EP0368470A1 - Verfahren zur Ablagerung von Deckschichten auf anodisierbaren Metall-Substraten und die erhaltenen Produkte - Google Patents

Verfahren zur Ablagerung von Deckschichten auf anodisierbaren Metall-Substraten und die erhaltenen Produkte Download PDF

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Publication number
EP0368470A1
EP0368470A1 EP89310173A EP89310173A EP0368470A1 EP 0368470 A1 EP0368470 A1 EP 0368470A1 EP 89310173 A EP89310173 A EP 89310173A EP 89310173 A EP89310173 A EP 89310173A EP 0368470 A1 EP0368470 A1 EP 0368470A1
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EP
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Prior art keywords
anodised
layer
pore
pores
metal
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP89310173A
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English (en)
French (fr)
Inventor
Dan Fern
Barry Richard Best
Gregory Ross Jessup
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Rio Tinto Alcan International Ltd
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Alcan International Ltd Canada
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Publication of EP0368470A1 publication Critical patent/EP0368470A1/de
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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
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium

Definitions

  • This invention is concerned with improvements in or relating to methods for depositing finish coatings on substrates of anodisable metals, such as aluminum and its anodisable alloys, and to the products of such methods, and especially but not exclusively to methods for plating finish coatings of chromium on aluminum and its alloys.
  • chromium and other metals suitable as "finish" coatings on a substrate usually steel or aluminum
  • Plating on less easily oxidized metals such as steel is relatively routine, involving for example the deposition of a layer of copper directly on the steel substrate, followed in succession by a thick "semi-bright” nickel layer, a thinner "bright” nickel layer, and an even thinner finish layer of the chromium; the chromium is semi-transparent and the bright appearance is actually provided by the bright nickel layer seen through the finish chromium layer.
  • Plating on anodisable metals is considerably more difficult owing to their relative ease of oxidation, and the consequent inevitable presence of an oxide coating which must be removed if adequate adhesion of the deposited layers to the underlying metal substrate is to be obtained.
  • the art currently is dominated by two methods of preparing the substrate surface, namely zincate and stannate immersion. In these processes the substrate surface is immersed in a suitable zincate or stannate solution, usually of the sodium salt, together with other additions that have been found in practice to increase the appearance and adhesion of the coatings.
  • the zinc or tin atoms respectively displace aluminum atoms at the surface, in the process removing the oxide layer, to result in an adherent zinc or tin layer on which other layers, for example copper followed by nickel, can be deposited to constitute the finish layer, or to constitute a support layer receiving a finish layer, e.g. of chromium.
  • Both of these processes are relatively expensive and are therefore mainly used on expensive commodities.
  • the stannate immersion processes are reported to provide better anti-corrosion performance and adhesion of the resultant coatings, but are the more expensive of the two because of the more expensive components and longer processing time.
  • Suggested chemicals are stannous chloride and orthobutyl titanate to form respectively stannous oxide and conductive titanium oxide (Ti2O3); with titanium the surface can be further treated after plating of the finish coating to convert the (Ti2O3) to insulating titanium dioxide (TiO2).
  • a new method of depositing a layer of a finish metal on a surface of a substrate of an anodisable metal including the steps of:
  • a new method of depositing a layer of a finish metal on a surface of a substrate of an anodizable metal including the steps of:
  • the acid most widely used for porous anodising is sulfuric acid because of its ready availability and lower cost, although phosphoric, oxalic and chromic acids, and mixtures of these and other acids, can also be used.
  • the anodised layer is inherently porous in structure because of the manner of its formation, and a typical structure of a layer 10 obtained by sulfuric acid anodising of an aluminum substrate 12 is shown in Figure 1. For convenience in drawing the surfaces of the layers are shown as flat, but in practice, even at quite low magnification these surfaces will be seen to be highly irregular.
  • Figure 1 shows an anodised layer 10 of aluminum oxide (Al2O3) of about 5 micrometres (50,000 Angstroms) thickness, that typically will be produced using sulfuric acid at about 20°C and of about 165g/litre or 15% by weight concentration, employing an anodising voltage of about 15-20 volts for 10 minutes.
  • Al2O3 aluminum oxide
  • the porous structure obtained is relatively uniform, although highly idealised as shown in Figure 1 for convenience in drawing, and typically the pores will be found to average 0.015 micrometres (150 Angstroms) in transverse dimension, spaced on average about 0.024 micrometres (240 Angstroms) from one another.
  • the pores do not end at the surface of the aluminum substrate, but instead they are on average spaced about 0.015 micrometres (150 Angstroms) from that surface to form a continuous non-porous barrier layer of the relatively non-conductive aluminum oxide, the thickness of this layer depending principally directly on the value of the anodising voltage. Usually with sulfuric acid anodising this thickness averages about 0.0010 to 0.0014 micrometres (10 to 14 Angstroms) per volt. It may be noted that references herein and in the literature to pore sizes, etc. are usually made in Angstroms, while references to thicknesses are made in micrometres, merely to avoid the need to refer to small fractions, 1 micrometre being equal to 10,000 Angstroms.
  • Figure 2 shows an anodised layer 10 of aluminum oxide (Al2O3) of about 2 micrometres (20,000 Angstroms) thickness that typically will be produced using phosphoric acid at about 20°C and of about 100g/litre or 10% by weight concentration,employing an anodising voltage of about 50-60 volts for 10 minutes.
  • the pores themselves are of much larger transverse dimension to give a much lower length/width ratio (20:1 in this example), and they are much more widely spaced apart at an average value of about 0.07 micrometres (700 Angstroms).
  • the barrier layer is thicker because of the higher voltage used; e.g. 60 volts gives a layer of about 700 Angstroms thickness.
  • Figure 3 is a cross-section through an aluminum substrate 12 at the surface of which there has been formed an anodised layer 10 of aluminum oxide in accordance with this invention, a portion 4 of which is shown to a larger scale in Figure 4.
  • a pore-filling metal, semi-bright nickel in this embodiment is deposited on the anodised layer to form a support layer 14, and then a layer 15 is deposited to the desired thickness, which again in this embodiment is semi-bright nickel.
  • This semi-bright nickel layer 15 is followed by a layer 16 of bright nickel and a thin finish layer 18 of chromium.
  • the layer 10 is formed by means of a first anodising step at the surface of the substrate 12 to produce a first layer portion having relatively large transverse dimension pores 20 which open to the substrate free surface.
  • This first step is stopped when the corresponding layer portion is sufficiently thick, and a second anodising step is then employed to produce a second layer portion having relatively small transverse dimension pores 22 that open into the large pores 20, the barrier layer 24 being formed between this second layer portion and the substrate 12.
  • the pores 20 are of 0.09 micrometre (900 Angstroms) transverse dimension and about 1.5 micrometres (15,000 Angstroms) depth, being spaced about 0.07 micrometre (700 Angstroms) from one another while the small pores 22 of the second layer communicating with the large pores 20 are of 0.015 micrometre (150 Angstroms) transverse dimension and about 2.5 micrometres (25,000 Angstroms) depth, being spaced about 0.024 micrometre (240 Angstroms) from one another.
  • Such a composite structure can be filled with the metal of the layer 14 without disruption of the pores and/or of the barrier layer, while providing the necessary good adhesion between the layers 10 and 14, and also the necessary strength of the layer.
  • the preferred method of depositing the pore-filling metal of the layer 14 into the composite pores 20 and 22 without damage to the barrier layer is by use of one of the known systems employing what is referred to herein and in the appended claims as a modified A.C. current, preferably one in which a predetermined negative-going D.C. current has been superimposed on the A.C. current.
  • a modified A.C. current preferably one in which a predetermined negative-going D.C. current has been superimposed on the A.C. current.
  • Such a system avoids the disruption of the barrier layer that would be produced by a pure D.C. current.
  • an A.C. current alone will produce deposition of the metal and production of a support layer sufficient for relatively thin anodic coatings e.g. 2 micrometres. For thicker coatings such unmodified A.C.
  • deposition gives insufficient pore penetration and at too slow a deposition rate to produce the support layer.
  • the rate and thickness are therefore increased by increasing the D.C. component to the maximum level that does not cause disruption.
  • This method of deposition is disclosed for example in U.S. Patent No. 4,226,680, issued to Alcan Research and Development Limited, the disclosure of which is incorporated herein by this reference.
  • Other "modified A.C.” systems are also possible.
  • the superimposed D.C. component is commonly produced by means of a negative bias, which is increased as necessary, while the equivalent effect can be obtained by reduction of positive bias.
  • Another system offsets the A.C. waveform in a manner that will produce an effective negative bias.
  • a further way is to increase the amplitude of the negative portion of the waveform relative to that of the positive portion, which again has the same effect.
  • the substrate is first phosphoric acid anodised with the anodising voltage starting in the usual higher range of values for phosphoric acid, and is decreased during this step until at the end of the phosphoric acid anodising it has reached the range of lower values suitable for sulfuric acid anodising, when the electrolyte is changed, usually by moving the article from the phosphoric acid bath to the sulfuric acid bath, with thorough water rinsing in between, thereby avoiding the sudden application of electric potentials that may deleteriously affect the coating.
  • anodic film before plating introduces the possibility, if desired, of a reduction in the thickness of the subsequent plated layers with consequent cost savings. Further reductions are possible by using a thicker and/or stronger anodic film such as that produced using low temperature sulfuric acid anodising. It will be understood that this industry is particularily cost conscious, especially with regard to the relatively expensive corrosion-resistant metals that are employed in the intermediate and finish coatings, so that any saving that can be achieved in their thickness for an equivalent performance in protection and/or appearance is commercially important.
  • the anodised layer 10 can be of thickness in the range 0.5 - 50 micrometres, usually in the range 1-10 micrometres, preferably in the range 2-6 micrometres, and more preferably 3-5 micrometres, with a thickness of 5 micrometres being usually commercially suitable.
  • the pore-filling material need not form a support coating of more than about 2 micrometres thickness and excellent results can be obtained with the application of a single thin finish coating of chromium over the pore-filling metal layer.
  • the preferred pore-filling metal is nickel. Metals other than nickel, such as cobalt, tin or copper, can also be used.
  • the support layer of the pore-filling metal preferably is of thickness in the range 0.5 - 3 micrometres, and more preferably in the range 1-2 micrometres.
  • the chromium layer preferably is of thickness in the range of 2-3 micrometres.
  • the anodising processes described employing acid baths in the temperature range 20-35°C are usually characterised as"conventional" anodising, but "hard” anodising processes can also be employed for the invention, the usual bath temperature being in the range 3-7°C.
  • Such hard anodised layers are usually thicker than the conventional anodised layers.
  • Such hard layers are also the basis for the pore-filling metal deposition of nickel or cobalt, which can be the support layer for further deposits, which further deposits can be thinner than those normally previously used.
  • Another aspect of the present invention provides deposition processes in which a single stage sulfuric acid anodisation of the surface of an anodisable substrate is followed by a step in which the pores are completely filled with pore-filling metal using an A.C. with superimposed D.C. or other modified A.C. deposition current, and the deposition is continued until there is a layer of the pore-filling metal of only about 2 micrometres on the surface of the anodised layer.
  • Prior processes have been disclosed for example, as in the above-mentioned U.S. Patent No. 4,226,680, and also U.S. Patent No. 4,251,330, the disclosure of which is also incorporated herein by this reference, in which sulfuric acid anodising is followed by only partial filling of the pores with metal to produce a desired colour.
  • the aluminum substrate is pretreated, usually by cleaning with appropriate alkaline and/or acid solutions, and is then anodised using 10% concentration by weight of phosphoric acid at 21°C.
  • the voltage is held at 60 VDC for 2 minutes then decreased progressively to 15 VDC over a period of 3 minutes and held at 15 VDC for 2 minutes.
  • the article is then rinsed in water and moved to a sulfuric acid anodising bath with 15% by weight concentration acid at 21°C and held at 15 VDC for 5 minutes.
  • Nickel is then deposited in the pores using a Watts nickel bath employing for example 240 g/L nickel sulphate (NiSO4.7H2O), 60 g/L nickel chloride (NiCl2.6H2O) and 45 g/L of boric acid (H3BO3), the bath being held at a pH of 4.5 and temperature of 21°C.
  • the bath is employed with AC current taking 1 minute to increase the voltage to 12 1/2 VAC; the voltage is then held at 12 1/2 VAC for 2 minutes and subsequently is held for 8 minutes at 12 1/2 VAC with a -2 VDC bias to provide the main deposition current.
  • Further nickel and chromium layers are then deposited using any suitable conventional processes.
  • the temperature of the phosphoric acid electrolyte can be in the range 21°C - 35°C, and the time for increase to 60 VDC can be in the range 2-5 minutes.
  • a substrate of mechanically buffed aluminum of type AA6463, as commonly used for architectural application, is pretreated in appropriate alkaline and acid cleaning solutions, and is then anodised using 10% by weight phosphoric acid at 21°C; the voltage is held at 60VDC for 2 minutes then decreased progressively to 15VDC over a period of 3 minutes and held at 15VDC for 2 minutes.
  • the article is then rinsed in water and moved to a 15% by weight sulphuric acid bath at 21°C and held at 15VDC for 5 minutes.
  • a support layer of nickel is deposited using the bath of example 9 below and the electrical protocol of example 10 below; thereafter a 25 micrometres thick layer of electroless nickel is applied, using a process as suggested for example 5.
  • a support layer of nickel is deposited as in example 10 below followed by a 40 micrometres thick layer of semi-bright nickel, a 15 micrometre thick layer of bright nickel, and a 2 micrometre thick layer of chromium, all applied using conventional plating techniques.
  • the resulting product has a bright "chromium" finish, as is desired for such an automotive application.
  • a substrate of mechanically buffed aluminum of type AA6063 which is a non-bright material as commonly used for non-decorative architectural purposes, is pretreated and anodised as in example 2.
  • a support layer of nickel is deposited as in example 10, followed by a 15 micrometre thick layer of bright nickel and a 2 micrometre thick layer of chromium, applied using conventional plating techniques. The resulting product had a bright "chromium" finish.
  • the production of the porous anodised layer 10 with a pore-filling metal and a support layer as described in Example 1, is followed by electroless deposition, the metal being selected from nickel, cobalt and copper.
  • electroless compositions suitable for this purpose as disclosed for example in an article by N. Feldstein in Metal Finishing, 51st Guidebook and Directory Issue, 1983, Vol. 81, No. 1A entitled Electroless (Autocatalytic) Plating (pp 468-476), the disclosure of which is incorporated herein by this reference. Because of the additional strength and adherence of the anodised layer the electroless layer can be made much thicker than the support layer, up to about 25 micrometres, to result in a mirror-bright finish suitable for decorative application.
  • a substrate of mechanically buffed aluminum of type AA6061 which is an extruded material for general application, such as machine stock, is pretreated in appropriate alkaline and acid cleaning solutions. It is then anodised using 10% byweight phosphoric acid at 21°C, the voltage being held at 60 VDC for 2 minutes then decreased progressively to 20 VDC over a period of 3 minutes and held at 20 VDC for 2 minutes. The article is then rinsed in water and hard anodised by moving to a 15% by weight sulphuric acid bath at 5°C and held at 20 VDC for 5 minutes. A support layer of nickel and a 25 micrometre layer of electroless nickel are added as in examples 2 and 5. The resulting product has a "stainless steel" appearance combined with good abrasion resistance, making it very suitable for engineering applications requiring a hard surface
  • An aluminum substrate is pretreated and then anodised using a 15% concentration bath of sulfuric acid at 21°C and for 10 minutes at 15 VDC ,producing an anodised layer of about 5 micrometres thickness.
  • This is then plated using either the Watts nickel plating bath of example 1 or a cobalt plating bath, for example one consisting of 100 g/L of cobalt sulfate (CoSO4.7H2O), 40 g/L of boric acid (H3BO3), and 150 g/L of magnesium sulfate (MgSO4.7H2O), the pH being 4.4 and the bath being operated at 16°C
  • a substrate of bright rolled aluminum of type AA5657, as used commercially for bright automotive trim is pretreated in appropriate alkaline and acid cleaning solutions, followed by chemical brightening in a phosphoric acid based solution. It is then anodised to result in a porous anodised layer of 2 micrometres thickness using sulphuric acid of 15% by weight (165g/L) at 20°C, and employing a voltage of 15VDC for 4 1/2 minutes. After thorough rinsing, cobalt is deposited into the pores using the electrolyte of example 6 with A.C. current applied at 12 1/2 VAC for 5 minutes. A thin chromium layer of 2 micrometres is then applied using conventional plating techniques. The resulting product had the appearance typical of stainless steel.
  • a substrate of bright rolled aluminum of type AA5252, also used commercially for bright automotive trim is bright anodised to a thickness of 2 micrometres, as described in example 8.
  • nickel is deposited into the pores using the same electrical parameters as in example 8 and using a Watt's nickel bath of 240g/L nickel sulphate (NiSO4.7H2O), 60g/L nickel chloride (NiCl2.6H2O) and 45g/L boric acid (H3BO4) the bath being held at a pH of 4.5 and temperature of 21°C.
  • a thin chromium layer of 2 micrometres thickness is then applied using conventional plating techniques. The resulting product had the appearance typical of stainless steel.
  • nickel is deposited into the pores using a Watt's nickel bath as described in example 8.
  • A.C. current is used by ramping over a period 1 minute to 12 1/2 VAC, held at this voltage for 2 minutes then a negative 2 VDC shift is superimposed on the A.C. for a further 8 minutes.
  • a layer of 5 micrometres thickness of electroless nickel is then applied using a conventional electroless plating technique. The resulting product had the appearance characteristic of polished stainless steel.
  • a substrate of bright rolled aluminum of type AA5657 is bright anodised to a thickness of 5 micrometres as described in example 8 for 10 minutes.
  • nickel is deposited into the pores using a Watt's nickel bath as described in example 9.
  • the A.C. voltage is set initially at 12 1/2 VAC with a negative 2 VDC bias and the current is ramped up to this level over a period of 1 minute and maintained at this level for 10 minutes.
  • a layer of 5 micrometres thickness of electroless nickel is then applied using a conventional electroless plating technique. The resulting product had the same appearance as with example 10.
  • the processes of the invention are not limited to the production of architectural, automotive and decorative finishes, and an example of an alternative application is the deposition of a black chrome finish layer on a nickel support layer for solar selective absorber applications.
  • a similar process can be employed for the production of magnetic discs, also involving the production of a support layer of nickel followed by a chromium layer.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Electroplating Methods And Accessories (AREA)
EP89310173A 1988-10-14 1989-10-04 Verfahren zur Ablagerung von Deckschichten auf anodisierbaren Metall-Substraten und die erhaltenen Produkte Withdrawn EP0368470A1 (de)

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CA580280 1988-10-14

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1642745A3 (de) * 2004-10-04 2006-05-24 Konica Minolta Medical & Graphic, Inc. Aluminiumträger für eine Flachdruckplatte, Herstellungsverfahren und Material dafür
US7235142B2 (en) 2002-01-04 2007-06-26 University Of Dayton Non-toxic corrosion-protection rinses and seals based on cobalt
US7291217B2 (en) 2002-01-04 2007-11-06 University Of Dayton Non-toxic corrosion-protection pigments based on rare earth elements
US7294211B2 (en) 2002-01-04 2007-11-13 University Of Dayton Non-toxic corrosion-protection conversion coats based on cobalt
US7789958B2 (en) 2003-01-13 2010-09-07 University Of Dayton Non-toxic corrosion-protection pigments based on manganese
US20180051388A1 (en) * 2016-08-17 2018-02-22 Fengyan Hou Method to create thin functional coatings on light alloys
CN110168145A (zh) * 2016-07-13 2019-08-23 英奥创公司 电化学方法、组件和组成
CN115341169A (zh) * 2021-05-14 2022-11-15 北京小米移动软件有限公司 表面处理方法
CN115336845A (zh) * 2021-05-14 2022-11-15 北京小米移动软件有限公司 终端设备

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JP2014116328A (ja) 2011-03-31 2014-06-26 Sanyo Electric Co Ltd 素子搭載用基板、電池および電池モジュール
CN115210411A (zh) * 2020-03-06 2022-10-18 富士胶片株式会社 填充微细结构体及输送方法

Citations (3)

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US4226680A (en) * 1977-06-06 1980-10-07 Alcan Research And Development Limited Process for electrolytic coloration of anodized aluminium
EP0121880A1 (de) * 1983-04-07 1984-10-17 Hoechst Aktiengesellschaft Zweistufiges Verfahren zur Herstellung von anodisch oxidierten flächigen Materialien aus Aluminium und deren Verwendung bei der Herstellung von Offsetdruckplatten
EP0178831A1 (de) * 1984-10-17 1986-04-23 Alcan International Limited Poröse Folien und Verfahren zu ihrer Herstellung

Patent Citations (3)

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US4226680A (en) * 1977-06-06 1980-10-07 Alcan Research And Development Limited Process for electrolytic coloration of anodized aluminium
EP0121880A1 (de) * 1983-04-07 1984-10-17 Hoechst Aktiengesellschaft Zweistufiges Verfahren zur Herstellung von anodisch oxidierten flächigen Materialien aus Aluminium und deren Verwendung bei der Herstellung von Offsetdruckplatten
EP0178831A1 (de) * 1984-10-17 1986-04-23 Alcan International Limited Poröse Folien und Verfahren zu ihrer Herstellung

Non-Patent Citations (1)

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Title
S. WERNICK et al.: "The Surface Treatment and Finishing of Aluminium and its Alloys", vol. 2, Fifth Edition, 1986, pages 1011-1016 *

Cited By (21)

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Publication number Priority date Publication date Assignee Title
US7235142B2 (en) 2002-01-04 2007-06-26 University Of Dayton Non-toxic corrosion-protection rinses and seals based on cobalt
US7291217B2 (en) 2002-01-04 2007-11-06 University Of Dayton Non-toxic corrosion-protection pigments based on rare earth elements
US7294211B2 (en) 2002-01-04 2007-11-13 University Of Dayton Non-toxic corrosion-protection conversion coats based on cobalt
US7407711B2 (en) 2002-01-04 2008-08-05 University Of Dayton Non-toxic corrosion-protection conversion coats based on rare earth elements
US7422793B2 (en) 2002-01-04 2008-09-09 University Of Dayton Non-toxic corrosion-protection rinses and seals based on rare earth elements
US7833331B2 (en) 2002-01-04 2010-11-16 University Of Dayton Non-toxic corrosion-protection pigments based on cobalt
US7789958B2 (en) 2003-01-13 2010-09-07 University Of Dayton Non-toxic corrosion-protection pigments based on manganese
EP1642745A3 (de) * 2004-10-04 2006-05-24 Konica Minolta Medical & Graphic, Inc. Aluminiumträger für eine Flachdruckplatte, Herstellungsverfahren und Material dafür
CN110168145B (zh) * 2016-07-13 2021-08-06 英奥创公司 电化学方法、组件和组成
CN110168145A (zh) * 2016-07-13 2019-08-23 英奥创公司 电化学方法、组件和组成
EP3485068A4 (de) * 2016-07-13 2020-04-22 Iontra LLC Elektrochemische verfahren, vorrichtungen und zusammensetzungen
WO2018033862A1 (en) * 2016-08-17 2018-02-22 Hou Fengyan Method to create thin functional coatings on light alloys
CN110114517A (zh) * 2016-08-17 2019-08-09 席勒斯材料科学有限公司 在轻合金上生成薄功能涂层的方法
US10519562B2 (en) 2016-08-17 2019-12-31 Auckland Uniservices Limited Method to create thin functional coatings on light alloys
EP3500695A4 (de) * 2016-08-17 2020-03-25 Cirrus Materials Science Limited Verfahren zur erzeugung dünner funktionsschichten auf leichtmetalllegierungen
US20180051388A1 (en) * 2016-08-17 2018-02-22 Fengyan Hou Method to create thin functional coatings on light alloys
TWI762503B (zh) * 2016-08-17 2022-05-01 紐西蘭商西洛斯材料科學有限公司 在輕合金上創建薄功能塗層之方法
AU2017314185B2 (en) * 2016-08-17 2022-07-14 Cirrus Materials Science Limited Method to create thin functional coatings on light alloys
CN110114517B (zh) * 2016-08-17 2022-12-13 席勒斯材料科学有限公司 在轻合金上生成薄功能涂层的方法
CN115341169A (zh) * 2021-05-14 2022-11-15 北京小米移动软件有限公司 表面处理方法
CN115336845A (zh) * 2021-05-14 2022-11-15 北京小米移动软件有限公司 终端设备

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