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CN1093884C - Decorative aluminium alloy member and its production method - Google Patents

Decorative aluminium alloy member and its production method Download PDF

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CN1093884C
CN1093884C CN99122168A CN99122168A CN1093884C CN 1093884 C CN1093884 C CN 1093884C CN 99122168 A CN99122168 A CN 99122168A CN 99122168 A CN99122168 A CN 99122168A CN 1093884 C CN1093884 C CN 1093884C
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aluminum alloy
aluminium alloy
molded body
molding
weight
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CN1254028A (en
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桥仓学
服部久雄
锻冶俊彦
武田义信
谷田部光信
城户幸雄
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Casio Computer Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon

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Abstract

一种装饰用的铝合金构件(10)包括由铝合金制成的基体(1)和形成在该基体表面上的阳极氧化膜(2)。构成基体(1)的铝合金包含重量百分比为0.1%至3%的Zr、重量百分比为0.1%至15%的含铈的稀土元素合金(Mm)、重量百分比为0.1%至5%的Mg以及剩余部分的Al。

Figure 99122168

A decorative aluminum alloy member (10) includes a base (1) made of aluminum alloy and an anodized film (2) formed on the surface of the base. The aluminum alloy constituting the base (1) comprises 0.1% to 3% by weight of Zr, 0.1% to 15% by weight of a cerium-containing rare earth element alloy (Mm), 0.1% to 5% by weight of Mg, and The rest of the Al.

Figure 99122168

Description

Ornamental aluminium alloy element and production method thereof
The present invention relates to a kind of ornamental aluminium alloy element and a kind of method that is used to produce this member.
In the prior art of this technical field, bar or the plate made by the fused aluminium alloy are pressed into a kind of required shape by cold forming or hot-die, by anodic oxidation this pressing are carried out surface treatment then.
In the prior art, it has been recognized that the physical strength of molten aluminum is lower.In order to increase the intensity of molten aluminum, in aluminium, add Mg (magnesium) and the interpolation element such as Cu (copper), Si (silicon) and Zn (zinc).Resulting aluminium alloy is carried out surface treatment by anodic oxidation or by low temperature anodic oxidation (hard anodic oxidation treatment), thereby makes its surface hardening.The aluminium alloy of so handling is used as a kind of decoration element, for example is used as the exterior part of wrist-watch.
As mentioned above, in the prior art, consider the intensity in the use temperature scope of the exterior part of for example wrist-watch, often use to include and add for example molten aluminium alloy of Mg, Cu, Si and Zn of element.Yet because molten aluminium alloy has comprised these elements, so the physical strength in the processing temperature scope of this aluminium alloy also is enhanced relatively, consequently, this aluminium alloy of cold forming or hot moulding is just relatively more difficult.Specifically, because the viscous deformation when cold forming or hot moulding, so the obvious distortion of Metallic Solids can appear, and increase internal stress, just mechanical hardening.Therefore, cold forming performance or hot moulding degradation.Like this, when this aluminium alloy is molded into a kind of shape of complexity, need mold pressing stage by stage, to obtain the net shape of this complexity, this can cause very high cost.
This extruded aluminium alloy will carry out anodic oxidation after through selected machined into or boring processing, to obtain for example finished product exterior part of wrist-watch, will polish subsequently.Yet, the aluminium alloy before the anodic oxidation, just the surface hardness of the initial crystalline structure of aluminium alloy is lower.
Say that exactly this surface hardness Hv is 100 to the maximum.This is because the present inventor with this aluminium alloy cold forming three times, and measures the surface hardness Hv of this pressing according to JIS A5052-O, thereby finds that described surface hardness Hv is about 70.
Because the surface hardness of the aluminium alloy in the prior art is low as mentioned above, so this alloy is highly susceptible to damaging necessary significant care when handling.When this alloy carries out industrialized mass production, need to consider that output has a certain amount of reduction.
Furtherly, by anodic oxidation or low temperature anodic oxidation are carried out in the surface of above-mentioned pressing, owing to its surface hardening, thus can guarantee its erosion resistance, and further guarantee its wear resistance.But in general, the thickness of the film that produces by anodic oxidation or low temperature anodic oxidation at most only is about 20 μ m.Due to the fact that with the lower hardness of the initial crystalline structure of above-mentioned aluminium alloy, when with the alloy of this anodic oxidation during as the exterior part of wrist-watch, it is easy to by damage.
Therefore, the method that the purpose of this invention is to provide a kind of ornamental aluminium alloy element and produce this member, described this aluminium alloy element is moulded to complicated shape easily, and the hardness height of its aluminium alloy crystalline structure.
Another object of the present invention provides a kind of ornamental aluminium alloy element, and its aluminium alloy crystalline structure has high rigidity, and its anode oxide film is transparent and colourless or light color is arranged, for example canescence or silvery white.
According to a first aspect of the present invention, a kind of ornamental aluminium alloy element is provided, it comprises matrix of being made by aluminium alloy and one deck anode oxide film that forms on this matrix surface, it is that 0.1% to 3% Zr, weight percent are that 0.1% to 15% mischmetal (hereinafter it being abbreviated as Mm), weight percent are 0.1% to 5% the Mg and the Al of remainder that described aluminium alloy comprises weight percent.
According to a second aspect of the present invention, a kind of ornamental aluminium alloy element is provided, and it comprises matrix of being made by aluminium alloy and the anode oxide film that forms on this matrix, wherein, the hardness HRB of this matrix is 50-100, and the brightness of this anode oxide film is 50 or higher.
Furtherly, according to the present invention, a kind of method of producing ornamental aluminium alloy element is provided, this method may further comprise the steps: (a) form a mold pressing base substrate of being made by the aluminium alloy with following component content, the component content of described aluminium alloy is: weight percent is that 0.1% to 3% Zr, weight percent are that 0.1% to 15% Mm, weight percent are 0.1% to 5% the Mg and the Al of remainder; (b) be under 2 ℃/second or the higher condition this mold pressing base substrate to be heated to 200 ℃-600 ℃ temperature at temperature rise rate; (c) process the mold pressing base substrate that this has heated; And (d) finished mold pressing base substrate is carried out anodic oxidation treatment.Usually, begin this mold pressing base substrate is heated to 200 ℃-600 ℃ from room temperature (envrionment temperature).
Fig. 1 is the partial cross-section cut-away view that schematically shows the structure of watch case, and watch case described here is an example as the ornamental aluminium alloy element of the present invention;
Fig. 2 is the synoptic diagram that first step in the method for watch case shown in Figure 1 is produced in expression;
Fig. 3 is the synoptic diagram that second step in the method for watch case shown in Figure 1 produced in expression;
Fig. 4 is the synoptic diagram that the 3rd step in the method for watch case shown in Figure 1 produced in expression;
Fig. 5 is the synoptic diagram that the 4th step in the method for watch case shown in Figure 1 produced in expression;
Fig. 6 is the synoptic diagram that the 5th step in the method for watch case shown in Figure 1 produced in expression;
Fig. 7 is the synoptic diagram that the 6th step in the method for watch case shown in Figure 1 produced in expression;
Fig. 8 is the synoptic diagram that the 7th step in the method for watch case shown in Figure 1 produced in expression;
Fig. 9 is the synoptic diagram that the 8th step in the method for watch case shown in Figure 1 produced in expression.
The inventor conducts extensive research, and has found a kind of composition of aluminium alloy, and this aluminium alloy can easily be molded into complicated shape, and the hardness of its initial aluminum crystal structure of alloy can be modified.
Specifically, the invention provides a kind of ornamental aluminium alloy element, it comprises the matrix of being made by aluminium alloy and is formed on one deck anode oxide film on this matrix surface, and it is that 0.1% to 3% Zr, percentage by weight are that 0.1% to 15% Mm, percentage by weight are 0.1% to 5% Mg and the Al of remainder that described aluminium alloy comprises percentage by weight.
Aluminium alloy intensity under processing temperature with above-mentioned composition is low, the easy like this shape that is moulded to complexity. Therefore, few in order to the comparable number of times of the prior art of the mold pressing number of times that obtains net shape, thus can cut down finished cost.
In addition, aluminium alloy of the present invention has improved hardness, thereby can prevent before the anodic oxidation that aluminium alloy element damages when processing. If this member is carried out industrialized mass production, then its output can be higher than the output of prior art. Because the hardness of aluminium alloy of the present invention is improved, so after anode oxide film formed, even described aluminium alloy element is subject to External Force Acting, this member also was not easy damaged.
In addition, the inventor has been found that the matrix at the aluminium alloy with above-mentioned composition forms in the situation of anode oxide film, and this anode oxide film can be made to transparent and colourless, linen or argenteous. Consequently, make in the painted situation of this anode oxide film, can not be subjected to this anode oxide film primitive color impact and obtain required color. Therefore, aluminium alloy element of the present invention is very suitable for as such ornament, that is, this ornament requires to have light tone.
Below will describe add the content of element.
Zr has a kind of like this effect, that is, add a spot of Zr the crystalline grain-size of aluminium is diminished, to improve the hardness of aluminium alloy.Yet if Zr has formed oversaturated sosoloid and kept sosoloid after hot-work when solidifying rapidly, the anode oxide film that the anodic oxidation by aluminium alloy produces will present dark color.Therefore, by making Zr not form sosoloid and making Zr to separate out with the form of aluminium formation intermetallic compound, this anode oxide film can be made into transparent and colourless, linen or argenteous.
In aluminium alloy of the present invention, it is in 0.1% to 3% the scope that the content of Zr is set at weight percent.If the weight percent content of Zr less than 0.1%, then can not obtain to add the effect of Zr.If the weight percent content of Zr is greater than 3%, Al-Zr base intermetallic compound overgrowth then, thus make anode oxide film present dark color.
In order to obtain better properties, the weight percent content of Zr is preferably in 1.5% to 2.5%.
Mm has such effect, that is, add the intermetallic compound that a spot of Mm can cause having high rigidity and separate out in a large number, to improve the hardness of aluminium alloy.Yet if the crystal grain of the intermetallic compound of separating out is excessive, the anode oxide film that the anodic oxidation by aluminium alloy produces will present dark color.Therefore, less by the crystal grain that makes the intermetallic compound of separating out, the color of anode oxide film can be made canescence.
In aluminium alloy of the present invention, it is in 0.1% to 15% the scope that the content of Mm is set at weight percent.If the weight percent content of Mm less than 0.1%, then can not obtain to add the effect of Mm.If the weight percent content of Mm is greater than 15%, then intermetallic compound growth is excessive, thereby makes anode oxide film present dark color.
In order to obtain better properties, the weight percent content of Mm is preferably in 4.0% to 5.0%.
Mg has such effect, that is, it forms a large amount of supersaturated solid solutions in alpha-aluminum, to improve hardness.
In aluminium alloy of the present invention, it is in 0.1% to 5% the scope that the content of Mg is set at weight percent.If the weight percent content of Mg less than 0.1%, then can not obtain to add the effect of Mg.If the weight percent content of Mg is greater than 5%, then anode oxide film presents dark color.
In order to obtain better properties, the weight percent content of Mg is preferably in 4.0% to 5.0%.
Also with polishing or similar method its surface is polished subsequently if the aluminium alloy with above-mentioned composition is carried out hot moulding, then can easily obtain metalluster on the surface of this aluminium alloy.
In the present invention, aluminum matrix alloy preferably also comprises at least a metallic element that chooses from one group of metallic element being made up of Mo, W, Nb, Ag and Ta, and its weight percent content is 0.1% to 5%.
Mo, W, Nb, Ag and Ta have such effect, that is, add the intermetallic compound that these metallic elements can cause having high rigidity on a small quantity and separate out in a large number, to improve the hardness of aluminium alloy.Yet if the crystal grain of the intermetallic compound of being separated out is excessive, the anode oxide film that the anodic oxidation by aluminium alloy produces will present dark color.Therefore, the crystal grain of the intermetallic compound of separating out by making is less, the color of anode oxide film can be made pastel shade.
As mentioned above, the weight percent content of the metallic element of these interpolations is 0.1% to 5%.If the weight percent content of these elements less than 0.1%, then can not obtain to add the effect of these elements.If the weight percent content of these elements is greater than 5%, then the intermetallic compound growth of being separated out is excessive, thereby makes anode oxide film present dark color.
As mentioned above, the inventor has been found that according to a first aspect of the invention composition makes the hardness of matrix improve, and make that anode oxide film is transparent and it is colourless to be, linen or argenteous.More particularly, the hardness HRB of aforesaid alloy matrix aluminum of the present invention (the B scale of Rockwell hardness) can reach 50-100, and the brightness of anode oxide film (L*) can reach 50 or higher.
Therefore, according to second aspect, the invention provides a kind of ornamental aluminium alloy element, it comprises matrix that is made of aluminium alloy and the anode oxide film that forms on this matrix surface, wherein, the hardness HRB of matrix (the B scale of Rockwell hardness) is 50-100, and the brightness of anode oxide film (L*) is 50 or higher.
According to a second aspect of the present invention, hardness HRB is 50-100.Impaired like this, in process of production fraction defective can be much smaller than according to the fraction defective under the situation of for example existing molten aluminium alloy of JIS A5052.Furtherly, the brightness of anode oxide film (L*) is 50 or higher.Like this, can obtain required color and can not be subjected to the influence of the primitive color tone of anode oxide film.
Brightness here (L*) is the brightness in the defined L*a*b* color specification system in JIS Z8729, and it utilizes spectrographic technique to measure by means of colourimeter.Employed light source is D65 (International Commission on Illumination, an iso standard light) in measurement, and its colour temperature is 6504K.
According to a second aspect of the present invention, the hardness of described matrix is set in the scope of 50-100.If this hardness is less than 50, then aluminium alloy element is easy to be damaged.If this hardness is greater than 100, then its limit jumping-up rate and unit elongation (describing hereinafter) under room temperature (20 ℃) will reduce.
In the present invention, the electroconductibility of described matrix 20%IACS or higher preferably.
The inventor has been found that, when the electroconductibility of this matrix is higher, the solid solution scale of construction of matrix element that enters into anode oxide film is less, thereby the color that makes anode oxide film becomes colorless or light color, the inventor also finds, for the color that makes anode oxide film becomes colorless or becomes pastel shade, the electroconductibility of this matrix must be 20%IACS or higher.And the inventor has been found that the electroconductibility of the matrix in the aluminium alloy element of the present invention can be changed into 20%IACS or higher.Because the electroconductibility of matrix in aluminium alloy element of the present invention can be changed into 20%IACS or higher, thus anode oxide film become colorless or become light tone.In addition, the present invention can be applicable to the occasion to matrix requirement high conductivity.
Still in second aspect, anode oxide film is preferably transparent and colourless, linen or argenteous.
Like this, aluminium alloy element of the present invention is very suitable for as such ornament, that is, this ornament requires to have light tone.
In the present invention, the aluminium alloy that constitutes matrix preferably has 70% or higher limit jumping-up rate under 200 ℃-600 ℃ temperature, at room temperature preferably has 10% or higher unit elongation.This makes and just can obtain complicated shape at an easy rate by hot-work once or twice under 200 ℃-600 ℃ temperature.
If limit jumping-up rate less than 70% or unit elongation at room temperature less than 10% situation under, under 200 ℃-600 ℃ temperature, obtain complicated shape by hot-work once or twice, crackle then can appear processing.
Described limit jumping-up rate is such upsetting ratio, that is, when thermosetting base substrate of upsetting under the 0.5mm/ forging speed of second, the edge section of this solidified base substrate begins to split under described jumping-up rate.Described jumping-up rate (L 0-L 1)/L 0* 100 (%) represent, L wherein 0Represent sample length along the upsetting direction before upsetting, L 1Represent this sample length along the upsetting direction after upsetting.
In the present invention, preferably, in the metallic crystalline structure of the aluminium alloy that constitutes matrix, aluminium crystalline average grain size is 500nm or littler, and the average grain size of intermetallic compound is 300nm or littler.This makes it possible to the hardness HRB of this matrix is arranged on 50-100, and feasible (mold pressing) better performances of forging.
If aluminium crystalline average grain size surpasses the average grain size of 500nm or intermetallic compound and surpasses 300nm, then the ductility of this aluminium alloy and limit jumping-up rate are improved, but hardness reduces.
In the present invention, the preferably parts or the household electrical appliance parts of exterior part, ornament or the electric installation of wrist-watch of ornamental aluminium alloy element.
According to the present invention, the method of producing ornamental aluminium alloy element may further comprise the steps: (a) form a mold pressing base substrate of being made by the aluminium alloy that comprises following component content, the component content of described aluminium alloy is: weight percent is that 0.1% to 3% Zr, weight percent are that 0.1% to 15% Mm, weight percent are 0.1% to 5% the Mg and the Al of remainder; (b) under temperature rise rate is 2 ℃/second or higher condition, this mold pressing base substrate is heated to 200 ℃-600 ℃; (c) process the mold pressing base substrate that this has heated; And (d) finished mold pressing base substrate is carried out anodic oxidation treatment.
According to the present invention, use aluminium alloy with above-mentioned composition, thereby can mold pressing have good moldability aluminium alloy, obtain high hardness and make the tone of anode oxide film be light color.
Surpass 600 ℃ or temperature rise rate less than 2 ℃/second if heat the temperature of this mold pressing base substrate, then in the crystalline structure of the aluminium alloy of this hot-work after, its aluminium grain or its intermetallic compound growth are excessive, thereby make its hardness reduction.If the temperature that heats this mold pressing base substrate is less than 200 ℃, then the adhesion to each other of solidified powder becomes insufficient rapidly, thereby aluminium alloy becomes frangible, causes limit jumping-up rate and the unit elongation under the room temperature in 200-600 ℃ of scope to reduce.Usually from room temperature this mold pressing base substrate is heated to described temperature.
In order to obtain better properties, the temperature range that heats this mold pressing base substrate is preferably 350-450 ℃.Preferably 400 ℃ of employed in this case die temperatures.
In the method for the invention, step (a) preferably includes the step of the quick-setting powder of an extruded aluminium alloy.This can make the aluminium crystal in the crystalline structure of aluminium alloy and the grain-size refinement of intermetallic compound.
In the method for the invention, step (c) preferably includes a mold pressing base substrate that will heat and is thermally processed into curing powder and subsequently this curing powder is carried out hot worked step.This makes and just can obtain complicated shape at an easy rate by processing once or twice.
In the method for the invention, preferably rod or plate shape of formed mold pressing base substrate.This makes it possible to select rightly the shape of described mold pressing base substrate.
In the method for the invention, step (b) preferably includes the step that a mode with induction heating is come the heating and mould pressing base substrate, and the time of heating this mold pressing base substrate is in one minute.This makes it possible to suppress the growth of crystal grain in the crystalline structure of aluminium alloy.
In the method for the invention, preferably the mode of in the process of step (c) the mold pressing base substrate that has heated being processed is hot moulding, and the mold pressing number of times is for 2 times or still less.
The composition of aluminium alloy of the present invention makes it possible to only just described aluminium alloy to be processed into complicated shape by processing once or twice.
In the method for the invention, above-mentioned 2 mold pressings preferably are divided into twice such mold pressing, that is, mold pressing for the first time is to make the profile of mold pressing base substrate reach net shape substantially, and mold pressing for the second time then is that shallow mold pressing is carried out on the surface of this mold pressing base substrate.This makes just can give aluminium alloy a shape by a spot of mold pressing number of times, and can decorate this aluminium alloy element with literal, pattern or similar mark.
In the method for the invention, the processing of in step (c) the mold pressing base substrate that heats being carried out preferably includes the mold pressing first time that the profile that makes the mold pressing base substrate reaches net shape substantially, and the mold pressing second time of the surface of mold pressing base substrate being carried out shallow mold pressing, mold pressing for the first time is hot moulding, and mold pressing for the second time is cold forming.Like this, just can give aluminium alloy a kind of profile, and can decorate it with letter, pattern or analogue by the mold pressing of a small amount of number of times.
In the method for the invention, step (d) preferably includes encapsulation process, and when encapsulation process, can adopt pressure steam sealing method or nickel acetate sealing method.By this encapsulation process, can improve the antiseptic property of anode oxide film.
In the method for the invention, step (d) preferably includes painted processing, and when painted processing, can adopt dyeing process, natural coloration method or electrolytic coloring method.This painted processing makes it possible to the antianode oxide film and carries out painted.
With reference to accompanying drawing, will present invention is described by hereinafter embodiment.
Fig. 1 is the partial section according to the watch case 10 of an example as ornamental aluminium alloy element of the present invention.Watch case 10 comprises the main body 1 and the anode oxide film 2 that are made of matrix or mold pressing base substrate, and described matrix or mold pressing base substrate are made by aluminium alloy, and the whole surface of main body 1 is all covered by anode oxide film 2.
As mentioned above, the composition that constitutes the aluminium alloy of main body 1 comprises that weight accounts for 0.1% to 3% Zr, weight and accounts for 0.1% to 15% Mm, weight and account for 0.1% to 5% the Mg and the Al of remainder.As mentioned above, the aluminium alloy of formation main body 1 comprises also that preferably weight accounts for 0.1% to 5% at least a metallic element of selecting from Mo, W, Nb, Ag and Ta one group element.
The hardness HRB of main body 1 is 50 to 100.The brightness of anode oxide film 2 (L*) is 50 or higher.The electroconductibility of main body 1 is 20%IACS or higher preferably.Anode oxide film 2 is preferably transparent or colourless, linen or argenteous.
For main body 1, preferably its limit jumping-up rate under the temperature from 200 ℃ to 600 ℃ is 70% or higher, and the unit elongation under the room temperature is 10% or higher.
For the aluminium alloy crystalline structure that constitutes main body 1, the average grain size of aluminium grain is 500nm or littler preferably, and the average grain size of intermetallic compound is 300nm or littler.
Use description to make the method for watch case shown in Figure 1 10 below.
Fig. 2 to Fig. 9 has represented to be used for to make each step of the method for watch case successively.At first, referring to Fig. 2, ready quick-setting Al alloy powder is arranged, it comprises that weight accounts for 0.1% to 3% Zr, weight and accounts for 0.1% to 15% Mm, weight and account for 0.1% to 5% the Mg and the Al of remainder.This quick-setting powder is squeezed into bar or the plate of being made by aluminium alloy.This bar or plate are cut into suitable size just made columniform bullet shape body 3.
Referring to Fig. 3, to use the load coil 4 that links to each other with power supply will play shape body 3 by induction heating in a short period of time and be heated to 460 ℃, described power supply can be regulated the electric energy and the service time of supply.The induction frequencies that is applied is 1KHz.Short period of time described here was preferably in one minute.The electric energy of input can be regulated in the following manner, i.e. heating can for example be finished in 10 seconds.
Referring to Fig. 4, the bullet shape body of described induction heating is placed in the hot pressing die of being made up of drift 5 and punch die 6, is pressed into the final mold pressing shape of watch case then by the friction press that can apply 150 tons of pressure.In this manner, just made the molded product 1 that forms main body.This mold pressing operation is only carried out once.Described hot moulding mould is heated to 200 ℃ by well heater.
Have following metallic crystalline structure at the preoperative aluminium alloy of this hot moulding, promptly wherein aluminium crystalline grain-size is 500nm or littler, and the grain-size of the intermetallic compound of separating out is 300nm or littler.Therefore, by the viscous deformation under the high temperature, under the indeformable situation of these crystal grain the slip of grain boundary can take place.This makes and reaches 70% or bigger in the limit jumping-up rate under 200 ℃ to 600 ℃ temperature.Therefore, above-mentioned hot moulding makes aluminium alloy can be only just be moulded to the net shape of watch case by extruding once.
Referring to Fig. 5, the redundance 1A of molded product 1 is cut in the deburring step to be fallen.
Referring to Fig. 6, to form assembled portion 1a and 1b, the glass and the moving parts that are assembled on the wrist-watch can be assemblied on described assembled portion 1a and the 1b molded product 1 by turning.
Referring to Fig. 7, molded product 1 is processed to form the hole 1c that is used to install knob, button or analogue.
Referring to Fig. 8, more attractive in appearance for the final surface that makes watch case, adopt 7 pairs of surfaces of polishing machine to polish.Has meticulous metallic crystalline structure owing to constitute the aluminium alloy of molded product 1, so just can reach enough surface smoothnesses by slight relatively polishing.
Referring to Fig. 9, molded product 1 is cleaned to remove greasy dirt with organic solvent.Next, in order to reach final smooth finish, available chemical rightenning or electrolytic polishing method are handled molded product 1.In order to reach frosted finish, the available hydrogen sodium oxide carries out hair side to molded product 1 to be handled.
Each the step all finish after, to molded product 1 carry out anodic oxidation treatment with on the whole surface of molded product 1 formation anode oxide film 2.This anodic oxidation treatment is performed such, and for example, forms and has the anode oxide film that thickness is 15 μ m by adopting the thiosulfonic acid method to carry out electrolysis.In the thiosulfonic acid method, for example, the thiosulfonic acid of employing 15% is as bath composition and adopt following condition.Electrolysis temperature: 20 ℃, strength of current: 1.5A/dm 3, and electrolysis time: 60 minutes.Also can adopt oxalic acid to replace sulfuric acid to carry out anodic oxidation treatment.In this case, can obtain higher wear resisting property.But final film is shown as yellow.Therefore, this oxalic acid treatment is more suitable for dying the golden product, and can not be used for dying the product for other color.
Under the situation that adopts existing molten aluminium alloy, the exterior part of wrist-watch often will pass through low temperature anodic oxidation treatment (being so-called herdamite processing) so that its surface hardening and improve wear resistance.And in the present invention, expectation adopts common thiosulfonic acid method (treatment temp: 20 ℃) to carry out anodic oxidation.In the present invention, aluminium alloy has above-mentioned meticulous metallic crystalline structure, so that aluminium alloy at room temperature has high intensity, hardness and toughness.Therefore, in the present invention, even without adopting low temperature anode oxide film (being the herdamite film), aluminium alloy also can be used as the exterior part of wrist-watch satisfactorily.
Stand in the wear resistant exterior part for wristwatch of existing molten aluminium alloy of low temperature anodic oxidation treatment (be so-called herdamite handle) the about at most 20um of oxide thickness that forms through handling in employing.Therefore, this aluminium alloy is more easily by outside destroy.The present invention has overcome this problem, because the hardness of aluminum alloy materials itself is very high.Certainly, clearly, if aluminium alloy of the present invention has passed through the low temperature anodic oxidation treatment, then from the intensity aspect, this aluminium alloy can be made better wear resistant exterior part for wristwatch.
Mold pressing base substrate 1 through anodic oxidation treatment can be selected to carry out painted.Painted in order to carry out, can adopt dyeing process, natural coloration method or electrolytic coloring method.Concerning the exterior part of wrist-watch, because they are decorations, so often need pastel shade.On the other hand, also require them to have the ability that adapts to weather, for example antiultraviolet.Color in order to form this light color, staining is the best approach of industrial employing.But some dyestuff, particularly organic dye do not have the ability of abundant adaptation weather.In this case, the normal dyestuff of selecting to have from inorganic dyestuff with the required color similar color carries out that the first time is painted, and described inorganic dyestuff has sufficient adaptation weather ability, but its color category is limited; In for the second time painted, from organic dye, select suitable dyestuff then to form required color with multiple color.It is minimum that fading of like this, just ultraviolet radiation can being caused drops to.
After this, anode oxide film 2 through encapsulation process to improve wear resistance.When this encapsulation process, for example adopt pressure steam sealing method or nickel acetate sealing method.The pressure steam sealing method is following treatment process: water cleans and has passed through the product of anodic oxidation treatment, this product is put into pressure kettle, and make product wherein be in 3-5kg/cm 2Steam (steam) pressure under 20-30 minute so that the hole on the film of sealing after the anodizing.In the present embodiment, product was maintained in the steam under the 0.5MPa pressure 15 minutes, to fill those holes.
The nickel acetate Sealing Method is that anode oxide film is immersed in the nickel acetate aqueous solution to seal the treatment process of hole.
In the above-described embodiments, invention has been described with reference to the watch case 10 as ornamental aluminium alloy element.But the present invention is not limited to this embodiment, but can be applied to: other exterior part of wrist-watch, for example wrist-watch strap, housing and backboard; Other decoration, for example bracelet, ring and tiepin; Electronic equipment part, for example notebook computer; The household electrical appliance parts; Vehicle part, for example parts of automobile and train.
Incidentally, can only by the following first step and second step bullet shape body 3 that has heated shown in Figure 3 be molded into the finished product, promptly as shown in Figure 4, mold pressing for the first time will play shape body 3 and be molded into net shape, and mold pressing for the second time is its surface of shallow pressure.Mold pressing for the second time is used to make the bullet shape body 3 of mold pressing to decorate letter, pattern or analogue.In this case, as preferably hot moulding of the described mold pressing first time of reference Fig. 4.Mold pressing for the second time can be cold forming or hot moulding.
Advantage of the present invention will more clearly embody by following example of the present invention and comparative examples.
Here adopted a gas atomization device to produce Al alloy powder, described Al alloy powder has the alloy composition shown in the following table 1 (example 1-14 and comparative examples 1-10).In order to atomize, nitrogen pressure is arrived 100kgf/cm 2And be ejected on the molten aluminium alloy that falls from nozzle, described nozzle has the hole that diameter is 2mm.Also can adopt rare gas elementes such as argon gas to replace nitrogen.
With above-mentioned same atomization condition under, produce 2014 Al alloy powders, estimate actual rate of cooling by the spacing between the crystallization branch (ingotism body) of measuring the powder crystal structure then.The result is, when the powder of the grain-size that obtains to have 150um, its rate of cooling is 1 * 10 3℃/second.
Secondly, have less than the powder of 150um size and from each Al alloy powder of above-mentioned formation, separate by filter screen.Each Al alloy powder is carried out mold pressing, then to the mold pressing base substrate with 2 ℃/second or faster temperature rise rate be heated to 350 to 550 ℃ of temperature in the scope, outgas simultaneously.After this, the mold pressing base substrate is inserted into die cavity under 400 ℃ temperature, then at 9 tons/cm 2Surface pressure solidify down.The curing powder of Zhi Zaoing detects through crystalline structure performance and mechanical property more under these conditions.
The crystalline structure of curing powder detects by high-resolution SEM photographic camera.As shown in table 1, the result has proved that in all examples 1 to 14 aluminium crystalline average grain size is 500nm or littler, and the average grain size of intermetallic compound is 300nm or littler.
In order to study the forging property of these curing powders, their limit jumping-up rates under 400 ℃ have been detected.Shown in following table 2, the result has proved that all examples 1 to 14 all have 70% or bigger limit jumping-up rate, thereby demonstrates excellent forging property.
Then process the surface of curing powder.After this,, then carry out anodizing, become 10um up to the thickness of final anodizing film with corrodibility soda water flushing curing powder.The color harmony smooth finish of the aluminium after the anodizing is detected.As shown in table 2, the result has proved that the color of the aluminium film (anode oxide film) after the anodizing in all examples 1 to 14 all is light, i.e. silvery white, canescence, light yellow or light grey.And these films all have gloss.
The crystalline structure of the boundary vicinity between anode aluminium film and the base phase is detected by high definition SEM photographic camera.From the reflected electron image of this crystalline structure, find in anode aluminium film, intermetallic compound is arranged, but amount seldom.Promptly very clear, if the amount of the intermetallic compound in the anode aluminium film is very little, then the tone of anode aluminium film will become light color coloured silk, for example silvery white or canescence.Also very clear, color in order to obtain light color, the area ratio of the intermetallic compound on the per unit area must be 20% or still less.
Relativeness between the tone of the electroconductibility of matrix and anode aluminium film is detected.The result is that clearly, when obtaining such as light color such as silvery white or canescence, electroconductibility is 20%IACS or bigger, and is as shown in table 2.Relativeness between the hue and luminance (L*) of anode aluminium film is detected.The result is that clearly, in order to obtain light color, the brightness (L*) of anode aluminium film is 50 or bigger, and is as shown in table 2.
In all examples 1 to 14, their parent phase hardness HRB is 50 to 100 under room temperature (20 ℃), and the unit elongation under room temperature (20 ℃) is 10% or bigger.
On the other hand, the result of comparative examples is as follows.
Comparative examples 1 to 3 is such two kinds of situations, and promptly the temperature rise rate when the heating and mould pressing base substrate is lower than 2 ℃/second, and Heating temperature is higher than 600 ℃.In both cases, in the crystalline structure of curing powder, their aluminium grain and intermetallic compound have been grown up after the hot-work.Like this, their hardness reduces greatly.
In comparative examples 2, the Heating temperature of mold pressing base substrate is lower than 200 ℃.In this case, it is higher relatively that hardness becomes, dull but the tone of anode aluminium film becomes.
In comparative examples 4, the weight percent of Zr is higher than 3%.In this case, it is bigger that intermetallic compound becomes, and the quantitative change of the compound of separating out gets very big so that its hardness increases.But unit elongation under the room temperature and the limit jumping-up rate under the high temperature have reduced.Remaining intermetallic compound is still stayed in the anode aluminium film of anodic oxidation treatment.Like this, the tone of anode aluminium film becomes dull.
In comparative examples 5, the weight percent content of Mm is higher than 15%.In this case, intermetallic compound is grown up, and the quantitative change of the compound of separating out gets very big so that its hardness increases.But unit elongation under the room temperature and the limit jumping-up rate under the high temperature have reduced.A large amount of intermetallic compounds makes remaining intermetallic compound still stay in the anode aluminium film of anodic oxidation treatment.Like this, the tone of anode aluminium film becomes dull.
In comparative examples 6, the weight percent content of Mg is higher than 5%.In this case, intermetallic compound is grown up, and the quantitative change of the compound of separating out gets very big so that its hardness increases.But unit elongation under the room temperature and the limit jumping-up rate under the high temperature have reduced.A large amount of intermetallic compounds makes remaining intermetallic compound still stay in the anode aluminium film of anodic oxidation treatment.Like this, the tone of anode aluminium film becomes dull.
In comparative examples 7 to 9, the weight percent content of Mo or W is higher than 5%.In these cases, the tone of anode aluminium film also becomes dull.
In comparative examples 10, the weight percent content of Zr is lower than 0.1%.In this case, aluminium grain has been grown up, thereby its hardness is reduced.
As mentioned above, in example 1 to 14, adopted aluminium alloy (Zr: weight from 0.1% to 3% with composition as shown in table 1; Mm: weight from 0.1% to 15%; Mg: weight from 0.1% to 3%; Remaining is Al), and the condition that is used for the heating and mould pressing base substrate shown in the employing table 1 (Heating temperature: 200 ℃ or higher, but at 600 ℃ or following; Temperature rise rate: 2 ℃/second or higher).Therefore, might obtain having high rigidity, the ornamental aluminium alloy of light anode aluminium film and good formability.
As mentioned above, ornamental aluminium alloy element of the present invention can be moulded to complicated shape at an easy rate.Its matrix has very high hardness, and its film color through anodizing is bright.
Top the disclosed embodiments and example only are schematic and nonrestrictive.Scope of the present invention should not be limited to above-mentioned disclosed content and should be determined by claim.The present invention includes the equivalent way of all modification and claim.
Table 1
Curing powder Form (weight ratio %) The heating condition of mold pressing base substrate The Al grain-size The intermetallic compound size
Reach temperature Temperature rise rate
Example 1 Al-2Zr-8Mm-4Mg 400℃ 10 ℃/second 500nm 200nm
2 300℃ 10 ℃/second 400nm 200nm
3 550℃ 10 ℃/second 500nm 300nm
4 400℃ 5 ℃/second 500nm 300nm
5 Al-3Zr-13Mm-3Mg 400℃ 10 ℃/second 500nm 300nm
6 Al-1Zr-4.5Mm-1Mg 400℃ 10 ℃/second 500nm 300nm
7 Al-3Zr-13.5Mm-2Mg 400℃ 10 ℃/second 400nm 250nm
8 Al-2Zr-9Mm-2Mg-3Mo 350℃ 10 ℃/second 500nm 300nm
9 Al-2Zr-6Mm-2Mg-3Nb 400℃ 10 ℃/second 450nm 300nm
10 Al-2Zr-5Mm-3Mg-2Ag 350℃ 10 ℃/second 300nm 200nm
11 Al-3Zr-5Mm-4Mg-2W 400℃ 10 ℃/second 500nm 300nm
12 Al-3Zr-6Mm-4Mg-2Ta 400℃ 10 ℃/second 500nm 200nm
13 Al-3Zr-13.5Mm-2Mg 400℃ 10 ℃/second 400nm 300nm
14 Al-3Zr-5Mm-2Mg-2Ag 400℃ 10 ℃/second 500nm 200nm
Comparative examples 1 Al-2Zr-8Mm-4Mg 400℃ 0.5 ℃/second 1100nm 300nm
2 150℃ 10 ℃/second 300nm 200nm
3 620℃ 10 ℃/second 1800nm 600nm
4 Al-5Zr-8Mm-4Mg 400℃ 10 ℃/second 500nm 300nm
5 Al-1Zr-16Mm-4Mg 400℃ 10 ℃/second 500nm 800nm
6 Al-2Zr-5Mm-10Mg 400℃ 10 ℃/second 500nm 200nm
7 Al-2Zr-9Mm-3Mg-7Mo 400℃ 10 ℃/second 500nm 700nm
8 Al-2Zr-21Mm-3Mg-7Mo 400℃ 10 ℃/second 500nm 1000nm
9 Al-2Zr-8Mm-2Mg-10W 400℃ 10 ℃/second 500nm 800nm
10 Al-0.06Zr-8Mm-4Mg 400℃ 10 ℃/second 3500nm 200nm
Table 2
Curing powder Hardness under the room temperature (HRB) Unit elongation under the room temperature (%) The jumping-up temperature (℃) Limit jumping-up rate (%)
Example 1 84 11 400 88
2 88 10 300 80
3 78 14 300 85
4 80 13 300 85
5 75 13 400 81
6 71 20 400 90
7 84 14 400 85
8 88 12 500 92
9 91 10 500 88
10 88 14 400 80
11 91 13 400 80
12 90 13 400 85
13 84 14 400 85
14 86 11 400 81
Comparative examples 1 45 16 400 90
2 91 1 400 60
3 49 20 400 91
4 60 12 400 85
5 75 13 400 88
6 94 10 400 75
7 91 8 400 69
8 91 2 400 50
9 90 5 400 62
10 41 23 400 95
(continuation)
Table 2
Curing powder The tone of anodizing film Electroconductibility (%IACS) The brightness of anodizing film (L*)
Example 1 Silvery white 24.5 78.6
2 Greyish white 23.0 66.2
3 Silvery white 25.5 76.6
4 Silvery white 27.0 73.8
5 Pale yellow 26.5 58.6
6 Pale yellow 24.0 55.1
7 Pale yellow 24.5 56.2
8 Greyish white 20.0 66.1
9 Greyish white 21.0 64.9
10 Greyish white 21.5 69.2
11 Greyish white 24.0 63.0
12 Greyish white 22.0 64.2
13 Greyish white 26.5 56.7
14 Silvery white 29.7 75.2
Comparative examples 1 Silvery white 25.0 77.1
2 Dull gray 11.0 41.2
3 Silvery white 30.0 74.9
4 Dull gray 15.0 36.2
5 Dull gray 16.0 39.5
6 Dull gray 13.0 42.8
7 Dull gray 11.0 38.5
8 Dull gray 12.0 36.7
9 Dark palm fibre 13.0 33.2
10 Silvery white 29.0 74.6

Claims (18)

1.一种装饰用的铝合金构件，其特征在于，它包括：1. A decorative aluminum alloy member, characterized in that it comprises: 一个由铝合金制成的基体，所述铝合金包含重量百分比为0.1％至3％的Zr、重量百分比为0.1％至15％的Mm、重量百分比为0.1％至5％的Mg和剩余部分的Al；以及A substrate made of an aluminum alloy comprising 0.1 to 3% by weight of Zr, 0.1 to 15% by weight of Mm, 0.1 to 5% by weight of Mg and the remainder of Al; and 在该基体表面上形成的一层阳极氧化膜。An anodized film formed on the surface of the substrate. 2.一种装饰用的铝合金构件，其特征在于，它包括一个由铝合金制成的基体和在该基体表面上形成的一层阳极氧化膜；2. A decorative aluminum alloy member, characterized in that it comprises a substrate made of aluminum alloy and an anodized film formed on the surface of the substrate; 其中，所述基体的硬度HRB为50至100，所述阳极氧化膜的亮度为50或更高。Wherein, the hardness HRB of the substrate is 50 to 100, and the brightness of the anodized film is 50 or higher. 3.根据权利要求1或2所述的装饰用的铝合金构件，其特征在于，所述基体还包括重量百分比为0.1％至5％的、从Mo、W、Nb、Ag和Ta一组元素中选出的至少一种金属元素。3. The aluminum alloy component for decoration according to claim 1 or 2, wherein the matrix further comprises a group of elements from Mo, W, Nb, Ag and Ta in a weight percentage of 0.1% to 5%. At least one metal element selected from 4.根据权利要求1或2所述的装饰用的铝合金构件，其特征在于，所述基体导电性为20％IACS或更高。4. The decorative aluminum alloy member according to claim 1 or 2, characterized in that the electrical conductivity of the matrix is 20% IACS or higher. 5.根据权利要求1或2所述的装饰用的铝合金构件，其特征在于，所述阳极氧化膜是透明和无色、灰白色或银白色的。5. The decorative aluminum alloy member according to claim 1 or 2, characterized in that the anodized film is transparent and colorless, off-white or silver-white. 6.根据权利要求1或2所述的装饰用的铝合金构件，其特征在于，构成基体的所述铝合金在200℃至600℃的温度下的极限镦粗率是70％或更高，在20℃下的延伸率是10％或更高。6. The aluminum alloy member for decoration according to claim 1 or 2, wherein the aluminum alloy constituting the matrix has an ultimate upsetting rate of 70% or higher at a temperature of 200°C to 600°C, and at The elongation at 20°C is 10% or more. 7.根据权利要求1或2所述的装饰用的铝合金构件，其特征在于，所述铝合金的金属晶体结构包括铝晶体和金属间化合物，铝晶体的平均晶粒尺寸是500nm或更小，而金属间化合物的平均晶粒尺寸是300nm或更小。7. The decorative aluminum alloy member according to claim 1 or 2, characterized in that the metal crystal structure of the aluminum alloy includes aluminum crystals and intermetallic compounds, and the average grain size of the aluminum crystals is 500 nm or less , while the average grain size of the intermetallic compound is 300 nm or less. 8.根据权利要求1或2所述的装饰用的铝合金构件，其特征在于，它是手表的一个外部零件、一个装饰件或一个用于电子设备或家用电器的部件。8. The aluminum alloy member for decoration according to claim 1 or 2, characterized in that it is an exterior part of a watch, a decorative part or a component for electronic equipment or household appliances. 9.一种生产装饰用的铝合金构件的方法，其特征在于，它包括以下步骤：9. A method for producing an aluminum alloy component for decoration, characterized in that it comprises the following steps: (a)形成一个由具有以下成份含量的铝合金制成的模压坯体，所述铝合金的成份含量为：重量百分比为0.1％至3％的Zr、重量百分比为0.1％至15％的Mm、重量百分比为0.1％至5％的Mg和剩余部分的Al；(a) forming a molded body made of an aluminum alloy having a composition content of: 0.1% to 3% by weight of Zr, and 0.1% to 15% by weight of Mm , 0.1% to 5% by weight of Mg and the remainder of Al; (b)在温升率为2℃/秒或更高的条件下将该模压坯体加热到200℃至600℃的温度；(b) heating the molded body to a temperature of 200°C to 600°C at a temperature rise rate of 2°C/sec or more; (c)加工已加热的模压坯体；以及(c) processing the heated molded body; and (d)对加工过的模压坯体进行阳极氧化处理。(d) Anodizing the processed molded body. 10.根据权利要求9所述的方法，其特征在于，所述步骤(a)包括一个模压所述铝合金的快速固化的粉末的步骤。10. The method of claim 9, wherein said step (a) includes a step of molding said fast solidifying powder of said aluminum alloy. 11.根据权利要求9或10所述的方法，其特征在于，所述步骤(c)包括这样一个步骤，即将加热的模压坯体热加工成固化粉末，随后热加工固化的粉末。11. The method according to claim 9 or 10, wherein said step (c) comprises a step of thermally processing the heated molded body into a solidified powder, followed by thermal processing of the solidified powder. 12.根据权利要求9或10所述的方法，其特征在于，所述模压坯体成型为具有杆状或板状的形状。12. The method according to claim 9 or 10, characterized in that the molded body is shaped to have a rod-like or plate-like shape. 13.根据权利要求9或10所述的方法，其特征在于，所述步骤(b)包括这样一个步骤，即通过感应加热来对模压坯体进行加热，用于加热模压坯体的时间在一分钟以内。13. The method according to claim 9 or 10, wherein said step (b) includes a step of heating the molded body by induction heating, and the time for heating the molded body is within a within minutes. 14.根据权利要求9或10所述的方法，其特征在于，对加热的模压坯体的加工操作是热模压，模压次数是2次或更少。14. The method according to claim 9 or 10, characterized in that the processing operation on the heated molded body is hot molding, and the number of times of molding is 2 or less. 15.根据权利要求9或10所述的方法，其特征在于，2次模压是这样进行的，即第一次模压将模压坯体的外形压成一个大体上的最终形状，第二次模压是对模压坯体的表面进行浅模压。15. according to the described method of claim 9 or 10, it is characterized in that, 2 times molding is carried out like this, promptly the first time molding presses the profile of molded green body into a substantially final shape, and the second time molding is Shallow embossing is performed on the surface of the molded body. 16.根据权利要求9或10所述的方法，其特征在于，对已加热的模压坯体的所述加工操作包括：将模压坯体的外形压成一个大体上的最终形状的第一次模压，和对模压坯体的表面进行浅模压的第二次模压：16. Method according to claim 9 or 10, characterized in that said working operation of the heated molded body comprises a first molding which presses the contour of the molded body into a substantially net shape , and a second overmolding that shallowly overmoldes the surface of the molded body: 所述第一次模压是热模压，所述第二次模压是冷模压。The first molding is hot molding, and the second molding is cold molding. 17.根据权利要求9或10所述的方法，其特征在于，所述步骤(d)包括密封处理，并且在密封处理时，采用了压力蒸汽密封方法或醋酸镍密封方法。17. The method according to claim 9 or 10, characterized in that the step (d) includes sealing treatment, and during the sealing treatment, a pressure steam sealing method or a nickel acetate sealing method is used. 18.根据权利要求9或10所述的方法，其特征在于，所述步骤(d)包括着色处理，并且在着色处理时，采用了染色方法、自然显色方法或电解着色方法。18. The method according to claim 9 or 10, characterized in that the step (d) includes coloring treatment, and during the coloring treatment, a dyeing method, a natural coloring method or an electrolytic coloring method is used.
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EP0778158A1 (en) * 1995-12-04 1997-06-11 Bayer Corporation Lithographic printing plates having a smooth, shiny surface

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI753264B (en) * 2018-06-28 2022-01-21 瑞士商柯瑪豆股份有限公司 Decorative parts and method for manufacturing the same

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CN1254028A (en) 2000-05-24
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JP2000144489A (en) 2000-05-26

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