CN101418435A - Method for forming protective layer on contour of work piece - Google Patents

Method for forming protective layer on contour of work piece Download PDF

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Publication number
CN101418435A
CN101418435A CNA2007101669130A CN200710166913A CN101418435A CN 101418435 A CN101418435 A CN 101418435A CN A2007101669130 A CNA2007101669130 A CN A2007101669130A CN 200710166913 A CN200710166913 A CN 200710166913A CN 101418435 A CN101418435 A CN 101418435A
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alloy
workpiece
inorganic layer
protective layer
processing procedure
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林新智
陈敏璋
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Abstract

The invention provides a method for forming a protective layer on an outline of a workpiece. The workpiece is made of at least one metal and/or at least one alloy. The method is to use an atomic layer deposition process and/or a plasma enhanced atomic layer deposition process (or a plasma-assisted atomic layer deposition process) to form an inorganic layer on the outline of the workpiece, wherein the inorganic layer is the protective layer.

Description

On the profile of workpiece, form the method for protective layer
Technical field
The present invention relates to a kind of method that on the profile of workpiece (workpiece), forms protective layer (protection layer); be particularly related to that a kind of (Atomic Layer Deposition, ALD) processing procedure forms the method for protective layer on the profile of workpiece with ald.
Background technology
Common metal or alloy workpiece owing to be subjected to the infringement of external environment, may corrode the breakoff phenomenon that (corrosion), erosion (erosion) or abrasion (wear) etc. hate the sight of, and then influence the work-ing life of workpiece.
Generally speaking; on the contour surface of workpiece, form layer protective layer; the various characteristics of can certain degree ground strengthening workpiece; for example; erosion resistance (corrosion resistance), abrasion-resistance (erosionresistance), wear resistant (wear resistance), fatigue resistance (fatigue resistance) ... etc. characteristic, and then the work-ing life of lifting workpiece.In addition; be formed on the characteristic that protective layer on the contour surface of workpiece also can change the contour surface of workpiece; for example, characteristics such as insulating characteristics (heat insulation), insulation characterisitic (insulation), wetting ability (hydrophilic), hydrophobicity (hydrophobic), bioaffinity (bioaffinity), surface color and polish.
Traditionally, the technician often by electroplating (plating), sputter (sputtering), hot dip process methods such as (hot-dipping), forms protective layer on the profile of workpiece.Yet shortcomings such as the protective layer that forms with traditional method usually has that gauge control is not good, surface coverage scarce capacity or compactness extent deficiency.The not good protective layer of this type of quality can't be very helpful in the workpiece lifting in work-ing life.
Summary of the invention
A purpose of the present invention provides a kind of method that forms protective layer on the profile of workpiece, and it utilizes the ald processing procedure to form protective layer.Whereby, can provide the excellent protection effect, strengthen the various characteristics of workpiece, and then promote the work-ing life of workpiece.
The method of a preferred embodiment of the present invention is by an ald (Atomic LayerDeposition; ALD) processing procedure and/or an electricity slurry strengthen ald (plasma-enhanced ALD) processing procedure (or auxiliary ald (plasma-assisted ALD) processing procedure of an electricity slurry); form an inorganic layer (inorganic layer) on the profile of workpiece, wherein said inorganic layer is promptly as described protective layer.
Therefore, method of the present invention is to utilize the ald processing procedure to form protective layer on the profile of workpiece.Whereby; the excellent protection effect can be provided; strengthen the various characteristics of workpiece; for example; erosion resistance (corrosion resistance), abrasion-resistance (erosion resistance), wear resistant (wearresistance), fatigue resistance characteristics such as (fatigue resistance), and then the work-ing life of lifting workpiece.In addition; method of the present invention is formed on the characteristic that protective layer on the profile of workpiece also can change the contour surface of workpiece; for example; characteristics such as insulating characteristics (heat insulation), insulation characterisitic (insulation), wetting ability (hydrophilic), hydrophobicity (hydrophobic), bioaffinity (bioaffinity), surface color and polish; and then make the purposes of workpiece more extensive, and then improve its economic worth.
Description of drawings
For above and other objects of the present invention, feature and advantage can be become apparent, preferred embodiment of the present invention is described in detail below in conjunction with accompanying drawing:
Fig. 1 is the synoptic diagram of the method for a preferred embodiment of the present invention.
Fig. 2 A to Fig. 2 D is the composition of inorganic layer among Fig. 1 and the synopsis of raw material thereof.
Fig. 3 is the polarization curve of three kinds of workpiece.
Embodiment
See also Fig. 1, Fig. 1 is the synoptic diagram of the method for a preferred embodiment of the present invention.The method of a preferred embodiment of the present invention is in order to form protective layer on the profile 12 of workpiece 10.Workpiece 10 can be made by metal and/or alloy.Can be magnesium (Mg), titanium (Ti), aluminium (Al), chromium (Cr), iron (Fe), nickel (Ni), copper (Cu), cobalt (Co), platinum (Pt), palladium (Pd) or gold (Au) in order to the metal of making workpiece 10, but not as limit.Can be magnesium alloy, aluminium alloy, titanium alloy, Chrome metal powder, nickelalloy, copper alloy, cobalt-base alloy, platinum alloy, palldium alloy, iron-nickel alloy, ferroplatinum, magnalium, magnesium lithium alloy, Al-Li alloy, stainless steel, TiNi base memorial alloy, TiNiCu base memorial alloy, CoCrMo, TiAlV, nickel based super alloy, cobalt-base superalloy or iron nickel based super alloy in order to the alloy of making workpiece 10, but not as limit.
As shown in Figure 1, workpiece 10 is inserted design as in the reaction cavity (reaction chamber) 20 of carrying out the ald processing procedure.
Then, by the ald processing procedure, on the profile 12 of workpiece 10, form inorganic layer (inorganiclayer) 14.Described inorganic layer 14 is promptly as the protective layer of workpiece 10.When practical application, also can cooperate the electricity slurry to strengthen ald processing procedure or the auxiliary ald processing procedure of electricity slurry simultaneously, on the profile 12 of workpiece 10, form inorganic layer 14, by the Ionized mode of part material is reduced process temperatures, to improve the quality of processing procedure.It is noted that, the ald processing procedure has another name called atomic shell brilliant (AtomicLayer Epitaxy of heap of stone, ALE) (Atomic Layer ChemicalVapor Deposition, ALCVD), above-mentioned processing procedure is actually with a kind of processing procedure for processing procedure or atomic layer chemical vapor deposition.
In this embodiment, described inorganic layer 14 can be after finishing deposition further carries out anneal (annealing) under the temperature of scope from 100 ℃ to 1500 ℃.
See also Fig. 2 A to Fig. 2 D, Fig. 2 A to Fig. 2 D is the composition of inorganic layer 14 among Fig. 1 and the synopsis of raw material thereof.In this embodiment, the composition of inorganic layer 14 can be Al 2O 3, AlN, AlP, AlAs, Al XTi YO Z, Al XCr YO Z, Al XZr YO Z, Al XHf YO Z, Bi XTi YO Z, BaS, BaTiO 3, CdS, CdSe, CdTe, CaS, CaF 2, CuGaS 2, CoO, Co 3O 4, CeO 2, Cu 2O, CuO, FeO, GaN, GaAs, GaP, Ga 2O 3, GeO 2, HfO 2, Hf 3N 4, HgTe, InP, InAs, In 2O 3, In 2S 3, InN, LaAlO 3, La 2S 3, La 2O 2S, La 2O 3, La 2CoO 3, La 2NiO 3, La 2MnO 3, MoN, Mo 2N, MoO 2, MgO, MnO x, NiO, NbN, Nb 2O 5, PbS, PtO 2, Si 3N 4, SiO 2, SiC, SnO 2, Sb 2O 5, SrO, SrCO 3, SrTiO 3, SrS, SrS 1-XSe X, SrF 2, Ta 2O 5, TaO XN Y, Ta 3N 5, TaN, Ti XZr YO Z, TiO 2, TiN, Ti XSi YN Z, TiHf YO Z, WO 3, W 2N, Y 2O 3, Y 2O 2S, ZnS 1-XSe X, ZnO, ZnS, ZnSe, ZnTe, ZnS 1-XSe X, ZnF 2, ZrO 2, Zr 3N 4, Zr XSi YO ZOr other similar compound, or be the mixture (mixture) of above-claimed cpd, but not as limit.The composition of inorganic layer 14 and the synopsis of raw material thereof are shown in Fig. 2 A to Fig. 2 D.
In the synopsis shown in Fig. 2 A to Fig. 2 D, thd is meant 2,2,6,6 ,-tetramethyl-3,5-heptanediode.Alkaline earths and yttrium thd mixture may comprise neutral addition compound (adduct) or may handle (oligomerized) through the oligomerization of too small degree.In the synopsis shown in Fig. 2 A to Fig. 2 D, acac is meant acetyl acetonate, iPr is meant CH (CH 3) 2, Me is meant CH 3, tBu is meant C (CH 3) 3, apo is meant 2-amino-pent-2-en-4-onato, dmg is meant dimethylglyoximato, (Bu tO) 3SiOH is meant tris (tert-butoxy) silanol (((CH 3) 3CO) 3SiOH), La ( iPrAMD) 3Be meant tris (N, the lanthanum of N '-diisopropylacetamidinato).
As shown in Figure 1, be example to generate the alumina atom layer by the ald processing procedure, the ald processing procedure is described.Reactions steps in the cycle of an ald can be divided into four parts:
1. utilize carrier gas 22 with H 2O molecule 24 imports in the reaction cavity 20, H 2O molecule 24 can be adsorbed on profile 12 surfaces of workpiece 10 after entering reaction cavity 20, in the profile 12 surface adsorption simple layer O-H bonds of workpiece 10.
2. feed carrier gas 22 and utilize Pu (pump) 28 of group the unnecessary H that is not adsorbed on base material 10 2O molecule 24 is taken away.
3. utilize carrier gas 22 that TMA (Trimethylaluminum) molecule 26 is imported in the reaction cavity 20, with the simple layer O-H bond that originally is adsorbed on profile 12 surfaces of workpiece 10, reaction forms the Al-O bond of simple layer on the profile 12 of workpiece 10, and by product is an organic molecule.
4. feed carrier gas 22 and utilize group Pu 28, take away the organic molecule by product that unnecessary TMA molecule 26 and reaction produce.
Wherein carrier gas 22 can adopt highly purified argon gas or nitrogen.More than four steps be called cycle (ALD cycle) of an ald, can on all surfaces of the profile 12 of workpiece 10, the grow up film of single atomic layer level thickness of the cycle of an ald, this characteristic is called " limitting film forming certainly " (self-limiting), this characteristic makes ald on the control film thickness, and precision can reach an atomic shell (one monolayer).Utilize the cycle times of controlling ald can control the thickness of film accurately.
In this preferred embodiment, the process temperatures setting range can be from room temperature to 600 ℃.It should be noted that because process temperatures is lower, can reduce equipment failure and/or damage that high temperature causes, and then improve processing procedure reliability and the appropriate rate of equipment.
The inorganic layer that forms by the ald processing procedure has following advantage:
1. high surface coverage ability.
2. Jing Mi gauge control, precision can reach an atomic shell.
3. fault in material density is low, no hole structure.
4. material growth temperature is lower.
5. the control of material composition accurately.
6. the raw material uniformity coefficient requires low.
7. processing procedure stability and multiplicity are high.
See also Fig. 3, Fig. 3 is the polarization curve of three kinds of workpiece.Workpiece A (not shown), workpiece B (not shown) and workpiece C (not shown) are all the workpiece made from magnesium alloy.Workpiece A has the protective layer of alumina of the 100nm thickness that forms by the ald processing procedure.Workpiece B has the protective layer of alumina of the 50nm thickness that forms by the ald processing procedure.Workpiece C does not have protective layer.As shown in Figure 3, the corrosion potential of workpiece A is greater than the corrosion potential of workpiece B, and the former two's corrosion potential is again greater than the corrosion potential of the workpiece C that does not have protective layer.Moreover the corrosion current of workpiece A is less than the corrosion current of workpiece B, and the former two's corrosion current is again less than the corrosion current of the workpiece C that does not have protective layer.Can judge to have the erosion resistance of the workpiece A and the workpiece B of protective layer of alumina with this, will go up many well than the workpiece C that does not have protective layer.This shows, workpiece to be had the provide protection of certain degree by the protective layer that the ald processing procedure forms.
Compare in prior art, the method for manufacturing workpiece of the present invention is to utilize the ald processing procedure to form protective layer on the profile of workpiece.Advantages such as the protective layer that forms by the ald processing procedure has high surface coverage ability, accurate gauge control, low fault in material density, material composition control accurately, the raw material uniformity coefficient requires low and processing procedure stability and multiplicity be high.Whereby; the excellent protection effect can be provided; strengthen the various characteristics of workpiece; for example; erosion resistance (corrosion resistance), abrasion-resistance (erosion resistance), wear resistant (wear resistance), fatigue resistance characteristics such as (fatigueresistance), and then the work-ing life of lifting workpiece.In addition; the method according to this invention is formed on the characteristic that protective layer on the contour surface of workpiece also can change the contour surface of workpiece; for example; characteristics such as insulating characteristics (heat insulation), insulation characterisitic (insulation), wetting ability (hydrophilic), hydrophobicity (hydrophobic), bioaffinity (bioaffinity), surface color and polish; and then make the purposes of workpiece more extensive, and then improve its economic worth.
Below preferred embodiment of the present invention is specified, but the present invention is not limited to described embodiment, those of ordinary skill in the art also can make all modification that is equal to or replacement under the prerequisite of spirit of the present invention, modification that these are equal to or replacement all are included in the application's claim institute restricted portion.

Claims (12)

1, a kind of method that forms a protective layer on a profile of a workpiece is characterized in that described workpiece is made by at least one metal and/or at least one alloy, and described method comprises the following step:
Strengthen the ald processing procedure by an ald processing procedure and/or an electricity slurry, form an inorganic layer on the described profile of described workpiece, wherein said inorganic layer is promptly as described protective layer.
2, the method for claim 1 is characterized in that: described inorganic layer is to form under the process temperatures of scope from room temperature to 600 ℃.
3, the method for claim 1 is characterized in that: described inorganic layer further carries out anneal under the temperature of scope from 100 ℃ to 1500 ℃ after finishing deposition.
4, the method for claim 1 is characterized in that: described at least one metal comprises one of them that is selected from the group that is made up of magnesium, titanium, aluminium, chromium, iron, nickel, copper, cobalt, platinum, palladium and gold.
5, the method for claim 1 is characterized in that: described at least one alloy comprises one of them that is selected from the group that is made up of magnesium alloy, aluminium alloy, titanium alloy, Chrome metal powder, nickelalloy, copper alloy, cobalt-base alloy, platinum alloy, palldium alloy, iron-nickel alloy, ferroplatinum, magnalium, magnesium lithium alloy, Al-Li alloy, stainless steel, TiNi base memorial alloy, TiNiCu base memorial alloy, CoCrMo, TiAlV, nickel based super alloy, cobalt-base superalloy and iron nickel based super alloy.
6, the method for claim 1 is characterized in that: the composition of described inorganic layer comprises and is selected from by Al 2O 3, AlN, AlP, AlAs, Al XTi YO Z, Al XCr YO Z, Al XZr YO Z, Al XHf YO Z, Bi XTi YO z, BaS, BaTiO 3, CdS, CdSe, CdTe, CaS, CaF 2, CuGaS 2, CoO, Co 3O 4, CeO 2, Cu 2O, CuO, FeO, GaN, GaAs, GaP, Ga 2O 3, GeO 2, HfO 2, Hf 3N 4, HgTe, InP, InAs, In 2O 3, In 2S 3, InN, LaAlO 3, La 2S 3, La 2O 2S, La 2O 3, La 2CoO 3, La 2NiO 3, La 2MnO 3, MoN, Mo 2N, MoO 2, MgO, MnO x, NiO, NbN, Nb 2O 5, PbS, PtO 2, Si 3N 4, SiO 2, SiC, SnO 2, Sb 2O 5, SrO, SrCO 3, SrTiO 3, SrS, SrS 1-XSe X, SrF 2, Ta 2O 5, TaO XN Y, Ta 3N 5, TaN, Ti XZr YO Z, TiO 2, TiN, Ti XSi YN Z, TiHf YO Z, WO 3, W 2N, Y 2O 3, Y 2O 2S, ZnS 1-XSe X, ZnO, ZnS, ZnSe, ZnTe, ZnS 1-XSe X, ZnF 2, ZrO 2, Zr 3N 4And Zr XSi YO ZIn the group that is formed one of them is individual.
7, a kind of method that forms a protective layer on a profile of a workpiece is characterized in that described workpiece is made by at least one metal and/or at least one alloy, and described method comprises the following step:
By an ald processing procedure and/or the auxiliary ald processing procedure of an electricity slurry, on the described profile of described workpiece, form an inorganic layer, wherein said inorganic layer is promptly as described protective layer.
8, method as claimed in claim 7 is characterized in that: described inorganic layer is to form under the process temperatures of scope from room temperature to 600 ℃.
9, method as claimed in claim 7 is characterized in that: described inorganic layer further carries out anneal under the temperature of scope from 100 ℃ to 1500 ℃ after finishing deposition.
10, method as claimed in claim 7 is characterized in that: described at least one metal comprises one of them that is selected from the group that is made up of magnesium, titanium, aluminium, chromium, iron, nickel, copper, cobalt, platinum, palladium and gold.
11, method as claimed in claim 7 is characterized in that: described at least one alloy comprises one of them that is selected from the group that is made up of magnesium alloy, aluminium alloy, titanium alloy, Chrome metal powder, nickelalloy, copper alloy, cobalt-base alloy, platinum alloy, palldium alloy, iron-nickel alloy, ferroplatinum, magnalium, magnesium lithium alloy, Al-Li alloy, stainless steel, TiNi base memorial alloy, TiNiCu base memorial alloy, CoCrMo, TiAlV, nickel based super alloy, cobalt-base superalloy, iron nickel based super alloy.
12, method as claimed in claim 7 is characterized in that: the composition of described inorganic layer comprises and is selected from by Al 2O 3, AlN, AlP, AlAs, Al XTi YO Z, Al XCr YO Z, Al XZr YO Z, Al XHf YO Z, Bi XTi YO Z, BaS, BaTiO 3, CdS, CdSe, CdTe, CaS, CaF 2, CuGaS 2, CoO, Co 3O 4, CeO 2, Cu 2O, CuO, FeO, GaN, GaAs, GaP, Ga 2O 3, GeO 2, HfO 2, Hf 3N 4, HgTe, InP, InAs, In 2O 3, In 2S 3, InN, LaAlO 3, La 2S 3, La 2O 2S, La 2O 3, La 2CoO 3, La 2NiO 3, La 2MnO 3, MoN, Mo 2N, MoO 2, MgO, MnO x, NiO, NbN, Nb 2O 5, PbS, PtO 2, Si 3N 4, SiO 2, SiC, SnO 2, Sb 2O 5, SrO, SrCO 3, SrTiO 3, SrS, SrS 1-XSe X, SrF 2, Ta 2O 5, TaO XN Y, Ta 3N 5, TaN, Ti XZr YO Z, TiO 2, TiN, Ti XSi YN Z, TiHf YO Z, WO 3, W 2N, Y 2O 3, Y 2O 2S, ZnS 1-XSe X, ZnO, ZnS, ZnSe, ZnTe, ZnS 1-XSe X, ZnF 2, ZrO 2, Zr 3N 4And Zr XSi YO ZIn the group that is formed one of them is individual.
CNA2007101669130A 2007-10-26 2007-10-26 Method for forming protective layer on contour of work piece Pending CN101418435A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103205729A (en) * 2012-01-11 2013-07-17 中国科学院微电子研究所 Method for growing gallium nitride film through using ALD apparatus
CN107164744A (en) * 2017-03-20 2017-09-15 南昌大学 A kind of Mg alloy surface anti-corrosion coating preparation method
CN107236878A (en) * 2017-06-23 2017-10-10 巢湖市兰天大诚门窗幕墙有限公司 High-strength aluminum alloy composite gate
CN107254677A (en) * 2017-06-23 2017-10-17 巢湖市兰天大诚门窗幕墙有限公司 A kind of high-strength, antioxidant aluminium alloy compound door processing technology
CN109659375A (en) * 2019-01-31 2019-04-19 中建材蚌埠玻璃工业设计研究院有限公司 A kind of preparation method of biomimetic features hollow Nano silicon dioxide granule antireflective film
CN110230038A (en) * 2016-04-27 2019-09-13 应用材料公司 Method and chamber part
CN113337808A (en) * 2021-05-10 2021-09-03 西安交通大学 Method for strengthening inner and outer surfaces of voltage reduction element with complex structure
US12002657B2 (en) 2017-01-20 2024-06-04 Applied Materials, Inc. Multi-layer plasma resistant coating by atomic layer deposition

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013104200A1 (en) * 2012-01-11 2013-07-18 中国科学院微电子研究所 Method for using ald device to grow gallium nitride film
CN103205729B (en) * 2012-01-11 2015-07-29 中国科学院微电子研究所 By the method for ALD equipment gallium nitride film growth
CN103205729A (en) * 2012-01-11 2013-07-17 中国科学院微电子研究所 Method for growing gallium nitride film through using ALD apparatus
CN110230038B (en) * 2016-04-27 2021-11-19 应用材料公司 Method and chamber component
US11326253B2 (en) 2016-04-27 2022-05-10 Applied Materials, Inc. Atomic layer deposition of protective coatings for semiconductor process chamber components
US11198937B2 (en) 2016-04-27 2021-12-14 Applied Materials, Inc. Atomic layer deposition of protective coatings for semiconductor process chamber components
CN110230038A (en) * 2016-04-27 2019-09-13 应用材料公司 Method and chamber part
US11198936B2 (en) 2016-04-27 2021-12-14 Applied Materials, Inc. Atomic layer deposition of protective coatings for semiconductor process chamber components
US12002657B2 (en) 2017-01-20 2024-06-04 Applied Materials, Inc. Multi-layer plasma resistant coating by atomic layer deposition
CN107164744A (en) * 2017-03-20 2017-09-15 南昌大学 A kind of Mg alloy surface anti-corrosion coating preparation method
CN107254677A (en) * 2017-06-23 2017-10-17 巢湖市兰天大诚门窗幕墙有限公司 A kind of high-strength, antioxidant aluminium alloy compound door processing technology
CN107236878A (en) * 2017-06-23 2017-10-10 巢湖市兰天大诚门窗幕墙有限公司 High-strength aluminum alloy composite gate
CN109659375A (en) * 2019-01-31 2019-04-19 中建材蚌埠玻璃工业设计研究院有限公司 A kind of preparation method of biomimetic features hollow Nano silicon dioxide granule antireflective film
CN113337808A (en) * 2021-05-10 2021-09-03 西安交通大学 Method for strengthening inner and outer surfaces of voltage reduction element with complex structure

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