01 | / | 0.05 | / | 0.01 | 0.01 |
| Lanthanum nitrate | / | 0.01 | / | 0.1 | / | 0.05 | / | / |
| Composite complexing agent | 0.5 | 3 | 0.5 | 2 | 0.5 | 5 | 2 | 2 |
| Water (W) | 32.3 | 56.33 | 47.27 | 48.02 | 40.8 | 51.53 | 25.48 | 26.89 |
The use parameters and effects of examples 1-8 of the present invention are shown in Table 2.
TABLE 2 parameters used and Effect of examples 1-8
From table 2, it can be seen that the phosphating solution of the invention has short phosphating time under the co-promotion action of graphene oxide and rare earth compounds, has thick film after phosphating, and can meet the requirements of various drawing and cold heading production processes.
In the embodiment 1, the 1000T wire is phosphated, the generated slag amount is 200-250Kg, the slag amount is obviously less than that of the common phosphating solution (the slag amount is 2-4T/1000T wire), and the slag amount of the other embodiments is basically 400-250 Kg/1000T wire.
The application of the environment-friendly phosphating solution is used by a plurality of companies in Guangdong, more than six months of phosphating solution is continuously used at present, the amount of phosphating wire rods is more than 10000T wire rods, the actual effect is reflected as fast phosphating speed, a film layer is compact after phosphating, and the amount of slag is less.
The phosphorization object of the phosphorization liquid is mainly used for annealing lines and wire coils made of carbon steel and stainless steel, and other devices capable of being phosphorized are also protected by the invention.
It is to be understood that the invention is not limited to the specific embodiments described above, but is intended to cover various insubstantial modifications of the inventive process concepts and solutions, or its application to other applications without modification.
Claims (7)
1. An environment-friendly phosphating solution containing graphene oxide is characterized in that: calculated by 100 parts, the composite material comprises 15-35 parts of phosphoric acid, 5-15 parts of zinc oxide, 5-16 parts of nitric acid (68%), 6-15 parts of calcium nitrate, 0.01-0.1 part of graphene oxide, 0.2-1 part of isopropanol, 0.01-0.1 part of additive, 0.5-5 parts of composite complexing agent and the balance of water.
2. The environmentally friendly phosphating solution containing graphene oxide according to claim 1, characterized in that: the graphene oxide is of a nano single-layer structure.
3. The environmentally friendly phosphating solution containing graphene oxide according to claim 1 or 2, characterized in that: the additive is one of cerium nitrate and lanthanum nitrate in a rare earth compound.
4. The environmentally friendly phosphating solution containing graphene oxide according to claim 1 or 2, characterized in that: the complex complexing agent is two or more of citric acid, tartaric acid, gluconic acid, sulfosalicylic acid, hydroxy ethylidene diphosphonic acid (HEDP), phenanthroline and phytic acid.
5. The environmentally friendly phosphating solution containing graphene oxide according to claim 1, characterized in that: the specific components comprise, by weight, 100 parts of phosphoric acid 30 parts, zinc oxide 15 parts, nitric acid (68%), calcium nitrate 6 parts, graphene oxide 0.1 part, isopropanol 1 part, cerium nitrate 0.1 part, composite complexing agent citric acid 0.2 part, hydroxyethylidene diphosphonic acid (HEDP)0.3 part and water 32.3 parts.
6. The graphene oxide-containing environment-friendly phosphating solution according to claim 1 or 5, which is characterized in that: the weight ratio of the environment-friendly phosphating solution containing graphene oxide is 1.4-1.6, 6-10% of the solution is grooved, the total acid is controlled to be 17-40pt, the free acid is controlled to be 4-8pt, and the acid ratio is controlled to be 4.5-7.
7. The method for preparing the environmentally friendly phosphating solution containing graphene oxide according to claim 1, comprising the following steps:
(1) group A raw materials: putting a proper amount of water into a stainless steel container, adding a proper amount of zinc oxide, stirring the zinc oxide into paste, slowly adding a proper amount of phosphoric acid, putting the mixture into a stirrer, stirring for 10-20min, adding a proper amount of nitric acid, continuously stirring for 10-30min, continuously adding calcium nitrate, and stirring for 20-40min to obtain a colorless transparent solution;
(2) b group of raw materials: taking a stainless steel container again, adding a proper amount of graphene oxide, adding a proper amount of phosphoric acid, water and isopropanol, and performing ultrasonic treatment for 30min-2.5h to fully disperse the graphene oxide in the solution, wherein the solution is brown;
(3) adding the group B raw materials into the group A raw materials, mixing and stirring for 20-30min, continuously adding the additive, stirring for 5-15min, adding a proper amount of the composite complexing agent, mixing and stirring for 10min, complementing water, stirring for 30min-1h, packaging and warehousing after being detected to be qualified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910737342.4A CN112391618A (en) | 2019-08-12 | 2019-08-12 | Environment-friendly phosphating solution containing graphene oxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910737342.4A CN112391618A (en) | 2019-08-12 | 2019-08-12 | Environment-friendly phosphating solution containing graphene oxide and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112391618A true CN112391618A (en) | 2021-02-23 |
Family
ID=74602127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910737342.4A Pending CN112391618A (en) | 2019-08-12 | 2019-08-12 | Environment-friendly phosphating solution containing graphene oxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112391618A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113969406A (en) * | 2021-10-29 | 2022-01-25 | 南京科润工业介质股份有限公司 | Phosphorus-free pretreatment agent for metal surface treatment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB932845A (en) * | 1960-06-23 | 1963-07-31 | Stefan Klinghoffer | Method of phosphate-coating metal workpieces and phosphating solution used therefor |
| CN102121103A (en) * | 2010-01-11 | 2011-07-13 | 张华斌 | Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof |
| CN107012453A (en) * | 2017-03-31 | 2017-08-04 | 华南理工大学 | A kind of method that green low temperature quickly prepares phosphating coat |
-
2019
- 2019-08-12 CN CN201910737342.4A patent/CN112391618A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB932845A (en) * | 1960-06-23 | 1963-07-31 | Stefan Klinghoffer | Method of phosphate-coating metal workpieces and phosphating solution used therefor |
| CN102121103A (en) * | 2010-01-11 | 2011-07-13 | 张华斌 | Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof |
| CN107012453A (en) * | 2017-03-31 | 2017-08-04 | 华南理工大学 | A kind of method that green low temperature quickly prepares phosphating coat |
Non-Patent Citations (1)
| Title |
|---|
| 唐春华: "成膜处理剂(Ⅲ)", 《电镀与环保》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113969406A (en) * | 2021-10-29 | 2022-01-25 | 南京科润工业介质股份有限公司 | Phosphorus-free pretreatment agent for metal surface treatment |
| WO2023071899A1 (en) * | 2021-10-29 | 2023-05-04 | 南京科润工业介质股份有限公司 | Phosphorus-free pretreatment agent for metal surface treatment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107345297A (en) | A kind of alkaline cleaning fluid, phosphating solution and metal surface treating method | |
| CN101760743A (en) | Tin stripping liquid | |
| CN106148974A (en) | A kind of iron and steel derusting and phosphorating agent | |
| CN104372342A (en) | Chemical stainless steel polishing solution | |
| CN109972186B (en) | Stainless steel passivation treatment method | |
| CN113106434A (en) | Environment-friendly aluminum alloy chemical oxidation liquid and chemical oxidation method | |
| CN111748817A (en) | Tin stripping water additive | |
| CN112391618A (en) | Environment-friendly phosphating solution containing graphene oxide and preparation method thereof | |
| CN105483682B (en) | A kind of phosphating solution for metal processing and preparation method thereof | |
| CN105483681B (en) | A kind of preparation method of zinc system metal treatment fluid | |
| CN112359362A (en) | Acid-washing, phosphorizing and saponifying method for bearing steel | |
| CN105369173A (en) | Compound plating aid for hot-dip tinning of copper alloy and preparation method of compound plating aid | |
| CN109574524B (en) | Method for improving early hydration activity of steel slag | |
| CN1401820A (en) | Ordinary temp. parkerizing liquid | |
| CN106149042A (en) | A kind of kirsite electrolysis stripping copper agent | |
| CN102605364B (en) | Intermediate-temperature low-sediment and low-emission thick membrane phosphorizing liquid and phosphorizing method thereof | |
| CN101824624A (en) | Hot-rolled plate chlorohydric acid pickling fog-resistant accelerator | |
| CN112095096A (en) | Zinc-series low-slag phosphating agent and preparation method thereof | |
| CN102534619A (en) | Aluminium molybdenum etching liquid and preparation method thereof | |
| CN101586243B (en) | Hot rolled plate hydrochloric acid pickling corrosion inhibition accelerator | |
| CN104962896A (en) | Zinc-system phosphating solution additive and use method thereof | |
| CN111349920B (en) | Environment-friendly phosphating solution containing rare earth composite accelerator and using method | |
| CN113151832B (en) | Magnetic graphene oxide/carboxymethyl chitosan compound corrosion inhibitor and preparation method and application thereof | |
| CN101285191B (en) | Process for preparing corrosion inhibitor | |
| CN104131272B (en) | A kind of zero-emission type chemical nickel-plating liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210223 |
|
| RJ01 | Rejection of invention patent application after publication |