CN105586625A - Titanium-based multi-element thin film bicolor anode forming method and product thereof - Google Patents
Titanium-based multi-element thin film bicolor anode forming method and product thereof Download PDFInfo
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- CN105586625A CN105586625A CN201410566432.9A CN201410566432A CN105586625A CN 105586625 A CN105586625 A CN 105586625A CN 201410566432 A CN201410566432 A CN 201410566432A CN 105586625 A CN105586625 A CN 105586625A
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 138
- 239000010936 titanium Substances 0.000 title claims abstract description 137
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000010409 thin film Substances 0.000 title abstract 8
- 239000000463 material Substances 0.000 claims abstract description 69
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 56
- 230000003647 oxidation Effects 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 150000003608 titanium Chemical class 0.000 claims description 33
- 239000004411 aluminium Substances 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 27
- 238000012545 processing Methods 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- PEQFPKIXNHTCSJ-UHFFFAOYSA-N alumane;niobium Chemical compound [AlH3].[Nb] PEQFPKIXNHTCSJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 238000011161 development Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 241000208340 Araliaceae Species 0.000 claims 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims 1
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- 235000008434 ginseng Nutrition 0.000 claims 1
- 239000010408 film Substances 0.000 abstract 2
- 235000010210 aluminium Nutrition 0.000 description 22
- 239000003292 glue Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002932 luster Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- VQYHBXLHGKQYOY-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[Al+3].[Ti+4] VQYHBXLHGKQYOY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 210000000981 epithelium Anatomy 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 241000669618 Nothes Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YTPZWYPLOCEZIX-UHFFFAOYSA-N [Nb]#[Nb] Chemical compound [Nb]#[Nb] YTPZWYPLOCEZIX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- Physical Vapour Deposition (AREA)
Abstract
A titanium-based multi-element thin film bicolor anode forming method includes the following steps that a base material is provided; the base material is washed; a titanium-based multi-element thin film is deposited on the base material, wherein the titanium-based multi-element thin film contains titanium and at least one type of another metal; a mask is formed on the base material; the base material with the titanium-based multi-element thin film is used as an anode to be soaked in an electrolyte; a first direct-current voltage is led in so that the surface of the titanium-based multi-element thin film can be oxidized and a first titanium-based multi-element oxidation film layer can be generated on the base material; the mask is removed; the base material is used as the anode to be soaked in the electrolyte to be subjected to anodic treatment; a second direct-current voltage lower than the first direct-current voltage is led in so that the surface of the titanium-based multi-element thin film can be oxidized and a second titanium-based multi-element oxidation film layer can be generated on the base material; and the base material is washed. The invention further provides a product which comprises the titanium-based multi-element thin film and is subjected to bicolor anodic treatment.
Description
Technical field
The present invention is about the double-colored anodic formation method of a kind of titanium Quito element film and goods thereof, specialRefer to that a kind of surface in base material forms titanium Quito element oxidation film layer, makes the two or more metal light of base material toolThe color in pool, and the goods that utilize the method to make.
Background technology
Portable electric product is very universal now, such as mobile phone, personal digital assistant, computer etc. DisappearExpense person more and more focuses on its outward appearance, and therefore the housing of various electronic products has bright surface, spy conventionallyBe not metal surface, multiple formality in addition, makes it have attracting smooth surface and gloss conventionally.
For at the surface coloring of housing, known technology utilizes anodic oxidation metal surface shape at presentBecome titanium oxide layer and colorific method. This kind of mode only limits to solid color, cannot produce gradually layerThe variation of look. Process the titanium oxide layer producing through anode and produce different colours, thickness because thickness is differentBe decided by the factors such as voltage, if the titanium oxide layer that will form different-thickness on same housing to produce notSame color is very difficult in practical operation.
Moreover in order to form another kind of color, have to attach one deck plastic film on metal shell, pad pastingCan cover metal shell, real metallic luster and sense of touch cannot be provided.
Therefore how to produce color and the tool metal sense of touch of two or more metallic luster on the surface of housing, thisPatent application people once proposed TaiWan, China patent and disclosed No. 201305392 and approved " double-colored anodeTitanium film forming method and goods thereof ", but titanium film is with 10 volts of anode pencil hardness after treatment of voltage approximatelyFor 3H, still having can improvements.
Summary of the invention
Technical problem to be solved by this invention, is to provide a kind of titanium Quito element film double-colored anode shapeOne-tenth method and goods thereof, utilize anode treatment method, forms the color of two or more metallic luster on base material,And increase the hardness of anode processing rear oxidation layer.
In order to solve the problems of the technologies described above, according to wherein a kind of scheme of the present invention, provide a kind of titanium QuitoThe double-colored anodic formation method of element film, comprises following step: provide a base material; Clean this base material;Deposit titanium Quito element film on this base material, wherein this titanium Quito element film contain titanium with extremelyFew another metal; Forming one is masked on this base material; This base material with this titanium Quito element film is doneFor anode, immerse electrolyte; Pass into the first DC voltage to be oxidized the surface of this titanium Quito element film,And produce first titanium Quito element oxidation film layer on this base material; Remove this mask; Using this base material as sunThe utmost point, immerses electrolyte, carries out anode processing; Pass into the second DC voltage of forcing down than the first direct current withBe oxidized the surface of this titanium Quito element film, and produce second titanium Quito element oxidation film layer on this base material;And clean this base material.
According to an embodiment of the present invention, wherein the thickness of this titanium Quito element film be 2 microns to 3.5Micron.
Another embodiment according to the present invention, when wherein the thickness of this titanium Quito element film is 2 microns,Color development voltage is below 70 volts; When wherein the thickness of this titanium Quito element film is 3.5 microns, color developmentVoltage is below 150 volts.
Another embodiment according to the present invention, wherein this another metal of this titanium Quito element film be aluminium,Niobium or aluminium niobium.
Another embodiment according to the present invention, wherein deposits this titanium Quito element film in the step of this base materialComprise: a titanium aluminium melting target is provided, and wherein the composition ratio of titanium aluminium is 1 to 1; And in sputter modeTitanium atom and the aluminium atomic deposition of above-mentioned titanium aluminium melting target are sputtered to this base material.
Another embodiment according to the present invention, wherein the parameter of deposition step comprises: the back pressure vacuumizing is5e-4Millibar (mbar); Be heated to 50 to 100 DEG C; Voltage is 100 to 200 volts and carries out 20 to 30Minute Ions Bombardment is clean; Deposition section passes into argon flow amount 400 to 600sccm; Substrate bias sets 30To 100 volts, frequency 30 is to 70kHz; Target current settings is that the paramount electric current of low current increases pattern;Wherein imposing low current sputtering time is 10 to 20 minutes, and the current gradient time is 10 to 20 minutes;Wherein imposing high electric current sputtering time is 90 to 160 minutes; After wherein deposition finishes, be cooled to 100 DEG CBelow, then shift out this base material.
Another embodiment according to the present invention, wherein the electrolyte of this anode processing is sulfuric acid, concentration is 0.5Vol% to 2vol%; Determine voltage, electrolyte temperature is controlled at normal temperature to 40 DEG C; The anode processing time is10 to 60 seconds.
Another embodiment according to the present invention, wherein this first DC voltage is 4 to 150 volts, removesAfter this mask, second voltage is set lower than the first voltage more than 2 volts.
Another embodiment according to the present invention, the first voltage of its Anodic processing is 35 volts; The second electricityPressure is 20 volts. According to said method of the present invention, the present invention also provides a kind of tool titanium Quito element filmThe goods of double-colored anode processing, utilize said method to make, and it comprises a base material; And one be formed at this baseTitanium Quito element film on material surface, wherein this titanium Quito element film contains titanium and another gold at leastBelong to; Wherein the surface of this titanium Quito element film has the first titanium Quito being oxidized partly in its surfaceElement oxidation film layer and one is oxidized second titanium Quito element oxide layer in its surface all sidedly, wherein shouldFirst titanium Quito element oxidation film layer shows the first color, and this second titanium Quito element oxidation film layer is in shape notBecome the region of this first titanium Quito element oxidation film layer to show the second color.
According to an embodiment of the present invention, wherein the thickness of this titanium Quito element film be 2 microns to 3.5Micron.
Another embodiment according to the present invention, wherein this another metal of this titanium Quito element film be aluminium,Niobium or aluminium niobium.
The present invention has following beneficial effect: the present invention is by the tool first forming with high voltage anodic oxidationFirst titanium Quito element oxidation film layer of the first color, then the tool second forming with low voltage anodic oxidationSecond titanium Quito element oxidation film layer of color can easily form its spontaneous color, richness on metal shellThere is metallic luster. In addition, titanium deposition Quito element film is compared with deposition titanium film, and anode is after treatment hardDegree can significantly increase, and is treated to example with 10 volts of anodes of voltage, and the anode film pencil hardness of titanizing film is3H, and the anode film pencil hardness of titanium Quito element film can be increased to 7H.
Technology, method and the effect taked for reaching set object in order further to understand the present invention,Refer to following relevant detailed description of the present invention, accompanying drawing, believe object of the present invention, feature and feature,When being goed deep into thus and concrete understanding, but appended accompanying drawing and annex only provide reference and explanation use,Not be used for the present invention to be limited.
Brief description of the drawings
Fig. 1 is the double-colored anodic formation method of titanium of the present invention Quito element film schematic diagram.
Fig. 2 is preparation flow process A step schematic diagram of the present invention.
Fig. 3 is the step schematic diagram of the present invention's anodic oxidation flow process for the first time B1.
Fig. 4 is the step schematic diagram of the B2 of anodic oxidation flow process for the second time in the present invention.
Fig. 5 is the stereogram that the present invention is applied to the housing of electronic product.
[symbol description]
Preparation flow process A
Anodic oxidation B1 for the first time
Remove mask A2
Anodic oxidation B2 for the second time
Housing 100
Base material 102
Titanium Quito element film 104
First titanium Quito element oxidation film layer 104 '
Second titanium Quito element oxidation film layer 104 "
Mask 106
Detailed description of the invention
Please refer to Fig. 1, is the double-colored anodic formation method of titanium of the present invention Quito element film schematic diagram. ThisThe double-colored anodic formation method of titanium Quito element film of invention can be divided into preparation flow process A, anodic oxygen for the first timeChange flow process B1, remove mask flow process A2 and the B2 of anodic oxidation flow process for the second time. Below explanation is each respectivelyFlow process.
[preparation flow process A]
Please refer to Fig. 1 and Fig. 2, Fig. 2 shows preparation flow process A step schematic diagram of the present invention. In stepA11, provides a base material 102, and base material 102 is mainly metal material, can be a metal shell, for exampleThe housing of aluminium, aluminium alloy, stainless steel or magnesium alloy can be even also non-metal shell.
Then steps A 12, about the part of metal shell, what optionally have need to clean this base material 102Make it to be applicable to anode processing. The process of cleaning roughly comprises degreasing, pickling, washing and oven dry. De-before thisFat, to remove the oil content on base material 102 surfaces, is removed surperficial oil content and can be utilized cleaning fluid to soak removal; AcidWash, its object, removing rust staining or the oxide layer of metallic surface, is used different pickling to different metalsLiquid. For example the general conventional pickle of iron and steel can be hydrochloric acid or sulfuric acid, adds corrosion inhibiter to subtract while needsFew corrosion; Stainless steel uses the mixed acid of nitric acid and hydrofluoric acid etc.; Aluminium and alloy thereof use thin nitric acid.Washing, its objective is for the residue in acid cleaning process is cleaned up from substrate surface. Then dryButt material.
Steps A 13, deposits titanium Quito element film 104 on base material 102, wherein this titanium Quito unitElement film 104 contains titanium and another metal at least; The mode of deposition can be physical vapour deposition (PVD)(PhysicalVaporDeposition, PVD), for example vacuum splashing and plating or evaporation, contain to form oneTitanium Quito element film on base material, the thickness of above-mentioned titanium Quito element film 104 can be 2 microns extremely3.5 micron. The present invention can be applicable to the base material of various metal material, even non-by this modeThe base material of metal material.
Above-mentioned titanium Quito element film 104 is containing titanium and another metal at least, and this another metal can beAluminium, niobium (Niobium) or aluminium niobium, film can be that titanium aluminium (TiAl), titanium niobium (TiNb) or titanium aluminium niobium closeThe different element ratios such as gold (Nb-TiAl) or the allotment of different deposition parameter, be formed on base material.
The present embodiment, taking titanium aluminium as example, illustrates that this titanium Quito element film of deposition is in step and the phase of this base materialRelated parameter. First be to provide a titanium aluminium melting target, wherein the composition ratio of titanium aluminium is 1 to 1; Then,In sputter mode, the titanium atom of above-mentioned titanium aluminium melting target and aluminium atomic deposition are sputtered to this base material 102. OnThe parameter of stating deposition step is exemplified below, and comprising: the back pressure (backingpressure) vacuumizing is 5e-4Millibar (mbar); Be heated to 50 to 100 DEG C; Voltage is 100 to 200 volts to carry out 20 to 30 minutesIons Bombardment is clean; Deposition section passes into argon flow amount 400 to 600sccm; (sccm is standardThe abbreviation of cubiccentimeterperminute, the meaning is under standard state, namely 1 largeAir pressure, under 25 degrees Celsius, the flow of 1 milliliter (1ml/min) per minute); Substrate bias set 30 to100 volts, frequency 30 is to 70kHz; Target current settings is that the paramount electric current of low current increases pattern; ItsIn to impose low current sputtering time be 10 to 20 minutes, the current gradient time (ramptime) be 10 to20 minutes; Wherein imposing high electric current sputtering time is 90 to 160 minutes; After wherein deposition finishes, coldBelow but to 100 DEG C, then shift out this base material 102.
Steps A 14, forms a mask 106 on base material 102. Mask 106 is in anodic oxygen for the first timeChange and in flow process B1, will retain to anodised region for the second time. The present invention so far completes preparation flow process ATo enter the flow process of colouring for the first time, utilize anodic oxidation to produce the first color.
Aforementioned mask 106 can be adhesive tape, and better can be peelable glue, can be in order to replace adhesive tape, and its spyPoint is with low cost, simple to operate, noresidue vestige. One preferably mode is, mask 106 withPeelable glue (PeelableMask) is formed on base material 102 via the mode of screen painting, and can printBecome a figure (pattern). Peelable glue is often applied to the part that printed circuit board (PCB) needs protection, and is that one isAqueous protectiveness ink. After screen painting peelable glue, the step that can dry, so that peelable glue shapeBecome membranaceous.
[B1 of anodic oxidation flow process for the first time]
Refer to Fig. 1 and Fig. 3, Fig. 3 is the step schematic diagram of the present invention's anodic oxidation flow process for the first time B1.First the B1 of anodic oxidation flow process for the first time comprises step B11, and anode is processed this base material 102; To there is titaniumThe base material 102 of Quito element film 104 immerses electrolyte (electrolyte) as anode. In the present invention,Electrolyte must be acidic electrolysis bath, for example sulfuric acid, sodium phosphate, chromic acid ... Deng. Lift with sulfuric acid solutionExample, its concentration can be 0.5vol% to 2vol%; Electrolyte temperature is controlled at normal temperature to 40 DEG C.Above are only and illustrate, the main chemical difference of each electrolyte, the epithelium after wherethrough reasonTissue is different, also therefore difference to some extent of character. Wherein sulfuric acid liquid processing procedure gained epithelium corrosion stability is good, andAnd attrition resistance is good.
Subsequent steps B12, passes into the first DC voltage of higher volt to be oxidized this titanium Quito element film102 surface, determines voltage and carries out anode processing. The first DC voltage of higher volt in the present invention, meaningRefer to that with respect to the second DC voltage of second plate oxidation flow process B2 be higher. The first DC voltage canBe 4 to 150 volts, the anode processing time is 10 to 60 seconds. The first DC voltage is preferably and exceedes 30DC voltage more than volt is to be oxidized the surface of this titanium Quito element film. Illustrate, wherein this titaniumWhen the thickness of aluminium film is 2 microns, the suggestion of anode color development voltage is below 70 volts; Wherein this titanium aluminium is thinWhen the thickness of film is 3.5 microns, the suggestion of anode color development voltage is below 150 volts. Mainly with anodic oxygenChange the dissolving degree of depth relevant, it is thinner that low-voltage is dissolved desired depth, and the degree of depth of the required dissolving of high voltage can be comparativelyThick. Through the oxidization time of 15 seconds, just, as shown in step B13, produce first titanium Quito element oxide-filmLayer 104 ' (being the first titanium oxide aluminum membranous layer at the present embodiment) is on base material 102. Or enough high at voltageSituation under, can make the thickness of first titanium Quito element oxidation film layer 104 ' exceed 2.2 microns (μ m),To increase its surface abrasion resistance consumption, being conducive to application needs the occasion of abrasion performance, the housing of for example electronic product.The present invention so far forms the first color on base material 102 by first titanium Quito element oxidation film layer 104 '.The epithelium of the titanium oxide aluminum membranous layer of above-mentioned formation is transparent, insulating film layer, and presenting of color is due to visibleLight is incident in after different titanium oxide aluminum membranous layers, the color reflecting. That is the upper surface of rete oneSecondary reflection light wave is crossing with the secondary reflection light wave of the lower surface of rete, and then forms interference of light look. NoThe oxide-film of stack pile will obtain the interference light of different colours. After completing, the present invention does not need sealing of hole processing.
Then by taking out base material 102 in electrolyte, the step of washing if desired and drying. DryStep contributes to remove peelable glue. Then, removing mask flow process A2 exposes to remove mask 106Unoxidized position, good carry out the B2 of anodic oxidation flow process for the second time and forms the second color.
[B2 of anodic oxidation flow process for the second time]
Refer to Fig. 1 and Fig. 4, Fig. 4 is the step signal of the B2 of anodic oxidation flow process for the second time in the present inventionFigure. Step B21, using above-mentioned base material 102 as anode, carries out anode processing, is also about to formThe base material 102 of one color is dipped in electrolyte again. Electrolyte can immerse anodic oxidation for the first time herein timeIn, need not change electrolyte.
Step B22, passes into the table of the second lower DC voltage with this titanium Quito element film of electrolytic oxidationFace; In this step, the second lower DC voltage refers to compared with the first direct current and forces down, wherein second voltageSuggestion is set lower than the first voltage more than 2 volts, and it differs at least 2 volts of suggestions to more than 5 volts.First DC voltage of the present embodiment can be 35 volts, and the second DC voltage is 20 volts.
Through the oxidization time of 10 to 15 seconds, as step B23, produce second titanium Quito element oxidation film layer104 " (the present embodiment is the second titanium oxide aluminum membranous layer) is on base material 102. The present invention finds with lower by theThe second titania based multielement rete 104 that two DC voltages form ", to the first titanium base first formingMultielement oxidation film layer 104 ' does not visually almost affect. That is the first titanium Quito element oxide-filmLayer 104 ' form the first color do not formed afterwards second titanium Quito element oxidation film layer 104 " secondColor impact.
In anode oxidation process, in the time that composition, the concentration of electrolyte change in certain scope, only meetingChange oxide-film aperture, minimum on the thicknesses of layers impact after stable, color is substantially constant. Affect thicknessMain factor be current density, practical application conventionally see through regulation voltage control. On voltageRise, the film thickness after stable is linear to be increased, and due to interference of light difference between the effects, surface presents notSame color.
If first with low-voltage surface after treatment, while then continuation with high voltage, rete will produce unstable againFixed situation, color also can continue to change. If first process the surface of base material with high voltage anode, then againCarry out anode processing for the second time with low-voltage, high voltage rete after treatment still can keep stablizing and color changeChange atomic little.
Carry out anode processing for the second time through experiment showed, with the voltage lower than anode processing for the first time, theAfter two-step anodization, the first color is influenced little. But, if anodic oxidation is for the first time 15 volts,Be for the second time 35 volts, through experiment find, the first color be subject to for the second time anodised affect very obvious,It is a lot of that color becomes.
Finally, clean base material 102. This cleaning step can comprise washing and oven dry, and bake out temperature canThat 120 degree approximately Celsius are to 150 degree.
The present invention is by above-mentioned formation method, can make the double-colored anode processing of tool titanium Quito element filmGoods, wherein the surface of this titanium Quito element film 102 has one and is oxidized partly in first of its surfaceTitanium Quito element oxidation film layer 104 ' and one is oxidized second titanium Quito elemental oxygen in its surface all sidedlyChange rete 104 ", wherein this first titanium Quito element oxidation film layer 104 ' shows the first color, and this is second years oldTitanium Quito element oxidation film layer 104 " in the region that does not form this first titanium Quito element oxidation film layer 104 'Show the second color.
The present invention, by utilizing the mode of peelable glue screen painting, can easily form various figures, for exampleWord or pattern. As shown in Figure 5, can be the housing 100 of electronic product, on base material 102 withThe first color of first titanium Quito element oxidation film layer 104 ' is as background color, and peelable glue hides into ABC letterPattern, with second titanium Quito element oxidation film layer 104 " the second color only show the position in ABC,Do not affect the first color.
In sum, the double-colored anodic formation method of titanium of the present invention Quito element film and goods thereof have at leastFollowing feature and function. With the embodiment of plating titanium aluminium, titanium oxide aluminium film because of mixTwo phase alumina, make it to produce distribution strengthening mechanism. In the time that this material is subject to external force, Two phase line and staff control andIts direction can absorb many energy, thereby improves integral surface hardness. Through test, with plating titanium aluminiumAfter base material is processed through the anode of 10 volts, hardness can reach pencil hardness 7H.
The present embodiment, with the base material of plating titanium aluminium, contrasts the base material of only titanizing, respectively with 10 volts to 70 voltsAfter the anode for the first time of special different voltages is processed, surface is detected by pencil hardness, arranges as following table:
| 10V | 20V | 30V | 40V | 50V | 60V | 70V | |
| Titanium aluminium | 7H | 7H | 7H | 5H | 5H | 5H | 7H |
| Titanium | 3H | 3H | 3H | 5H | 4H | 3H | 6H |
Experiment showed, that the case hardness of the anode film of all plating titanium aluminiums (TiAl) is all better than the sun of titanizing (Ti)The case hardness of utmost point film. The base material of sputter titaniferous Quito element (titanium aluminium) film, through overvoltage lower than 40After the anode of volt is processed, its hardness can significantly increase. With the control group comparison of only titanizing, hardness is improvedBenefit be increased to pencil hardness 7H by the anode film pencil hardness 3H of titanizing film. And voltage is higher than 40VAnode processing, all can have level more than 5H.
By first titanium Quito element oxide-film of first tool the first color forming with high voltage anodic oxidationLayer, then second titanium Quito element oxidation film layer of tool the second color forming with low voltage anodic oxidation,Can easily on metal shell, form its spontaneous color, be rich in metallic luster. The present invention is different with secondaryVoltage carries out anodic oxidation, and the second titanium Quito element oxidation film layer forming with low voltage can't affectThe color of the first titanium Quito element oxidation film layer previously having formed.
Manufacturing time of the present invention is short, is applicable to a large amount of production, forms special face on the surface of housing simultaneouslyLook. This color can repeat accurately by controlling anodised time, solution, voltage, therefore toolThere is good repeatability. The yield of product can greatly improve.
The foregoing is only better possible embodiments of the present invention, allly do according to the present patent application the scope of the claimsEqualization change with modify, all should belong to covering scope of the present invention.
Claims (12)
1. the double-colored anodic formation method of titanium Quito element film, is characterized in that, comprises following step:
One base material is provided;
Clean this base material;
Deposit titanium Quito element film on this base material, wherein this titanium Quito element film contain titanium withAt least another metal;
Forming one is masked on this base material;
Using this base material with this titanium Quito element film as anode, immerse electrolyte;
Pass into the first DC voltage to be oxidized the surface of this titanium Quito element film, and produce first titanium Quito unitElement oxidation film layer is on this base material;
Remove this mask;
Using this base material as anode, immerse electrolyte, carry out anode processing;
Pass into the second DC voltage forcing down than the first direct current to be oxidized the surface of this titanium Quito element film,And produce second titanium Quito element oxidation film layer on this base material; And
Clean this base material.
2. the double-colored anodic formation method of titanium as claimed in claim 1 Quito element film, wherein this titanium Quito elementThe thickness of film is 2 microns to 3.5 microns.
3. the double-colored anodic formation method of titanium as claimed in claim 2 Quito element film, wherein this titanium Quito elementWhen the thickness of film is 2 microns, color development voltage is below 70 volts; Wherein this titanium Quito element filmWhen thickness is 3.5 microns, color development voltage is below 150 volts.
4. the double-colored anodic formation method of titanium as claimed in claim 1 Quito element film, wherein this titanium Quito elementAnother metal of this of film is aluminium, niobium or aluminium niobium.
5. the double-colored anodic formation method of titanium as claimed in claim 4 Quito element film, wherein deposits this titanium QuitoElement film comprises in the step of this base material:
One titanium aluminium melting target is provided, and wherein the composition ratio of titanium aluminium is 1 to 1; And
In sputter mode, titanium atom and the aluminium atomic deposition of above-mentioned titanium aluminium melting target are sputtered to this base material.
6. the double-colored anodic formation method of titanium as claimed in claim 5 Quito element film, the wherein ginseng of deposition stepNumber comprises:
The back pressure vacuumizing is 5e-4Millibar;
Be heated to 50 to 100 DEG C;
Voltage is 100 to 200 volts, and to carry out 20 to 30 minutes Ions Bombardments clean;
Deposition section passes into argon flow amount 400 to 600sccm;
Substrate bias is set 30 to 100 volts, and frequency 30 is to 70kHz;
Target current settings is that the paramount electric current of low current increases pattern;
Wherein imposing low current sputtering time is 10 to 20 minutes, and the current gradient time is 10 to 20 minutes;
Wherein imposing high electric current sputtering time is 90 to 160 minutes;
After wherein deposition finishes, be cooled to below 100 DEG C, then shift out this base material.
7. the double-colored anodic formation method of titanium as claimed in claim 1 Quito element film, wherein this anode processingElectrolyte is sulfuric acid, and concentration is 0.5vol% to 2vol%; Determine voltage, electrolyte temperature is controlled at normal temperatureTo 40 DEG C; The anode processing time is 10 to 60 seconds.
8. the double-colored anodic formation method of titanium as claimed in claim 1 Quito element film, wherein this first direct currentPressure is 4 to 150 volts, removes after this mask, and second voltage is set lower than the first voltage more than 2 volts.
9. the double-colored anodic formation method of titanium as claimed in claim 8 Quito element film, of its Anodic processingOne voltage is 35 volts; Second voltage is 20 volts.
10. goods for the double-colored anode processing of tool titanium Quito element film, utilize side as claimed in claim 1Method is made, and it is characterized in that, comprising:
One base material; And
One is formed at titanium Quito element film of this substrate surface, and wherein this titanium Quito element film contains titaniumGenus and at least another metal;
Wherein the surface of this titanium Quito element film has the first titanium Quito being oxidized partly in its surfaceElement oxidation film layer and one is oxidized second titanium Quito element oxidation film layer in its surface all sidedly, wherein shouldFirst titanium Quito element oxidation film layer shows the first color, and this second titanium Quito element oxidation film layer is in not formingThe second color is showed in the region of this first titanium Quito element oxidation film layer.
11. as the goods of the double-colored anode processing of tool titanium Quito element film of claim 10, wherein this titanium baseThe thickness of multielement film is 2 microns to 3.5 microns.
12. as the goods of the double-colored anode processing of tool titanium Quito element film of claim 10, wherein this titanium baseAnother metal of this of multielement film is aluminium, niobium or aluminium niobium.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112760693A (en) * | 2020-12-26 | 2021-05-07 | 常州市钛宇新材料科技有限公司 | Colorful titanium alloy coating surface treatment method |
| CN112779583A (en) * | 2020-12-26 | 2021-05-11 | 常州市钛宇新材料科技有限公司 | Color and thick film combined titanium alloy surface treatment method |
| CN113622012A (en) * | 2021-09-10 | 2021-11-09 | 西安赛特思捷金属制品有限公司 | Preparation method of titanium alloy fishing rod |
| CN113684517A (en) * | 2021-09-10 | 2021-11-23 | 西安赛特思捷金属制品有限公司 | Titanium plate painting preparation method based on anodic oxidation |
| CN115896731A (en) * | 2022-12-06 | 2023-04-04 | 等离子体装备科技(广州)有限公司 | Preparation process and processing equipment for metal shell of electronic equipment |
| WO2024016182A1 (en) * | 2022-07-19 | 2024-01-25 | 得利钟表制品厂有限公司 | Surface modification method, color change method, and article |
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| CN102953109A (en) * | 2011-08-26 | 2013-03-06 | 可成科技股份有限公司 | Bicolor anode titanium film forming method and product |
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| CN102953109A (en) * | 2011-08-26 | 2013-03-06 | 可成科技股份有限公司 | Bicolor anode titanium film forming method and product |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112760693A (en) * | 2020-12-26 | 2021-05-07 | 常州市钛宇新材料科技有限公司 | Colorful titanium alloy coating surface treatment method |
| CN112779583A (en) * | 2020-12-26 | 2021-05-11 | 常州市钛宇新材料科技有限公司 | Color and thick film combined titanium alloy surface treatment method |
| CN112779583B (en) * | 2020-12-26 | 2023-07-07 | 常州市钛宇新材料科技有限公司 | Titanium alloy surface treatment method combining color and thick film |
| CN113622012A (en) * | 2021-09-10 | 2021-11-09 | 西安赛特思捷金属制品有限公司 | Preparation method of titanium alloy fishing rod |
| CN113684517A (en) * | 2021-09-10 | 2021-11-23 | 西安赛特思捷金属制品有限公司 | Titanium plate painting preparation method based on anodic oxidation |
| WO2024016182A1 (en) * | 2022-07-19 | 2024-01-25 | 得利钟表制品厂有限公司 | Surface modification method, color change method, and article |
| CN115896731A (en) * | 2022-12-06 | 2023-04-04 | 等离子体装备科技(广州)有限公司 | Preparation process and processing equipment for metal shell of electronic equipment |
| CN115896731B (en) * | 2022-12-06 | 2024-01-12 | 等离子体装备科技(广州)有限公司 | Preparation process and processing equipment for metal shell of electronic equipment |
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