CN1661132A - Hard coat and fabricating method - Google Patents
Hard coat and fabricating method Download PDFInfo
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- CN1661132A CN1661132A CN 200410004650 CN200410004650A CN1661132A CN 1661132 A CN1661132 A CN 1661132A CN 200410004650 CN200410004650 CN 200410004650 CN 200410004650 A CN200410004650 A CN 200410004650A CN 1661132 A CN1661132 A CN 1661132A
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Abstract
A plated hard film generated by physical vapour deposition is composed of a surface film containing Cr, C and at least one of V, Nb, Ta, Mo and W, and a bearing film containing Cr and at least one of V, Nb, Ta, Mo and W. Its advantages are high resistance to high temp, low friction coefficient and high adhesion to substrate. Its preparing process is also disclosed.
Description
Technical field
The invention relates to a kind of high temperature resistant hard plated film (hard coating) and manufacture method thereof.
Background technology
The instrument of durable use is a demand of making industry always, so the development of hard plated film is also arisen at the historic moment.The application of hard plated film is very extensive, the surface of various spare parts such as the turbine blade of various pushers, textile manufacturing machine all needs to be coated with hard coating in spare part, the space industries such as the used cutter of every Work machine, cutting tool (comprise car, strand, saw, mill, plane, mill, brill, spiral shell is attacked and punching press etc.), mould (be used for dashing, pressing or squeeze etc.), automotive industry engine, bent axle, wheel box, oil nozzle, the surface of wear-resisting in order to obtain, anticorrosive, high temperature resistant, tool oilness.
Present known hard attrition resistant characteristic that plated film all possesses, however its resistant to elevated temperatures character and character with oilness (low frictional properties) but are difficult to satisfactory to both parties.For example, chromium nitride is a kind of widely used hard plated film, its heat resisting temperature up to 800 ℃ and the contact angle of itself and water be about 70 °, therefore the surface that is formed by chromium nitride film plating has the high temperature resistant and anti-glutinous characteristic of being stained with, yet its shortcoming be the frictional coefficient on chromium nitride film plating surface up to 0.6, therefore be not suitable for the tool surfaces that needs low frictional properties matter (high lubricity matter).Chromium carbide is another kind of widely used hard plated film, its surperficial frictional coefficient only has 0.1-0.2,60 ° and heat resisting temperature have only 300 ℃ but the contact angle of itself and water is only had an appointment, though therefore the surface that is formed by the chromium carbide plated film has low frictional properties matter (high lubricity matter) and is difficult to anti-being stained with and sticks under the high temperature that also is not suitable for more than 400 ℃.
Yet, in the machinery of high speed operation, high heat resisting temperature, anti-be stained with glutinous character and low frictional properties matter often is indispensable, therefore need a kind of hard plated film at present badly and also have above-mentioned three kinds of character outside wear-resisting, the erosion-resisting characteristic simultaneously (high heat resisting temperature, anti-glutinous character and the low frictional properties matter of being stained with) having.
Summary of the invention
Main purpose of the present invention provides a kind of hard plated film of high temperature resistant and low frictional properties matter, overcomes or improve at least the problem of aforementioned prior art with this.
For reaching above-mentioned purpose, the invention provides a kind of hard plated film that forms with physical vapor deposition, it mainly comprises one and contains chromium, carbon and one of them top layer plated film of vanadium, niobium, tantalum, molybdenum or tungsten at least.This hard plated film preferably comprises one deck in addition and contains chromium and one of them bottom plated film of being formed of vanadium, niobium, tantalum, molybdenum or tungsten at least, and this bottom plated film helps the top layer plated film firmly is located on the base material.
The present invention provides a kind of hard plated film that forms with physical vapor deposition in addition, and it mainly comprises one and contains titanium or the element of other 4B family (for example zirconium or hafnium), nitrogen, carbon and one of them top layer plated film of chromium, vanadium, niobium, tantalum, molybdenum or tungsten at least.This hard plated film preferably comprises the bottom plated film of one deck titanium or the element of other 4B family (for example zirconium or hafnium) in addition, and containing the element (for example zirconium or hafnium) of nitrogen, titanium or other 4B family and one of them middle layer plated film of being formed of chromium, vanadium, niobium, tantalum, molybdenum or tungsten at least, this bottom plated film and this middle layer plated film help the top layer plated film firmly is located on the base material.
The present invention provides a kind of method that the hard plated film is formed at a substrate surface in addition.At first, base material is placed a physics vapour deposition system, in physics vapour deposition system, feed blunt gas then, again with the chromium metal and at least one of them pure metal of vanadium, niobium, tantalum, molybdenum or tungsten be the target source, with its simultaneously evaporation in this substrate surface to form this bottom plated film.Next step, can feed hydrocarbon gas in this physics vapour deposition system, again with the chromium metal and at least one of them pure metal of vanadium, niobium, tantalum, molybdenum or tungsten be target source (the preferable target source that forms the bottom plated film that is same as), at least two kinds of metals while evaporations that will be aforementioned in this bottom plated film to form this top layer plated film.
The present invention provides a kind of method that the hard plated film is formed at a substrate surface again.At first, base material being placed a physics vapour deposition system, feed argon gas then in physics vapour deposition system, is the target source with titanium or the element of other 4B family (for example zirconium or hafnium) metal again, with its evaporation in this substrate surface to form this bottom plated film.Then, in physics vapour deposition system, feed argon gas and nitrogen, with titanium or the element of other 4B family (for example zirconium or hafnium) metal and at least one of them pure metal of chromium, vanadium, niobium, tantalum, molybdenum or tungsten be the target source, with its simultaneously evaporation in this substrate surface to form this middle layer plated film.Next step, feed hydrocarbon gas, nitrogen and argon gas in this physics vapour deposition system, again with titanium or the element of other 4B family (for example zirconium or hafnium) metal and at least one of them pure metal of chromium, vanadium, niobium, tantalum, molybdenum or tungsten be target source (the preferable target source that forms the bottom plated film that is same as), at least two kinds of metals while evaporations that will be aforementioned in this bottom plated film to form this top layer plated film.
Advantage of the present invention: according to hard plated film of the present invention, its frictional coefficient is below 0.1, and about 80 degree of water contact angle, heat resisting temperature are at 600 to 800 ℃, therefore has the good anti-stickiness and high temperature resistant and have a low frictional properties of being stained with.In addition, the equipment of its processing procedure and use is identical with manufacturing chromium carbide plated film, does not therefore need additional cost in equipment and Production Flow Chart.
Description of drawings
Other purpose of the present invention, advantage and novel characteristics, from hereinafter with will be more clear and definite the detailed description of icons association:
Fig. 1: the object sectional view that has the hard plated film according to an embodiment of the invention;
Fig. 2: the simplified schematic diagram of physical vacuum steaming degree system according to an embodiment of the invention;
Fig. 3: the simplified schematic diagram of physical vacuum steaming degree system according to another embodiment of the present invention;
Fig. 4: the object sectional view that has the hard plated film according to another embodiment of the present invention; And
Fig. 5: the simplified schematic diagram of physical vacuum steaming degree system according to an embodiment of the invention.
Wherein:
110 base materials, 120 bottom plated films
130 top layer plated films
202 anode electrodes, 204 cathode electrodes
210 electricity slurry districts, 208 target sources
212 dark spaces
300 physical vacuum steaming degree systems
310 targets, 320 argon gas sources
330 reacting gas sources
410 base materials, 420 bottom plated films
430 middle layer plated films, 440 top layer plated films
500 physical vacuum steaming degree systems
510 targets, 520 argon gas sources
530 reacting gas sources, 540 reacting gas sources
Embodiment
The present invention discloses a kind of hard plated film, and it mainly comprises a top layer plated film, and this top layer plated film comprises chromium, carbon and has 5B family or 6B family (for example vanadium, niobium, tantalum, molybdenum or tungsten) element in the periodictable of identical body-centered cubic structure with chromium.More particularly, aforesaid top layer plated film by a kind of be doped with carbon composition metal plated film (being formed) by at least one element in chromium and vanadium, niobium, tantalum, molybdenum or the tungsten.The composition metal plated film that is defined in this manual be meant by two or more metals the plated film that jointly forms.
Figure 1 shows that the object that has the hard plated film according to an embodiment of the invention, it comprises a base material 110 and is coated with a bottom plated film 120 and aforesaid top layer plated film 130, this bottom plated film 120 then comprises the 5B family or the element of 6B family in chromium and the periodictable, and be preferably the 5B family or the composite metal film of the element of 6B family in chromium and the periodictable identical, make top layer plated film 130 good and stable combining be arranged with base material 110 (for example steel, aluminium, titanium, ultra-thin alloy or pottery) with this with the top layer plated film.
The present invention discloses a kind of hard plated film in addition, it mainly comprises a top layer plated film, and this top layer plated film comprises element (for example zirconium or hafnium), nitrogen, the carbon of titanium or other 4B family and has 5B family or 6B family (for example chromium, vanadium, niobium, tantalum, molybdenum or tungsten) element in the periodictable of identical body-centered cubic structure.More particularly, aforesaid top layer plated film is a kind of composition metal plated film (being made up of at least one element in titanium or the element of other 4B family (for example zirconium or hafnium) and chromium, vanadium, niobium, tantalum, molybdenum or the tungsten) that is doped with carbon and nitrogen.
Figure 4 shows that the object that has the hard plated film according to an embodiment of the invention, it comprises a base material 410 and is coated with a bottom plated film 420, middle layer plated film 430 and aforesaid top layer plated film 430, and the metal coating of the element that this bottom plated film 420 is titaniferous or other 4B family (for example zirconium or hafnium).This middle layer plated film 430 comprises the 5B family or the element of 6B family in the element (for example zirconium or hafnium) of titanium or other 4B family and the periodictable, and be preferably the 5B family or the composite metal film of the element of 6B family in the titanium or the element of other 4B family (for example zirconium or hafnium) and the periodictable identical, make top layer plated film 440 good and stable combining be arranged by this with middle layer plated film 430 with the top layer plated film.
One of feature of hard plated film of the present invention is that it is formed by physical vapor deposition (physical vapor deposition).Physical vapor deposition, as the term suggests be to carry out thin film deposition and do not relate to the process technique of chemical reaction with physical mechanism, so-called physical mechanism is the phase change phenomenon of material, vapor deposition source is converted into by gaseous state has the partly electricity slurry attitude of ionized gas.By on two corresponding battery lead plates (electrodes), imposing voltage, if the gas molecule concentration between battery lead plate is in a certain specific interval, the secondary electron (secondary electrons) that electrode plate surface is produced because of ion bombardment (ion bombardment), under the electric field that battery lead plate provided, enough energy will be obtained.With reference to Fig. 2, show that a cathode electrode plate 204 suffers the situation of ion bombardment.The positively charged ion that breaks away from electricity slurry district 210 under the electric field of dark space 212 quickens, will obtain high energy.When ion after cathode electrode produces bombardment, principle based on momentum conversion (momentum transfer), ion bombardment is except meeting produces secondary electron, also can give the atom in the target source 208 that is connected with battery lead plate 204 surfaces " strike " come out, this action, we are referred to as " splash (sputtering) ".These will be entered in the electricity slurry by target atoms of being hit, utilize the mode that waits such as diffusion (diffusion) then, be delivered to the base material 110 of desiring evaporation or 410 surface at last, and thereby deposit.
According to above-mentioned principle, the present invention also provides a kind of method of utilizing physical vapor deposition aforesaid hard plated film to be formed at substrate surface.The 3rd figure is physics vapour deposition system 300 sketches according to an embodiment of the invention.This physics vapour deposition system 300 is provided with four targets 310 around base material, each target 310 is provided with the pure metal spare of chromium and the pure metal spare of tantalum (or vanadium, niobium, tantalum, molybdenum or tungsten), and this system 300 also is equiped with an argon gas source 320 and reacting gas source 330 (in order to for example to provide hydrocarbon polymer such as methane, acetylene as reactant gases).
According to physical vaporous deposition of the present invention is to comprise magnetic control dc sputtering (magnetron DC sputtering) or reactive sputter (reactive sputteringdeposition).At first, with finishing the cathode electrode of the last system 300 of cleaning surfaces and exsiccant base material connection and inserting in the vacuum evaporation equipment 300, be pumped to vacuum chamber pressure and reach 2 * 10
-5Below the Torr, can carry out the evaporation processing procedure.During evaporation, charge into argon gas control vacuum chamber pressure, make evaporation pressure be maintained at about 1.0 * 10
-2Torr～9.0 * 10
-3Between the Torr, carry out evaporation again.The blunt gas that is suitable for evaporation coating technique also comprises helium, neon, krypton gas, xenon, nitrogen etc. in addition.During evaporation, utilize aforesaid target 310 as the evaporation targets source, (this target current is relevant with the evaporation mode, and during for example with the electric arc evaporation, target current is 30A～200A to control evaporation time and target current respectively; During with the sputter evaporation, target current is between 1A～5A), to form a bottom plated film (thickness is that about 0.1 μ m is between about 0.3 μ m).Then, feed methane or acetylene gas again, with the top layer plated film that is formed a doping carbon by the melts combine of evaporation in this bottom coated surface.
According to the prepared hard plated film of aforesaid method, the frictional coefficient on surface is below 0.1, and water contact angle about 80 is spent, and heat resisting temperature is 600
℃To 800 ℃, therefore obviously have anti-be stained with stickiness and thermotolerance and than the chromium nitride film plating good low frictional properties good than the chromium carbide plated film.
The present invention provides a kind of method of utilizing physical vapor deposition aforesaid hard plated film to be formed at substrate surface in addition.With reference to Fig. 5, at first, will finish the cathode electrode of the last system 500 of cleaning surfaces and exsiccant base material connection and insert in the vacuum evaporation equipment 500.This physics vapour deposition system 500 is provided with four targets 510 around base material, each target 510 is provided with the pure metal spare of titanium (or zirconium, hafnium) and the pure metal spare of tungsten (or chromium, vanadium, niobium, tantalum or molybdenum), and this system 500 also is equiped with an argon gas source 520 and reacting gas source 530 (in order to for example to provide hydrocarbon polymer such as methane, acetylene as reactant gases) and 540 (in order to nitrogen to be provided).
Then, be pumped to vacuum chamber pressure and reach 2 * 10
-5Below the Torr, can carry out the evaporation processing procedure.During evaporation, charge into argon gas control vacuum chamber pressure, make evaporation pressure be maintained at about 1.0 * 10
-2Torr～9.0 * 10
-3Between the Torr, carry out evaporation again.During evaporation, the target of utilization is as the evaporation targets source, and (this target current is relevant with the evaporation mode, and during for example with the electric arc evaporation, target current is 30A～200A to control evaporation time and target current respectively; During with the sputter evaporation, target current is between 1A～5A), to form a bottom plated film (thickness is that about 0.1 μ m is between about 0.3 μ m) that titanium (or zirconium, hafnium) only arranged.Then, feed nitrogen again, and the metal that makes two kinds of metallic targets by evaporation on the work package 410 with the metal composite middle layer plated film that is formed a doping nitrogen by the melts combine of evaporation in this bottom coated surface.Next step feeds nitrogen and methane or acetylene gas, forms the metal composite top layer plated film of a doping carbon and nitrogen in this middle layer coated surface.
According to the prepared hard plated film of aforesaid method, the frictional coefficient on surface is below 0.1, water contact angle is greater than 80 degree, and therefore heat resisting temperature obviously has anti-be stained with stickiness and thermotolerance and than the chromium nitride film plating good low frictional properties good than the chromium carbide plated film at 600 ℃ to 800 ℃.
Following examples system is not in order to limit its scope in order to explanation the present invention.In these embodiments, respectively multiple plated film is made up evaporation on a steel substrate, carry out sticking power and scratch test again,, test its frictional coefficient then to compare the situation of improving of plated film tack.
Embodiment 1
| The plated film combination | The sticking power test | Scratch test (N) (scratch test) | Frictional coefficient |
| Steel (base material)/chromium-tantalum | Sticking power is good | Be higher than 50 | ??＞0.6 |
| Steel (base material)/carbon (chromium-tantalum) | Poor adhesive force | Be lower than 50 | Film peels off |
| Steel (base material)/chromium-tantalum/carbon (chromium-tantalum) | Sticking power is good | Be higher than 50 | ??＜0.1 |
Sticking power between coating and work package system is with the structure and the different improvement that have in various degree of material of surface coating as seen from the above table.When evaporation one chromium-tantalum complex metal layer is on the steel work package, chromium-tantalum complex metal layer is splendid to the sticking power of steel work package, therefore the value of thrust of its scratch test can reach more than the 50N, yet the shortcoming of chromium-tantalum composition metal plated film be its frictional coefficient greater than 0.6, do not have the surface of low frictional properties.If when directly forming the chromium of one deck doping carbon-tantalum composition metal plated film on the steel work package, the chromium of doping carbon-tantalum composition metal plated film is bad to the sticking power of steel work package, so plated film peels off easily, can't carry out the test of frictional coefficient.When evaporation one chromium-tantalum complex metal layer on the steel work package to form a bottom plated film, again the chromium of evaporation one doping carbon-tantalum composition metal plated film on this bottom plated film when forming a top layer plated film, because the bottom plated film between work package and top layer plated film has good sticking power for the both, therefore the plated film of this structure is good to the sticking power of work package, the value of thrust of its scratch test can reach more than the 50N, and the frictional coefficient on surface is lower than 0.1, can have good low frictional properties matter.
Embodiment 2
| The plated film combination | The sticking power test | Heat resisting temperature (℃) | Water contact angle | Frictional coefficient |
| Steel (base material)/titanium | Sticking power is excellent | ????300 | ????40-50° | ???＞0.5 |
| Steel (base material)/titanium/nitrogen (titanium-tungsten) | Sticking power is excellent | ????500 | ????50-60° | ???＞0.4 |
| Steel (base material)/titanium/nitrogen (titanium-tungsten)/carbon nitrogen (titanium-tungsten) | Sticking power is excellent | ????800 | ????＞80° | ???＜0.1 |
Though the bonding force of bottom plated film and base material is good as seen from the above table, yet its thermotolerance, oilness (having low-friction coefficient) and the anti-stickiness (having bigger water contact angle) of being stained with are not good.Middle layer plated film and plated underlayer binding force of membrane are good, and its thermotolerance, oilness and the anti-stickiness of being stained with are good than the bottom plated film.Top layer plated film and middle layer plated film bonding force are good, and its thermotolerance, oilness and the anti-stickiness of being stained with are better than the middle layer plated film.
Though the present invention discloses with aforementioned preferred embodiment, so it is not in order to limiting the present invention, anyly has the knack of this skill person, without departing from the spirit and scope of the present invention, and when doing various changes and modification.Therefore protection scope of the present invention is as the criterion when looking accompanying the claim person of defining.
Claims (15)
1, a kind of hard plated film, it comprises:
One top layer plated film, this top layer plated film has:
One first composition is to be selected from the group that is made up of titanium, zirconium and hafnium;
One second composition is to be selected from the group that is made up of nitrogen and carbon; And
One the 3rd composition is to be selected from the group that is made up of chromium, vanadium, niobium, tantalum, molybdenum and tungsten.
2, by the described hard plated film of claim 1, it is characterized in that: also comprise a bottom plated film and be located between this a top layer plated film and the base material person of selecting of group that this bottom plated film comprises chromium and is made up of vanadium, niobium, tantalum, molybdenum and tungsten.
3, by the described hard plated film of claim 1, it is characterized in that: described top layer plated film is one to be doped with the composite metal film of carbon, the person of selecting of group that this composite metal film system comprises chromium and is made up of vanadium, niobium, tantalum, molybdenum and tungsten.
4, by the described hard plated film of claim 3, it is characterized in that: also comprise a bottom plated film be located in this a top layer plated film and a base material between, this bottom plated film is a composite metal film, the person of selecting of group that this composite metal film comprises chromium and is made up of vanadium, niobium, tantalum, molybdenum and tungsten.
5, by the described hard plated film of claim 4, it is characterized in that: the composition of the composite metal film of described bottom plated film is same as the composition of the composite metal film of this top layer plated film.
6, a kind of the hard plated film is formed at the method for a substrate surface, this method comprises the following step:
Base material is placed one simultaneously being the physics vapour deposition system in target source by chromium, titanium, zirconium, hafnium, the person of selecting of group that is made up of vanadium, niobium, tantalum, molybdenum and tungsten;
In this physics vapour deposition system, feed hydrocarbon gas; And when hydrocarbon gas was full of physics vapour deposition system, the person of selecting of the group evaporation that will be made up of chromium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum and tungsten formed a top layer plated film in this substrate surface simultaneously.
7, by claim 6 is described the hard plated film is formed at the method for a substrate surface, it is characterized in that also comprising:
Before feeding hydrocarbon polymer, blunt gas is fed this physics vapour deposition system; And when blunt gas is full of physics vapour deposition system, simultaneously the person of selecting of group that will form by chromium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum and tungsten simultaneously evaporation form a bottom plated film in this substrate surface.
8, by claim 7 is described the hard plated film is formed at the method for a substrate surface, it is characterized in that the step that forms the bottom plated film and form the top layer plated film is to use identical metallic target source.
9, be formed at the method for a substrate surface by the described hard plated film of claim 6, it is characterized in that: this hydrocarbon gas is an acetylene.
10, be formed at the method for a substrate surface by the described hard plated film of claim 6, wherein this hydrocarbon gas is a methane.
11, a kind of object with hard plated film is characterized in that comprising:
One base material, its material are by the person of selecting in steel, aluminium, titanium, ultra-thin alloy and the ceramic group that is formed; And
One hard plated film, it comprises a top layer plated film and comprises the person of selecting of group who is made up of chromium titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum and tungsten.
12, by the described object of claim 11 with hard plated film, it is characterized in that: also comprise a bottom plated film and be located between this top layer plated film and the substrate surface, this bottom plated film comprises the person of selecting of group who is made up of chromium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum and tungsten.
13, by the described object of claim 11 with hard plated film, it is characterized in that: this top layer plated film is one to be doped with the composite metal film of carbon, and this composite metal film comprises the person of selecting of group who is made up of chromium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum and tungsten.
14, by the described object of claim 11 with hard plated film, it is characterized in that: also comprise a bottom plated film and be located between this top layer plated film and this substrate surface, this bottom plated film is a composite metal film, and this composite metal film comprises the person of selecting of group who is made up of chromium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, aluminium and tungsten.
15, have the object of hard plated film by claim 14, it is characterized in that: the composition of the composite metal film of this bottom plated film is same as the composition of the composite metal film of this top layer plated film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410004650 CN1661132A (en) | 2004-02-26 | 2004-02-26 | Hard coat and fabricating method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410004650 CN1661132A (en) | 2004-02-26 | 2004-02-26 | Hard coat and fabricating method |
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| CN1661132A true CN1661132A (en) | 2005-08-31 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103060751A (en) * | 2013-01-09 | 2013-04-24 | 兰州理工大学温州泵阀工程研究院 | Superhard corrosion-resistant physical vapor deposition (PVD) coating for valve sealing component and plating process thereof |
| CN103182806A (en) * | 2011-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Working die and plated film layer |
| CN103898456A (en) * | 2014-03-19 | 2014-07-02 | 江苏科技大学 | Hard NbVN nano film and preparation method thereof |
| CN103898443A (en) * | 2012-12-26 | 2014-07-02 | 财团法人金属工业研究发展中心 | Work mold and making method thereof |
| WO2020140229A1 (en) * | 2019-01-03 | 2020-07-09 | 天王电子（深圳）有限公司 | Austenitic stainless steel and hardening method therefor |
| CN111607779A (en) * | 2019-11-13 | 2020-09-01 | 哈尔滨理工大学 | Cr-Mo-Nb-W alloying method by M50 steel pulse electron beam irradiation |
| CN113165045A (en) * | 2018-12-03 | 2021-07-23 | 日立金属株式会社 | Coated die for hot stamping |
-
2004
- 2004-02-26 CN CN 200410004650 patent/CN1661132A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103182806A (en) * | 2011-12-30 | 2013-07-03 | 财团法人金属工业研究发展中心 | Working die and plated film layer |
| CN103898443A (en) * | 2012-12-26 | 2014-07-02 | 财团法人金属工业研究发展中心 | Work mold and making method thereof |
| CN103898443B (en) * | 2012-12-26 | 2016-03-16 | 财团法人金属工业研究发展中心 | Work mould and manufacture method thereof |
| CN103060751A (en) * | 2013-01-09 | 2013-04-24 | 兰州理工大学温州泵阀工程研究院 | Superhard corrosion-resistant physical vapor deposition (PVD) coating for valve sealing component and plating process thereof |
| CN103898456A (en) * | 2014-03-19 | 2014-07-02 | 江苏科技大学 | Hard NbVN nano film and preparation method thereof |
| CN113165045A (en) * | 2018-12-03 | 2021-07-23 | 日立金属株式会社 | Coated die for hot stamping |
| WO2020140229A1 (en) * | 2019-01-03 | 2020-07-09 | 天王电子（深圳）有限公司 | Austenitic stainless steel and hardening method therefor |
| CN111607779A (en) * | 2019-11-13 | 2020-09-01 | 哈尔滨理工大学 | Cr-Mo-Nb-W alloying method by M50 steel pulse electron beam irradiation |
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