JP2005097735A - Method of producing aluminum and aluminum alloy - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of making the surface of aluminum or an aluminum alloy high in decorativeness having metallic luster and a crystal pattern. <P>SOLUTION: A pure aluminum or aluminum alloy material is subjected to pretreatment of crystal precipitation and grinding for one or more times. If required, etching treatment is additionally performed thereto, and next, anode oxidation treatment is performed thereto. Thus, an aluminum material high in decorativeness in such a manner that the difference in crystal orientation is vividly exhibited without losing luster and a metal crystal pattern by the reflection of light is floated up while maintaining its corrosion resistance is obtained. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a method for producing aluminum and aluminum alloys having gloss and crystal patterns with high decorativeness on the surface.

Aluminum alloys are used in large quantities in a wide range of fields such as structural materials and building materials because of their light weight, good thermal conductivity, corrosion resistance, and excellent plastic workability.
Aluminum and aluminum alloys have the advantage of being able to be molded into various shapes that require decorative properties, such as accessories, stationery, various cases, etc., by sheet metal such as bending, drawing, or pressing, forging, die casting, or the like. However, it has been difficult to simultaneously impart a crystal pattern decoration having a metallic luster to the alloy materials.
For example, Patent Document 1 proposes a method for producing an aluminum extruded material having a crystal pattern by performing an etching process with the Fe and Cu contents in an Al—Si—Mg-based extruded material at a predetermined ratio.
The processed material obtained by this method has a limited composition and it is difficult to produce a clean metallic luster and a highly decorative crystal pattern even when anodizing is performed after etching only.

JP-A-6-336682

An object of the present invention is to form a surface having a metallic luster and a crystal pattern on aluminum and an aluminum alloy material, which are insufficiently decorative in the prior art.

The present invention combines two steps of crystal precipitation and polishing as a pretreatment of aluminum or an aluminum alloy in an arbitrary order, and if necessary, combines three types of steps with an etching step added in an arbitrary order. This is a method for producing aluminum or an aluminum alloy having a surface having a metallic luster and a crystal pattern, characterized by performing anodization after repeating this one or more times.
As the aluminum or aluminum alloy used in the present invention, any of wrought material, cast material, and forged material is used, but it is a wrought material such as a rolled plate, a round bar, an extruded material, etc. Those having been subjected to are preferable. The macro-crystallization of the crystal grains includes a method of recrystallization by heat treatment and an aging treatment after solution hardening and a method of promoting crystal growth by performing plastic processing of about several percent.
On the other hand, aluminum or aluminum alloy material as a starting material can be bent, drawn, pressed, etc. good.
In this case, the existing product is heat treated at a temperature not higher than the recrystallization temperature of the raw material and not higher than the melting temperature within the range where the shape of the product is not significantly deformed for 10 minutes or more to crystallize the crystal grains. It is preferable to perform the pretreatment. A normal heat treatment temperature is in the range of 300 to 630 ° C., and a holding time of 30 minutes to 72 hours is practical. The product after the heat treatment is cooled at a cooling rate controlled so that a crystal grain of a desired size grows up to the recrystallization temperature or lower, for example, at 30 to 150 ° C./60 minutes, or by water cooling or oil cooling. It is preferable to cool to room temperature by rapid cooling or natural cooling by air cooling or standing.

Products used in this way include office supplies, projectors, DVDs, computers, scanners, printers, mice, paper knives, architectural walls, ceilings, brans, handles, batting plates, desks, chairs, lighting Equipment shades, bases, reflective interior parts, etc., exterior doors, gate pillars, fences, lighting equipment, reflective goods, shelves, vehicle-related parts, automobile interior parts, motorcycle parts, bicycle parts, wheelchair parts, mobile products As digital cameras, mobile phones, MDs, CD devices, video cameras, headphones, radios, general household appliance components, mini components, refrigerators, coolers, humidifiers, landline phones, clock-related dials, appearance, hands, Compact containers for cosmetics, containers for lipsticks, caps, tableware, dishes, balls, coasters, spoons as general supplies Kitchen articles such as hawks, knives, beer cups, sheds, jars, vases, jars, business card cases, accessories such as pendants, necklaces, bracelets, belts, earrings, rings, etc. Products that are part or all of are eligible. All of these products do not necessarily have to be made of an aluminum-based material.

Crystal precipitation methods include an alkaline treatment method or an acidic treatment method. In the alkaline treatment, liquid containing caustic soda, caustic potash and / or sodium phosphate, and in the acidic treatment, hydrofluoric acid, fluoride salt, acidic fluoride are used. Chloride salt, silicofluoride salt, hydrochloric acid, chloride salt, nitric acid, nitrate salt, nitrous acid, nitrite salt, phosphoric acid, phosphate salt, sulfuric acid, sulfate salt, aromatic or aliphatic fluorinated compounds, chlorine compounds as organic matter A solution containing one or two or more compounds of nitric acid compounds is used. In particular, a method of treating with an acidic aqueous solution is preferable, and hydrofluoric acid, hydrochloric acid, nitric acid, nitrous acid, phosphoric acid, sulfuric acid or a mixture thereof is preferably used as the acidic compound used at this time. Particularly preferred is a combination of nitric acid and hydrochloric acid and / or chloride.

The concentration of the compound contained in the aqueous solution used in the crystal precipitation treatment is 0.03 to 30 mol / L in total of the compounds, and particularly when the acid mixture is used, the concentration is preferably 6 to 15 mol / L. The treatment is performed by setting the bath temperature to 10 to 60 ° C. and immersing the material once or twice or more for 5 seconds to 20 minutes.

For the polishing performed in the present invention, either an electrolytic polishing method or a chemical polishing method is used. The bath composition is phosphoric acid, phosphoric acid sulfuric acid, and phosphoric acid chromic acid acid side in the case of electrolytic polishing, and the bath composition is phosphoric acid, phosphoric acid sulfuric acid, and phosphoric acid nitric acid in the case of chemical polishing. It is carried out on the acidic side or on the alkaline side of caustic soda and sodium phosphate.

The conditions for the electropolishing are preferably 10 to 18 mol / L in the total amount of one or more compounds having a liquid concentration, a bath temperature of 70 to 95 ° C., and a current density of 10 ± 5 A / dec square meter.
In chemical polishing, the liquid concentration is 10 to 18 mol / L, the bath temperature is 60 to 98 ° C., and the time is 30 seconds to 5 minutes. As the bath composition, a phosphoric acid + nitric acid solution is particularly preferable.

In the polishing step, glycerin and / or agar or both may be added to the polishing liquid as a gloss additive. The amount added is preferably about 0.1 to 1.0 mol / L for glycerin and about 3 to 30 g / L for agar.

Etching of the present invention can be performed on the alkaline side using caustic soda and caustic potash, or on the acidic side containing one or more acidic ammonium fluoride, sulfuric acid, nitric acid, and phosphoric acid.
The conditions for the etching treatment are preferably 40 to 80 ° C. and a time of 10 to 120 seconds in a solution having a liquid concentration of 0.5 to 6 mol / L.

The anodizing treatment of the present invention includes an aromatic or aliphatic organic acid having one or more carboxyl groups or sulfonic groups, or a mixed acid of these organic acids and sulfuric acid or phosphoric acid or both, It is preferable to carry out at an electric current density of 0.8 to 4 A / dec square meter and a voltage of 10 to 80 V in an electrolytic solution having a concentration of 0.5 to 10 mol / L. As the organic acid, oxalic acid is particularly preferable. In this case, the acid in the electrolytic aqueous solution is preferably 0.2 to 0.7 mol / L.
The anodizing treatment in the electrolytic solution adjusted in this way is particularly preferably performed at a bath temperature of -5 to 25 ° C. The crystal pattern produced only by the etching process is usually lost by virtue of anodizing, but the material treated by the present invention is deeper because it is a low temperature process even if anodized. It will be of a certain color, and vividness will not be lost.

In the present invention, the combination of two steps of crystal precipitation and polishing or three steps obtained by adding etching to the aluminum material may be any combination. For example, crystal precipitation under alkali and chemical polishing under alkali And there is an etching treatment combination under alkalinity. In the present invention, such an arbitrary combination of two or three kinds of steps is applied to the aluminum material at least once, and then the anodizing treatment is performed.

The aluminum material obtained in the present invention can be freely subjected to electrolytic coloring or dyeing treatment after anodizing to further enhance the decoration.
When the aluminum or aluminum alloy obtained in the present invention is in the form of a plate, it is molded into a casing of a mobile phone, a walkman or other various electrical parts by bending, drawing or pressing, etc. Used as a highly productive product.
When a material already processed into a product shape is used, it is used as a highly decorative product having a metallic luster as it is after being colored and dyed as necessary.

Aluminum or its alloy material obtained by the method of the present invention has a large and vivid metallic luster and crystal pattern on the surface, the degree of reflection of light changes depending on the viewing angle, and has a very rich aesthetics. Excellent materials or products can be obtained.

Next, the present invention will be specifically described with reference to examples. In the examples, “%” means “% by weight” unless otherwise specified.

Two plate-like samples made of JIS-A1050 material, which is pure aluminum that has been crystallized in advance, are degreased and then etched into a caustic soda solution having a concentration of 20 ± 2% (0.5 mol / L) as an etching process. It was immersed for 20 seconds at 73 ° C. and desmutted. Next, phosphoric acid (85%) 95V / V% (13.9 mol / L), sulfuric acid (98%) 3V / V% (0.44 mol / L) and nitric acid (67.5%) 1.5V / Chemical polishing was performed by immersing in a chemical polishing liquid consisting of V% (0.22 mol / L) and having a total acid concentration of 14.56 mol / L at 95 ° C. for 30 seconds. As a crystal precipitation step, nitric acid (67.5%) 150 ml / L (2.3 mol / L), hydrochloric acid (35%) 400 ml / L (4.5 mol / L), hydrofluoric acid (55%) 30 ml / The sample was immersed in a mixed solution of L (0.83 mol / L) (crystal precipitation solution having a total acid concentration of 7.63 mol / L) at 25 ± 2 ° C. for 25 seconds. Furthermore, this was immersed in the chemical polishing liquid for 10 seconds to perform chemical polishing.

The aluminum plate-like sample thus subjected to three kinds of pretreatments was subjected to an anodic oxidation electrolyte solution containing 13 V / V% (2.4 mol / L) sulfuric acid and 1% (0.08 mol / L) oxalic acid ( Anodization was performed at a bath temperature of 20 ° C., a current density of 0.9 A / dec square meter, and a voltage of 13.5 V for 10 minutes using a total acid concentration of 2.48 mol / L).
One of the two samples was subjected to a known nickel-based sealing treatment at 95 ° C. for 20 minutes after washing with water for gloss measurement. The gloss of this product was 76% when measured with a gloss meter at an incident / reflecting angle of 85 °. Since the surface of this sample has a large and complex crystal plane of aluminum, when the gloss level of the sample is measured at an incident / reflection angle determined at a fixed position, the surface of the sample (measurement surface) exhibits a different gloss. However, when the sample angle is changed, another crystal surface exhibits maximum gloss, and when this sample is exposed to natural light, it exhibits excellent decorativeness.
The other sample was immersed in a dyed food yellow No. 4 (made by Hodogaya Chemical Co., Ltd.) at a concentration of 5 g / L for surface dyeing at a liquid temperature of 50 ° C. for 10 minutes, washed with water and then known nickel. The system was sealed at 95 ° C. for 20 minutes. A surface photograph of this plate-like sample is shown in FIG.
(Comparative example)

For comparison, a pre-treatment including only an etching treatment was performed, and a sample subjected to the same anodizing treatment and sealing treatment as in Example 1 was prepared. The maximum glossiness of this comparative sample was 52%, which was significantly inferior to that of the present invention. Moreover, the surface photograph of the sample which performed dyeing | staining and sealing processing after the anodizing process is shown in FIG. This was small in crystal size and had a distinct difference in decorativeness from the sample of the present invention.

A plate sample made of a JIS-A5052 material, which is an aluminum-magnesium alloy that has been crystallized in advance, is subjected to degreasing, etching, chemical polishing, crystal precipitation, and chemical polishing under the same conditions as in Example 1. It was.
The aluminum material that had been subjected to the three types of pretreatment was anodized using the same anodizing electrolyte as in Example 1 at a bath temperature of 20 ° C., a current density of 0.9 A / dec square meter, and a voltage of 13 V for 20 minutes. . This was washed with water and then subjected to a known nickel-based sealing treatment at 95 ° C. for 20 minutes, and the maximum glossiness measured with a gloss meter (85 ° reflection angle) was 70%. For comparison, the maximum glossiness of a comparative product that was pretreated only by etching treatment and was subjected to the same anodizing treatment was 48%, which was significantly inferior to the product of the present invention.

A JIS-A1050 tableware that has not been crystallized in advance is heated and held at 550 ° C. for 24 hours, then gradually cooled to 200 ° C. at a cooling rate of 100 ° C./60 minutes, and then allowed to stand naturally. It was at room temperature. This product was subjected to degreasing, etching, chemical polishing, and crystal precipitation treatment under the same conditions as in Example 1, and further subjected to chemical polishing for 15 seconds with the above chemical polishing solution. After washing with water, the same anodizing electrolyte as in Example 1 was used, and anodization was performed at a bath temperature of 19 ° C., a current density of 1.0 A / dec square meter, and a voltage of 14 V for 20 minutes. Subsequently, it was immersed in a liquid containing 5 g / L of edible yellow No. 4 at a liquid temperature of 50 ° C. for 10 minutes, and after water washing, steam sealing (pressure 0.4 ± 0.01 MPa, 15 minutes) was performed. A glossy crystal pattern tableware with a maximum glossiness of 70% was obtained.

The same non-crystallized tableware used in Example 3 was heated and held at 550 ° C. for 5 hours, immersed in oil at about 30 ° C. for 300 seconds, and rapidly cooled to about 50 ° C., Thereafter, washing and degreasing were performed, and the next step was performed. This product was subjected to degreasing, etching, chemical polishing, and crystal precipitation treatment under the same conditions as in Example 1, and further subjected to chemical polishing for 15 seconds with the above chemical polishing solution. This was anodized under the same conditions as in Example 1, and the same dyeing and vapor sealing as in Example 3 were performed. The maximum glossiness of this dish was 73%.

A plate sample of two pure aluminum JIS-A1050 materials that had been crystallized in advance was subjected to degreased phosphoric acid 13.9 mol / L, sulfuric acid (98%) 0.44 mol / L and nitric acid (67. 5%) 0.22 mol / L, and chemical polishing was performed by dipping in a solution having a total acid concentration of 14.56 mol / L at 95 ° C. for 30 seconds. As a crystal precipitation step, a mixed solution of nitric acid (67.5%) 2.3 mol / L and hydrochloric acid (35%) 4.5 mol / L (crystal precipitation solution having a total acid concentration of 6.8 mol / L) It was immersed for 25 seconds at 25 ± 2 ° C. Furthermore, this was immersed in the chemical polishing liquid for 10 seconds to perform chemical polishing.

The aluminum plate-like sample thus subjected to two kinds of pretreatments was subjected to an anodic oxidation electrolyte solution containing 13 V / V% (2.4 mol / L) sulfuric acid and 1% (0.08 mol / L) oxalic acid ( Anodization was performed at a bath temperature of 20 ° C., a current density of 0.9 A / dec square meter, and a voltage of 13.5 V for 10 minutes using a total acid concentration of 2.48 mol / L).
One of these samples was subjected to a known nickel sealing treatment at 95 ° C. for 20 minutes after washing with water for gloss measurement. A large crystal plane of aluminum was present in a complicated manner on the surface of this sample, and the maximum glossiness was 87%. In the present invention, when the etching process is not added, the metallic gloss becomes larger and excellent decorativeness is exhibited.

As in Example 5, except that in the crystal precipitation step, a mixed solution of nitric acid (67.5%) 2.3 mol / L and sodium chloride 2.0 mol / L (the total concentration of the contained compounds is 4.3 mol) / L crystal precipitation solution) at 25 ± 2 ° C. for 25 seconds. Furthermore, this was immersed in the chemical polishing liquid for 10 seconds to perform chemical polishing. This was anodized in the same manner as in Example 5. The maximum glossiness at this time was 89%.

The surface photograph of the material obtained in Example 1 of this invention is shown. The surface photograph of the comparative material with respect to Example 1 is shown.

Claims (12)

  A metal characterized by combining two steps of crystal precipitation and polishing in an arbitrary order as a pretreatment of aluminum or an aluminum alloy, and performing an anodizing treatment after repeating the treatment once or twice or more. A method for producing aluminum or an aluminum alloy having a surface having a gloss and a crystal pattern.   The three processes of crystal precipitation, polishing, and etching are combined in an arbitrary order as a pretreatment of aluminum or an aluminum alloy, and this is repeated once or twice or more and then anodized. A method for producing aluminum or an aluminum alloy having a surface having a metallic luster and a crystal pattern. The aluminum or the aluminum alloy is a rolled material such as a rolled material, a round bar, a tube, or an extruded material, or a casting material such as a sand mold, a die, or a die cast, and has been subjected to crystallization in advance. 1 or 2 production method.   Aluminum or aluminum alloy is a stationery for office use, projector, DVD, PC, scanner, printer, mouse, paper knife, wall for construction, ceiling, bran, handle, pad, desk, chair, lighting fixture , Table, interior for reflection, gate as exterior, gate pillar, fence, lighting, reflection, shelf, vehicle, automobile interior, motorcycle, bicycle, wheelchair, digital camera as mobile product , Mobile phones, MDs, CD devices, video cameras, headphones, radios, general home appliance components, minicomponents, refrigerators, coolers, humidifiers, landline phones, clock-related dials, appearance, hands, cosmetics Compact, lipstick containers, caps, tableware, dishes, balls, coasters, cups as general supplies Molded into main parts and accessories such as pendants, necklaces, bracelets, belts, earrings, rings, etc. The manufacturing method according to claim 1 or 2, which is a part or all of the manufactured product. The product of claim 4, which has not been crystallized in advance as aluminum or aluminum alloy, is heated for 10 minutes or more at a temperature not lower than the recrystallization temperature and not higher than the melting temperature of the product, and then water-cooled, oil-cooled, air-cooled. Or the manufacturing method of Claim 1 or 2 using what was cooled to normal temperature by rapid cooling by standing and / or slow cooling.   Crystal precipitation is carried out by an alkaline or acidic treatment method, caustic soda, caustic potash or sodium phosphate solution for alkaline treatment, hydrofluoric acid, fluoride salt, acidic fluoride salt, silicofluoride salt, hydrochloric acid for acidic treatment , Chloride salt, nitric acid, nitrate, nitrous acid, nitrite, phosphoric acid, phosphate, sulfuric acid, sulfate, organic, aromatic or aliphatic fluoride, sulfonate, chloride, nitrate 6. The method according to claim 1, wherein the method comprises immersing aluminum or an aluminum alloy in a solution containing two or more.   The liquid concentration in the crystal precipitation step is 0.03 to 30 mol / L in total of one or two or more mixed liquids, bath temperature is 10 to 60 ° C., and the time is 5 seconds to 20 minutes. The manufacturing method according to claim 1, wherein:   Polishing is performed by electropolishing or chemical polishing. The bath composition is phosphoric acid-based, phosphoric acid-sulfuric acid-based, and phosphoric acid-chromic acid-chromic acid-based acid side when electropolishing, and the bath composition is phosphoric acid-based when chemical polishing is performed. The method according to any one of claims 1 to 7, which is carried out on the acidic side of phosphoric acid and sulfuric acid, or on the alkaline side of caustic soda and sodium phosphate. The liquid concentration in the electropolishing step is 10 to 18 mol / L in total of one or two or more mixed liquids, the bath temperature is 70 to 95 ° C., the time is 1 to 20 minutes, the current density is 10 ± 5 A / dec square meter, The liquid concentration in the chemical polishing step is that the total of one or two or more mixed liquids is 10 to 18 / L, the bath temperature is 60 to 98 ° C., and the time is 30 seconds to 5 minutes. The manufacturing method of Claim 1 thru | or 8. Etching is performed on the alkaline side using caustic soda, caustic potash, or on the acidic side containing one or more acidic ammonium fluoride, sulfuric acid, nitric acid, phosphoric acid, and the liquid concentration is 0.4 to The production method according to claim 2, wherein the immersion is performed at 6 mol / L, and the liquid temperature is 40 to 80 ° C. and the time is 10 to 300 seconds.   As an anodizing solution, one or two or more mixed organic acids having one or more aromatic or aliphatic carboxyl groups or sulfone groups, or a mixed solution containing these organic acids and sulfuric acid or phosphoric acid alone or mixed acids The manufacturing method according to claim 1, wherein the total is 0.5 to 10 mol / L, the bath temperature is -5 to 40 ° C, the current density is 0.6 to 5 A / dec square meter, and the voltage is 10 to 80 V. . 13. The method according to claim 1, wherein electrolytic coloring or dyeing is performed after the anodizing treatment.

Images