JPS63227699A - Lubrication treatment method for plastic working of high nickel alloy steel - Google Patents

Abstract

PURPOSE:To afford outstanding coefficient of friction and wear-resistant baking characteristics by forming an oxalate film on the surface of high-nickel alloy steel followed by treatment with an aqueous solution containing acrylic polymer and wax, etc., and then heating and baking. CONSTITUTION:An oxalate film is formed on the surface of high-nickel alloy steel such as incoloy, inconel or stainless steel containing >=20wt.% of nickel, followed by treatment with, as the lubricating agent, an aqueous solution made up of (A) 10-35pts.wt. of an acrylic resin with the glass transition point regulated to -50-10 deg.C, (B) 3-15pts.wt. of wax, (C) 0.5-5pts.wt. of a surfactant and (D) the rest of water with the weight ratio A/B regulated to 2-12, and the drying at normal temperature, heating and baking, thus accomplishing the objective lubricating treatment.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to high nickel-based alloy steels (for example, Incoloy,
Inconel or stainless steel with N120% or more), high nickel alloy steel is used in plastic processing, that is, head processing (hereinafter referred to as header processing), cold forging, plate press processing, rolling, wire drawing, drawing of steel pipes, etc. After forming an oxalate film, a lubricating film is formed by treatment with a water-dispersed resin lubricant,
The present invention relates to a lubrication treatment method that prevents seizure from occurring.

[Conventional technology] Conventionally, when plastic working high nickel alloy steel, a lubricant is applied to the metal in order to reduce friction and wear of the metal and mold tools. For high-temperature materials, lubricating oil containing extreme pressure agents and oiliness improvers is applied, and for highly processed materials, resin-based lubricants diluted with organic solvents are applied, and on top of that, lubricating oil is applied. Oil is applied.

In addition, in the case of ordinary stainless steel, an oxalate film + soap lubricant film is used as a lubrication treatment, but since high nickel alloy steel has excellent corrosion resistance, oxalate treatment significantly inhibits the reaction. and insufficient film formation. For this reason, the amount of etching agents such as fluorine compounds and chlorine compounds is increased in the oxalate treatment solution, but the treatment takes a long time and there is a problem that a satisfactory film is not formed even if a film is formed. In combination with this, there is a problem in that the oxalate film partially peels off during processing, and seizure occurs in the peeled part.

[Problems to be solved by the invention] In recent years, the uses of metal materials have diversified, and when the conditions for plastic working of difficult-to-work materials such as high nickel alloy steel are severe, lubricants such as oils and resins cannot be used. A problem that has arisen is that there are cases where the customer is not satisfied. Furthermore, resin-based lubricants used after being diluted with organic solvents are not good for environmental hygiene and may also pose a risk of fire. Furthermore, since the residual film after cold processing cannot be easily removed by alkali cleaner treatment and then pickling, problems have arisen such as unsuitability for processing sites.

Therefore, we used a water-dispersed lubrication treatment liquid that poses no risk of fire or other hazards, and it shows excellent lubrication performance during intense cold working, and also removes the film that remains on the metal surface after cold working by using an alkaline cleaner → pickling. There has been a need for metal lubricants that can be easily removed.

[Means for solving the problem] As a result of intensive research to develop a lubricant that meets the above-mentioned needs, after forming an oxalate film on the surface of high nickel-based alloy steel, a lubricant with a glass transition point was developed. = 10 to 35 parts by weight of acrylic resin adjusted to 50 to 10°C and 3 to 3 parts of wax
15 parts by weight, 0.5 to 5 parts by weight of surfactant, and the remainder contains water, and the acrylic resin/wax weight ratio is 2.
When treated with an aqueous liquid adjusted to 12 to 12, dried at room temperature, heated and baked, a lubricant film superior to that obtained using conventional lubricants could be obtained.

[Description of composition] The oxalate treatment in the present invention is described in Japanese Patent Publication No. 60-212, for example.
It can be treated with the treatment liquid described in No. 27.

The acrylic resin having a glass transition point of -50 to 10°C in the present invention has the general formula %) [In the formula, the order of Ra, Rb, and Rc is random, and R
a is vinyltoluene group, styrene group, methacrylic group, acrylonitrile group, acrylic acid and carbon number 1-1
Acrylic acid ester obtained by reaction with primary aliphatic alcohol having 2, methacrylic acid and carbon number 3 to 12
Rb is acrylic acid,
Phosphate ester compound of methacrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl methacrylate, 2-
1 selected from phosphate ester compounds of hydroxypropyl methacrylate or alkali neutralized products thereof
RC is 2-hydroxylethyl methacrylate, hydroxylpropyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, N-methylolacrylamide or its ester compound, di- 1 selected from acetone acrylamide or glycidyl methacrylate
It consists of 0 to 15% by weight of one or more species. ] can be used. n is a degree of polymerization of 1,000 to 50,000, but the glass transition point is -
Polymerize at 50-10°C.

For example, a desired glass transition point can be obtained by emulsion polymerizing a mixture of each hexamer at 50 to 60° C. for 5 to 7 hours. Other polymerization methods include, for example, solution polymerization and suspension polymerization. Depending on the polymerization method, a solvent other than water may be used; for example, ethanol, isopropyl alcohol, etc. may be used.

The waxes used in the present invention include petroleum paraffin wax, animal and vegetable oils, higher fatty acids, higher alcohols, higher fatty acids and higher alcohol esters, higher fatty acid amides,
Examples include amine salts of higher fatty acids, and it is preferable to use those with a melting point of 45° C. or higher in order to solidify the lubricant film. One way to raise the melting point is to eliminate double bonds by hydrogenation.

Surfactants are used to emulsify and disperse wax in water, and examples of the surfactants include anionic surfactants and nonionic surfactants. Examples of anionic surfactants include sodium alkylnaphthalene sulfonate, sodium alkylbenzenesulfonate, and funnel oil. Examples of nonionic surfactants include polyoxyethylene alkyl ether (the alkyl group is a higher alcohol) type, polyester, etc. Examples include oxyethylene nonylphenol ethers, fatty acids and polyethylene glycol esters, fatty acids and sorbitan esters, and ethylene oxide adducts. Although a certain degree of emulsification and dispersion can be achieved using a surfactant, mechanical stirring such as a homogenizer may be used in combination to further improve the emulsifying property.

A solid lubricant may be added to the lubricant/processing liquid of the present invention. Examples of the solid lubricant include graphite, molybdenum disulfide, talc, Teflon, boron nitride, calcium carbonate, and melamine-isocyanuric acid adduct.

[For production] Reason for using oxalate film; ■ Forms a film of iron oxalate or nickel oxalate.

■ It has the effect of retaining lubricant and forms a uniform film that prevents liquid clumps from forming. →It has a great effect in preventing push-in.

■ It is heat resistant, and the film does not soften even when processing heat is generated, so the film does not peel off even during ironing, so it has a great anti-seizure effect.

■ The lubricating film is removed when cold-worked materials are made into products, but the oxalate film can be easily removed by pickling.

Reason for using acrylic resin: Water dispersibility is made possible by introducing carboxylic acid or phosphoric acid ester into the skeleton of acrylic resin. In addition, since it has good adhesion to metals and oxalate coatings, it does not peel off and does not seize even when subjected to the straining action of cold working. Furthermore,
To prevent direct contact between metal and tool during cold working of metal,
It is necessary for the resin film to follow the elongation of the metal. Therefore, resin has a good structure with good flexibility.
As for the characteristic values of the resin itself, the softer it is, the better it stretches.
The film can easily follow the elongation of the metal.

Therefore, the lower the glass transition point is from 150 to 10°C, the softer and better the elongation. If the temperature is less than -50°C, the film becomes too soft and seizure is likely to occur during cold working. 10℃
In this case, the film becomes too hard, and its ability to follow the elongation of the metal during metal processing decreases, and film forming properties tend to deteriorate during the cold winter months, making it difficult to form a uniform film. The preferred temperature is -30 to 0°C.

It is also necessary to remove the lubricating film after cold working. For example, removal with an alkaline degreasing solution is effective if the RC contains many carboxylic acid groups, phosphoric ester groups, etc.
The higher the ratio, the better the removability.

The Ra of the general formula of the acrylic resin is 55 to 97% by weight, which gives the film hardness, tensile strength, and stretchability.
It is preferable to include it. Rb improves adhesion with metals, emulsification and dispersion properties, and alkali degreasing properties, and is 3 to 3.
The content is preferably 30% by weight. Rc is necessary to improve adhesion to metals and to cure by crosslinking with the carboxyl group of Rb when heated to improve heat resistance, and is preferably contained in an amount of 0 to 15% by weight.

If Ra is less than 55%, the flexibility of the resin film will be poor and the film will not elongate to keep up with the elongation of the metal during plastic working, resulting in film breakage and seizure, which is not good. 97%
If it exceeds this amount, the water dispersion stability of the resin will decrease and precipitation will occur easily. Furthermore, alkaline degreasing properties are also reduced.

When Rb is less than 3%, ■ Adhesion to metal decreases.

■ The film cannot be removed using alkaline degreasing solution.

■ Water dispersibility decreases.

If it exceeds 30%, (1) the viscosity of the treatment liquid becomes too high, resulting in poor workability and coating properties.

■ The formed film has high hygroscopicity, and if left for a long time after formation, the adhesion of the film will decrease due to moisture absorption.

If the RC exceeds 15%, (1) the film becomes too cross-linked and loses its flexibility, and the film cannot follow the elongation of the metal during plastic working, causing seizure, which is not good. The content of hydroxyalkyl methacrylate is preferably 15% or less, and the content of N-methylolacrylamide or glycidyl methacrylate is preferably 3% or less.

The mixing ratio of acrylic resin and wax is an important factor, and by mixing an appropriate amount of wax with the acrylic resin, the removability and lubricity of the resin film on the metal surface are improved. When the acrylic resin/wax weight ratio is less than 2, the adhesion of the film formed on the metal decreases, causing the film to break and seize during plastic deformation of the metal.

If it exceeds 12, the slipperiness will decrease and the friction between the metals will increase, resulting in seizure. Preferably, it is in the range of 4-6.

The appropriate addition concentration of surfactant in the lubricant treatment liquid is 0.5 to 0.5, considering the addition concentration and lubricity required for emulsification and dispersion, since adding too much will reduce the lubricity.
5 parts by weight is good. Examples of the surfactant include nonionic, anionic, cationic, and amphoteric surfactants. Preferred are anionic and anionic.

Applying the lubricant treatment liquid of the present invention to metal'? 1. After forming an oxalate film on high nickel synthetic steel that has been degreased and pickled in advance, a water-dispersed lubricant film is applied using the dipping method, spray method, brush coating method, sink GJ method, or [coal coater]. However, it is preferable to air-dry the film beforehand and then bake it at 80 to 120°C, as this improves the adhesion. Water dispersion Q to be formed
The amount of sebum in the resin lubricating film varies depending on the plastic deformation method, and in the case of light processing such as plates, it is 0.5 to 5 g/T.
11. , 5 to 309/m for heavy work such as pipes
The concentration of the treatment solution is changed to form a treatment.

[Example] Next, several examples will be described.

Examples 1 to 4 InD Roy 800 (Cr21%, Ni32.5%, Fe
46%) Steel pipes were pickled, rinsed with water, formed an oxalate film with the oxalate treatment solution shown in Table 1, and immersed in the treatment solution containing acrylic resin and wax shown in Tables 2 and 3. process(
20℃, 1 minute), drained the liquid for 1 hour, and dried naturally.
Dry with hot air at 00℃ for 30 minutes to form a solid film.
g/butt was formed. Drawing was performed using a tube drawing machine, and the appearance after drawing was observed and the method for removing the lubricant film was investigated. The results are shown in Table 4.

Tube drawing conditions - Incoloy 800 steel pipe 25φ x 2.5t x 2000fJ (mm)φ processing degree 32% - Pulling speed 17.8m/l 1lin Processing conditions 9
Immersed at 0°C for 60 minutes Table 3 Composition of lubricant treatment liquid and Inconel 600 50X 100X O, 7m material, test plates were prepared using the same treatment liquid and conditions, and the friction coefficient and sliding resistance until seizure were determined using a Bauden tester. The number of movements was measured. Not shown in Table 4.

[Bauden test, conditions] Indenter: 5UJ-25φ Load: 5Ky Sliding speed ftJ: 10mm / SeC sliding width: 30
mm Test plate: Inconel 60050x 100 x 0.7
mm Test temperature: 25°C Comparative Example 1 A steel pipe of Incoloy 800 similar to the example was pickled, washed with water, subjected to oxalate film chemical conversion treatment (treatment liquid shown in Table 1), and washed with water.
Then, after lubrication treatment (Bondalube 235 (product of Par Ising Co., Ltd. > 70 g/ρ, 80°C, 3 minutes treatment) and drying, handling was carried out under the same drawing conditions as in Example 1, and the Bowden test was carried out. The results are shown in Tables 4 and 5.

Comparative Example 2 The same Incoloy 800 steel pipe as in Example 1 was pickled, washed with water, dried, and then treated with a solvent-diluted resin [Hangstarfa 111Q].
D (manufactured by Hangstarf Co., Ltd.)] 1 to 1/2 times diluted with luene, immersed (1 minute at room temperature), air-dried for 1 day, and then coated with lubricating oil (J-1 (manufactured by Hangstarf Co., Ltd.)) rear,
Drawing and Bowden tests were performed under the same drawing conditions as in the examples. The resin adhesion amount was 10 g/yd. The results are shown in Tables 4 and 5.

Table 4 Test results Kamaro 33% Drawing performance of stainless steel pipe Table 5 Bowden test *1: The smaller the value, the better the slipperiness.

*2 has good anti-seizing performance for culms that undergo a large number of sliding movements.

Removal test of lubricating film after drawing A stainless steel pipe after drawing was immersed for 1 hour in an aqueous alkaline degreasing solution at 90°C containing 3% caustic soda, 15% sodium tripolyphosphate, and a surfactant, and then pickled with nitric-hydrofluoric acid. After that, the removal f1 of the lubricating film was visually determined.

As is clear from Table 4, the lubricating film formed on the surface of the Incoloy 800 pipe by the lubrication treatment method of the present invention exhibited superior lubricating effects in the drawing test compared to the comparative example. In addition, the removability of the lubricant film remaining on the surface of the steel plate after drawing was excellent in both examples as it was completely removed, whereas in the comparative example the removability was extremely poor and the result was far inferior. showed that. or,
As is clear from Table 4, the lubricating film formed on the surface of the Inconel steel sheet showed superior friction coefficient (the lower the slipperiness, the better the slipperiness) and wear resistance and seizure resistance in the Bowden test compared to the comparative example. Ta.

[Effect of the invention].

If metal is treated with the lubricant treatment liquid for cold working of the present invention and dried to form a solid film of 0.5 to 30 g/m on the surface, the solid film will be sufficient at the initial stage of cold working. It exhibits good lubricity and cannot be separated by ironing, so a film remains on the surface of the processed metal, preventing contact between the metal and the mold tool. During the deformation process, the metal surface rises by 100 to 150 degrees Celsius due to the heat of deformation and frictional heat of the metal, which improves the elongation of the resin film, which follows the deformation of the metal well and prevents the film from breaking, resulting in the seizure phenomenon. doesn't happen. After cold working, the residual film can be easily removed by an alkali cleaner followed by pickling treatment, resulting in excellent effects such as being suitable for workability at the working site.

Claims (1)

[Claims] After forming an oxalate film on the surface of high nickel alloy steel, 10 to 35 parts by weight of an acrylic resin with a glass transition point adjusted to -50 to 10°C as a lubricant and 3 to 3 parts of wax are added.
After treating with an aqueous liquid containing 15 parts by weight, 0.5 to 5 parts by weight of a surfactant, and the rest containing water, and the acrylic resin/wax weight ratio being adjusted to 2 to 12, and drying at room temperature, A lubrication treatment method for plastic working of high nickel alloy steel characterized by heating and baking.