CN1254028A - Decorative aluminium alloy member and its production method - Google Patents
Decorative aluminium alloy member and its production method Download PDFInfo
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- CN1254028A CN1254028A CN 99122168 CN99122168A CN1254028A CN 1254028 A CN1254028 A CN 1254028A CN 99122168 CN99122168 CN 99122168 CN 99122168 A CN99122168 A CN 99122168A CN 1254028 A CN1254028 A CN 1254028A
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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
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- 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
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- 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
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- 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
Abstract
An ornamental aluminum alloy member (10) has a substrate (1) made of an aluminum alloy, and an anodic oxidation film (2) formed on a surface of the substrate. The aluminum alloy forming the substrate (1) contains from 0.1% to 3% by weight of Zr, from 0.1% to 15% by weight of Mischmetal (Mm), from 0.1% to 5% by weight of Mg, and the rest of Al.
Description
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 A5052-0, 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-2?1Mm-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. ornamental aluminium alloy element is characterized in that it comprises:
It 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 that a matrix of being made by aluminium alloy, described aluminium alloy comprise weight percent; And
One deck anode oxide film that on this matrix surface, forms.
2. an ornamental aluminium alloy element is characterized in that, it comprises a matrix of being made by aluminium alloy and one deck anode oxide film that forms on this matrix surface;
Wherein, the hardness HRB of described matrix is 50 to 100, and the brightness of described anode oxide film is 50 or higher.
3. ornamental aluminium alloy element according to claim 1 and 2 is characterized in that, described matrix comprises that also weight percent is an at least a metallic element 0.1% to 5%, that select from Mo, W, Nb, Ag and Ta one group element.
4. ornamental aluminium alloy element according to claim 1 and 2 is characterized in that, described matrix electroconductibility is 20%IACS or higher.
5. according to the described ornamental aluminium alloy element of arbitrary claim in the claim 1 to 4, it is characterized in that described anode oxide film is transparent and colourless, canescence or argenteous.
6. according to the described ornamental aluminium alloy element of arbitrary claim in the claim 1 to 5, it is characterized in that, the limit jumping-up rate of described aluminium alloy under 200 ℃ to 600 ℃ temperature that constitutes matrix is 70% or higher, and the unit elongation under 20 ℃ is 10% or higher.
7. according to the described ornamental aluminium alloy element of arbitrary claim in the claim 1 to 6, it is characterized in that, the metallic crystalline structure of described aluminium alloy comprises aluminium crystal and intermetallic compound, aluminium crystalline average grain size is 500nm or littler, and the average grain size of intermetallic compound is 300nm or littler.
8. according to the described ornamental aluminium alloy element of arbitrary claim in the claim 1 to 7, it is characterized in that it is an exterior part of wrist-watch, a decoration or parts that are used for electronics or household electrical appliance.
9. method of producing ornamental aluminium alloy element is characterized in that it 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 ℃ to 600 ℃ temperature at temperature rise rate;
(c) process the mold pressing base substrate that has heated; And
(d) finished mold pressing base substrate is carried out anodic oxidation treatment.
10. method according to claim 9 is characterized in that, described step (a) comprises the step of the quick-setting powder of a described aluminium alloy of mold pressing.
11., it is characterized in that described step (c) comprises such step according to claim 9 or 10 described methods, the mold pressing base substrate that is about to heating is thermally processed into curing powder, subsequently hot-work solidified powder.
12., it is characterized in that described mold pressing blank forming is to have shaft-like or tabular shape according to the described method of arbitrary claim in the claim 9 to 11.
13., it is characterized in that described step (b) comprises such step, promptly comes the mold pressing base substrate is heated by induction heating according to the described method of arbitrary claim in the claim 9 to 12, the time that is used for the heating and mould pressing base substrate is in one minute.
14., it is characterized in that according to the described method of arbitrary claim in the claim 9 to 13, be hot moulding to the process operation of mold pressing base substrate of heating, the mold pressing number of times is for 2 times or still less.
15. according to the described method of arbitrary claim in the claim 9 to 14, it is characterized in that, 2 mold pressings are performed such, i.e. mold pressing for the first time is pressed into a net shape substantially with the profile of mold pressing base substrate, and mold pressing for the second time is that shallow mold pressing is carried out on the surface of mold pressing base substrate.
16. according to the described method of arbitrary claim in the claim 9 to 13, it is characterized in that, described process operation to the mold pressing base substrate that heated comprises: the profile of mold pressing base substrate is pressed into the mold pressing first time of a net shape substantially and the surface of mold pressing base substrate is carried out the mold pressing second time of shallow mold pressing:
The described mold pressing first time is hot moulding, and the described mold pressing second time is cold forming.
17., it is characterized in that described step (d) comprises encapsulation process according to the described method of arbitrary claim in the claim 9 to 16, and when encapsulation process, adopted pressure steam sealing method or nickel acetate sealing method.
18., it is characterized in that described step (d) comprises painted processing according to the described method of arbitrary claim in the claim 9 to 17, and when painted processing, adopted dyeing process, natural coloration method or electrolytic coloring method.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10311383A JP2000144489A (en) | 1998-10-30 | 1998-10-30 | Aluminum alloy member for ornament, and its manufacture |
| JP311383/98 | 1998-10-30 | ||
| JP311383/1998 | 1998-10-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1254028A true CN1254028A (en) | 2000-05-24 |
| CN1093884C CN1093884C (en) | 2002-11-06 |
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ID=18016530
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99122168A Expired - Fee Related CN1093884C (en) | 1998-10-30 | 1999-10-29 | Decorative aluminium alloy member and its production method |
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| Country | Link |
|---|---|
| EP (1) | EP0997545A1 (en) |
| JP (1) | JP2000144489A (en) |
| CN (1) | CN1093884C (en) |
| HK (1) | HK1027601A1 (en) |
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| CN100500905C (en) * | 2004-05-08 | 2009-06-17 | 埃尔布斯罗赫股份公司 | High mechanical strength aluminum alloy which can be anodized in a decorative manner, method for producing the same and aluminum product manufactured thereby |
| CN102206764A (en) * | 2011-02-12 | 2011-10-05 | 姜海 | Aluminum alloy substrate for high-grade electronic product shell and preparation method thereof |
| CN102699332A (en) * | 2011-02-02 | 2012-10-03 | 里奇蒙特国际股份有限公司 | Method for producing a watch case middle of reduced weight |
| CN105274398A (en) * | 2015-11-06 | 2016-01-27 | 广西南宁智翠科技咨询有限公司 | Outdoor anti-corrosion alloy wire |
| TWI560004B (en) * | 2014-12-05 | 2016-12-01 | Htc Corp | Electronic device housing and manufacturing method for manufacturing the same |
| US9970080B2 (en) | 2015-09-24 | 2018-05-15 | Apple Inc. | Micro-alloying to mitigate the slight discoloration resulting from entrained metal in anodized aluminum surface finishes |
| CN108103326A (en) * | 2016-11-24 | 2018-06-01 | 宁波江丰电子材料股份有限公司 | The forming method of aluminium alloy |
| US10174436B2 (en) | 2016-04-06 | 2019-01-08 | Apple Inc. | Process for enhanced corrosion protection of anodized aluminum |
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| JP2003042208A (en) * | 2001-07-24 | 2003-02-13 | Showa Corp | Piston rod for hydraulic shock absorber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0621304B2 (en) * | 1986-04-09 | 1994-03-23 | 昭和アルミニウム株式会社 | Method for improving aluminum alloys for superplasticity |
| US4818300A (en) * | 1986-12-08 | 1989-04-04 | Aluminum Company Of America | Method for making lithoplate |
| JPH01272739A (en) * | 1988-04-22 | 1989-10-31 | Showa Alum Corp | Aluminum alloy for self-color anodizing |
| JPH07145441A (en) * | 1993-01-27 | 1995-06-06 | Toyota Motor Corp | Superplastic aluminum alloy and its production |
| US5728503A (en) * | 1995-12-04 | 1998-03-17 | Bayer Corporation | Lithographic printing plates having specific grained and anodized aluminum substrate |
-
1998
- 1998-10-30 JP JP10311383A patent/JP2000144489A/en not_active Withdrawn
-
1999
- 1999-10-28 EP EP99121491A patent/EP0997545A1/en not_active Withdrawn
- 1999-10-29 CN CN99122168A patent/CN1093884C/en not_active Expired - Fee Related
-
2000
- 2000-10-27 HK HK00106858A patent/HK1027601A1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0997545A1 (en) | 2000-05-03 |
| CN1093884C (en) | 2002-11-06 |
| JP2000144489A (en) | 2000-05-26 |
| HK1027601A1 (en) | 2001-01-19 |
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