TWI248475B - Hard coating and method for producing the same - Google Patents

Abstract

A hard coating formed by a physical vapor deposition mainly comprises surface coating including chromium, carbon, and at least one of vanadium, niobium, tantalum, molybdenum, or tungsten. The surface coating possesses properties of high temperature resistance and low frictional resistance. The hard coating preferably includes a substrate coating comprising chromium and at least one of vanadium, niobium, tantalum, molybdenum, or tungsten. Thus, a surface coating with high temperature resistance and low frictional resistance is stably formed on a substrate. The present invention further provides a method for forming a hard coating on a substrate.

Description

1248475

[Related Applications] This case claims the domestic priority of “Hard Coating and Its Manufacturing Method” No. 09 1 1 32636 of the application for the Republic of China in November. TECHNICAL FIELD OF THE INVENTION The present invention relates to a high temperature resistant hard coating. [Prior Art] Durable tools have always been the demand of the manufacturing industry, so the development of hard coatings has emerged. Hard coatings are used in a wide range of applications, including tools for cutting machines, cutting tools (including cars, strands, saws, milling, planing, grinding, drilling, screwing, stamping, etc.) and molds (for punching, pressing or squeezing, etc.). ), the engine, crankshaft, gearbox, fuel injector and other components in the automotive industry, turbine blades, textile machinery and other components of the aerospace industry need to be covered with a hard coating for wear resistance. Corrosion resistant, high temperature resistant, lubricious surface. 'The hard coatings currently known are all wear resistant, but their high temperature resistance and lubricity (low friction) properties are difficult to achieve. For example, chromium nitride is a widely used hard coating with a heat resistance temperature of 80 ° C and a contact angle with water of about 7 〇. Therefore, the surface of the chrome-plated coating & has high temperature resistance and anti-stick properties, but its disadvantage is that the surface friction coefficient of the chromium nitride plated surface is as high as 〇·6, so it is not suitable for low friction properties. Lubricating properties) of the tool surface. Chromium carbide is another widely used hard coating with a surface friction coefficient of only 〇·〇·2, but its contact angle with water is only about 60. And the heat resistance temperature is only 3〇〇, so the surface formed by the chromium carbide coating has low friction property (high lubricating property) but is difficult to resist.

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Viscosity is also not applicable to 40 ° C to the temperature of the ^ ^ _. However, 'the machine with high speed operation _ and low friction properties are often lacking. The heat-resistant temperature and anti-adhesive properties of the coating are wear-resistant and corrosion-resistant::::, so there is a need for a hard type [invention] "viscosity and low friction properties" and a surface coating of at least one of chrome, tantalum, sharp, button, molybdenum or tungsten. The hard coating preferably further comprises a layer of titanium or other 4 lanthanum elements (eg or底层) an underlying coating, and an intermediate layer coating comprising nitrogen, titanium or other 4B elements such as erbium or yttrium, and at least one of chromium, vanadium, niobium, tantalum, molybdenum or tungsten, the underlying coating And the interlayer coating facilitates the stable coating of the surface coating on a substrate. The main object of the present invention is to provide a shell film 'to thereby overcome or at least improve the above object, and the present invention provides a coating film, Mainly comprising a surface mineral film containing one of chromium or tungsten. The chromium film and at least the hunger, sharp, new, molybdenum film 'the underlying coating layer helps to provide the surface layer of the invention with a physical gas to contain a Titanium or other Group 4B species are resistant to high temperature and low friction properties. The hard prior art of hard, charcoal and at least hunger, sharp, neon, and indium hard coatings formed by physical vapor deposition preferably further comprises a layer containing Or the bottom plating of one of the cranes is firmly disposed on a substrate. The hard coating formed by phase deposition, the main element (such as wrong or 铪), nitrogen, carbon, the present invention further provides a hard coating a method of forming a surface of a substrate. First, placing the substrate in a physical vapor deposition system, then introducing an blunt gas into the physical vapor deposition system, and then using chromium metal and at least Kay, sharp, bismuth, molybdenum or

00596.Tl-CAl.ptd

1248475

The pure metal of the medium is (four)', which is simultaneously distilled to the surface of the substrate to coat the underlayer. In the next step, a hydrocarbon gas can be introduced into the physics:: 2 system with a chrome metal and at least a pure metal of 35, button, molybdenum or tungsten a as a dry source (preferably the same as forming an underlying coating) The target source - : = is described) two metals are simultaneously evaporated on the underlying coating to form the

Further, the present invention provides a method of forming a hard coating film on the surface of a substrate. : First, the substrate is placed in a physical vapor deposition system, and then argon gas is introduced into the physical vapor deposition system, and then titanium or other elements of the 4β family (for example, yttrium or :) are attached to the genus*. As a target source, it is vapor-deposited on the surface of the substrate to form the underlying plating or argon gas into the physical vapor deposition system, and argon gas and nitrogen & For example, a hammer or bismuth metal and at least a chromium, vanadium, or a pure metal of one of the 5: or tungsten is used as a target source. The surface of the furnace 2 is simultaneously vapor-deposited to form the intermediate layer of the ore film. Next, a dioxane, a disordered gas, and an argon gas are applied to the physical gas to form a metal such as z (or zirconium or hafnium) and at least a chromium, hunger, and sharp film to form the surface layer (4). ν Two kinds of metal @ vapor deposition on the bottom g of its purpose, advantages, and novel features, from the following definitions - the detailed description of the details will be more clear.攸布又和图开 [Embodiment] This task reveals a hard mineral film, i

The layer coating comprises a final, 妒/, mainly comprising-surface ruthenium, the I ruin and a period of the same body-centered cubic structure as the chrome;

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V. INSTRUCTIONS (4) 5 B slaves or 6 B groups (for example, hungry, sharply speaking, the above-mentioned surface coating is a kind of looking / mesh or mine) & More specific (composed of chromium and vanadium, niobium, tantalum, turn or tungsten, a composite metal coating as defined in the specification). The coating formed in this case.糸 由 由 由 由 由 由 由 由 由 由 由 由 由 由 由 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图 图120 and the surface mineral film 130' described above, and the underlying coating film 120 comprises an element of the group 6B, and is preferably a borrowing of the element 5B or the group of the group BB in the chrome table. The 5B substrate 11〇 (for example, steel, aluminum/sign-in) in the same periodic coating is used to make the surface coating 130 and the stable bonded steel 35, titanium, ultra-thin alloy or ceramics have good and 2 It is also disclosed that a hard coating film mainly contains, or is a tantalum, a 4B or a 6B group of the periodic table of the same body-centered cubic structure. (for example, film: helmet, button, molybdenum or tungsten). More specifically, the surface layer is a composite metal coating doped with carbon and nitrogen (known as titanium or 1, 4B). Or giving) and chromium, hunger, sputum, group, molybdenum at least one element.) τ Du 4 is an implementation according to the present invention. The hard coating, the crucible 3 - the substrate 410 is covered with an underlying coating 42 〇, medium · 4 Q Π ΤΎ . I, J θ 曰刖 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广 广Titanium or he! B^, 疋素 (such as wrong or give) metal money film. The middle layer is coated with 糸匕s titanium or 疋 other 4 β group elements (such as wrong or 铪) and periodic table

00596-TW-CAl.ptd Page 8 1248475 V. Description of the invention (5) Element 5B or group of μ, and preferably (for example, wrong or 铪) and 盥表# 膜膜相^@疋, The composite metal film of the 5B group or the 杲fiR britging element of the periodic table of the element of the immortality of the genus of the genus of the genus is a good and stable combination. Gastric coating "Ο and interlayer coating = one of the characteristics of the hard coating is formed by physical vapor deposition Tianyi: two ν3Ρ〇Γ deP〇Slti〇n.) Physical vapor deposition, as the name suggests physical mechanism To carry out thin film deposition without involving chemical chemistry, the name is changed to Si; the mechanism is the phase change phenomenon of the substance, for example, by the plasma state of the 丨 ionized gas. By the two relative molecules are concentrated on the generation e Apply voltage, if the gas between the electrode plates / a certain interval, the surface of the electrode plate due to ion bombardment (i 〇n /men" generated by secondary electrons (SeC〇ndary electrons), "" provided by Under the electric field, sufficient energy will be obtained. Refer to the case where the second two cathode electrode plates 2〇4 are subjected to ion bombardment. The detachment of the positively charged positive ions will obtain the polar south under the electric field acceleration of the dark region 212. 1. When the ions are bombarded at the cathode electrode, based on the principle of momentum switching (m(10)ent, um_transf er), the ion bombardment will generate a second time, and the electrons will also be connected to the surface of the electrode plate 204. Source 2 0 8 atoms give a blow '' Come out 'this action, we call it, sputtering.') Attacking some of the helium atoms that are hit will enter the plasma, and then use methods such as diffusion & The surface of the substrate is n〇 or ^ 410, and thus deposited. According to the present invention, the present invention also provides a method for forming the aforementioned hard shell film on the surface of the substrate by physical vapor deposition. Method 3 is a schematic diagram of a physical vapor deposition system 3 according to an embodiment of the invention. The physical vapor deposition system 300 has four sides around the substrate. The target 3 1〇, each target 31〇 is provided with a pure metal piece of chromium and a pure metal piece of neon (or vanadium, niobium, knob, molybdenum or tungsten), and the system 300 is also provided with an argon gas source 32〇. And a reaction gas source 33 〇 (for supplying a hydrocarbon such as a sulphur or a fast gas as a reaction gas). The physical vapor deposition method according to the present invention includes magnetron DC sputtering or reactivity. Reactive sputtering deposition. First, it will have The surface cleaned and dried substrate is connected to the cathode electrode of the system 3 〇0 and placed in a vacuum evaporation apparatus 3 ,, and evacuated to a vacuum chamber pressure of 2x l〇-5 Torr or less to perform the vapor deposition process. During vapor deposition, argon gas is charged to control the vacuum chamber pressure, and the vapor deposition pressure is maintained at about l/xl (m〇rr~9.0x 10-3 Torr, and then vapor deposition is performed. It is suitable for plating, blunt The gas also contains helium, neon, xenon, xenon, nitrogen, etc. In the case of rhodium plating, the target 31〇 is used as the vapor deposition target source, plating = 'target current is 30A~200A; Dry to form an underlying coating (thickness is about. .... to: 1A 5 is then introduced with a methane or acetylene gas, and the surface of the vaporized ore is formed on the surface of the underlying coating - doped carbon surface coating.硬 Hard coating film prepared according to the above method, surface, below, water contact angle paste, heat resistance temperature at 6〇〇ud〇) has better anti-adhesion and heat resistance than chromium carbide coating. The film is good in low friction. ^ and more chromium nitride. The present invention further provides the use of physical vapor deposition to form the aforementioned hard ore film.

00596-TW-CAl.ptd Page 10 1248475 V. INSTRUCTIONS (7) Method of forming a surface on a substrate. Referring to Fig. 5, first, the substrate which has been cleaned and dried is connected to the cathode electrode of the system 5 〇 and placed in a vacuum evaporation apparatus 50. The physical vapor deposition system 5 is provided with four targets 51 around the substrate, and each target 510 is provided with a pure metal piece of titanium (or tantalum, niobium) and tungsten, tantalum, and Pure metal parts of sharp, new or molybdenum), and the system 5 〇〇 is equipped with an argon gas source 520 and a reactive gas source "o (to provide hydrocarbons such as methane, acetylene as a reaction gas) and 540 ( It is used to supply nitrogen.) Then, the pumping process can be carried out until the vacuum chamber pressure reaches 2 χ 1 〇5 Τ 0 rr, and the steaming process can be carried out. When vapor deposition, argon gas is charged to control the vacuum chamber pressure to make the vapor deposition pressure. Keep it between about 1 · 0 X 1 〇 -2 Torr ~ q Ω v 1 π - 3 τ ^ pa .. between rr y · ux 10 3T 〇 rr, and then carry out vapor deposition. The target source is controlled to control the evaporation time and the target current respectively. (The target current is related to the evaporation method. For example, when the arc is vapor-deposited, the target current is 30A to 200A; when sputtering is performed, the target current is u~5a. Between) to form an underlying coating of titanium (or zirconium, hafnium) (thickness between about 〇ι to about 约). Then, pass nitrogen And the metal sequence π of the two metal targets is combined with the vapor-deposited metal on the workpiece 4 to form a metal-doped intermediate layer coating film. Next, the access Nitrogen 耽 = and methane or acetylene gas, forming a doped carbon and a chaotic metal composite surface coating on the surface of the interlayer coating. = Hard coating prepared according to the method described above, the surface friction coefficient is gna % s The contact angle is more than 8 degrees, and the heat resistance temperature is between 60 ° C and 800 ° C. Therefore, the bright α has a good low friction resistance to the anti-adhesive chromium coating which is better than the chromium carbide coating. Mole

00596-TW-CAl.ptd Page 11 1248475 V. DESCRIPTION OF THE INVENTION (8) The following examples are intended to illustrate the invention, and are not intended to be used in the various embodiments. On the top, the adhesion and scratch test were performed to compare the coating = the shape of the steel substrate, and then the coefficient of friction was tested. , and the improvement of the situation ------------ coating combination ------- adhesion test - ------ scratch test (Ν) friction coefficient - ------ 言--------- (scratch test) steel (substrate) / chrome - group higher than 50 steel (substrate) / carbon (chromium - poor adhesion "" * ------- Less than 50 --- Membrane peeling button ) -------- Steel (substrate) / Chrome - button / carbon (complex - Syria) Good adhesion ----- — and 50 ^- From the above table, it can be seen that the adhesion between the coating and the workpiece is different and the material has different degrees of modification. Moreover, the π Jie layer is on the steel workpiece: t钽VAΛ chrome - New composite gold has excellent adhesion, so it has scratches; the inspection force on the steel shell work piece can be more than 50 拉, but the disadvantage of chrome-me metal is its friction system. The number is large, does not have the low 00596-TW-CAl.ptd Page 12 1248475 V. Description of the invention (9) The surface of the rubbing. If a layer of carbon-doped chrome-group composite metal ore film is formed directly on the steel work piece, the carbon-doped 钽-钽 composite metal coating has poor adhesion to the steel work piece, so the coating is easily peeled off, and the helmet is easily peeled off. The method is tested by the coefficient. When a chromium-ruthenium composite metal layer is vapor-deposited on the steel working piece to form an underlying coating film, and then a carbon-doped chromium or lanthanum composite metal is plated on the underlying plating film to form a surface mineral film. Because the underlying enamel film between the weigong and the film has good adhesion to both, this ^: the adhesion of the coating to the workpiece can be good to the tensile test of the trace test; 5ON or more 'And the friction coefficient of the surface is lower than the 〇1 nature. Example 2_ has a good low friction adhesion test heat test temperature steel (substrate) / titanium adhesion excellent 300 40-50 ° > 0.5 steel (substrate) / titanium / nitrogen (titanium - tungsten) adhesion Excellent 500 50-60° >0.4 Steel (substrate) / titanium / nitrogen (titanium - ^ carbon nitrogen (titanium - tungsten) adhesion excellent 800 _ > 80 ° < 0.1 friction coefficient from -% melon! Although the bonding strength of Xingfu Ke is good, its lubricity (with low friction coefficient) and anti-adhesion (with large water contact angle) are not good. The interlayer coating has good adhesion to the underlying coating and is heat-resistant. Sex, lubricity and anti-adhesion are better than the underlying coating. The surface coating 盥, interlayer coating adhesion is good, and its heat resistance, lubricity and anti-adhesion. Page 13 00596-TW-CAl.ptd 1248475 V. Invention Note that (10) is better than the intermediate layer mineral film. According to the hard coating of the present invention, the friction coefficient is less than 0.1, the water contact angle is about 80 degrees, and the heat temperature is 6 〇〇s8 〇 (rc, so it has good It is resistant to sticking and high temperature and has low friction. In addition, its process and equipment used to manufacture carbon The chrome plating film is completely the same, so the present invention is not required to be disclosed in the above-described preferred embodiments, and the present invention, any one skilled in the art, without departing from the scope of the present invention, is not limited thereto. , and the various changes and modifications may be made. Therefore, the spirit of the present invention and the scope of the patent application attached to it are subject to change.

1248475 Brief description of the drawings [Simplified description of the drawings] Fig. 1 is a cross-sectional view of an object having a hard coating according to the present invention. Fig. 2 is a schematic view of a physical vacuum evaporation system according to an embodiment of the present invention, Figure 4 is a schematic view of a physical vacuum evaporation system according to another embodiment of the present invention. Fig. 4 is a cross-sectional view of an article having a hard coating according to another embodiment of the present invention; and Fig. 5; A schematic of a physical vacuum evaporation system of an embodiment. Figure No. Description: 110 Substrate 120 Underlying Coating 130 Surface Coating 202 Anode Electrode 204 Cathode Electrode 208 Target 210 Plasma Zone 212 Dark Zone 300 Physical Vacuum Tomb $ w\ Degree System 310 Target 320 Argon Source Μ 330 Reagent Gas Source ί 410 Substrate 420 Underlying Coating 430 Intermediate Coating 440 Surface Coating 500 Physical Vacuum Steaming System

00596-TW-CAl.ptd Page 15 1248475 Schematic description 510 Target 530 Reactive gas source 5 2 0 Argon source 540 Reagent gas source

00596-TW-CAl.ptd Page 16 111·

Claims (1)

1248475 ... , __ Case No. 92112061_^ Year Month Day Correction _ VI. Patent Application Scope 1. A hard coating comprising: a surface coating comprising chromium, carbon and vanadium, niobium, tantalum, molybdenum and tungsten The group of members selected. 2. The hard coating according to item 1 of the patent application scope further comprises an underlying coating sandwiched between the surface coating and a substrate, the underlying coating comprising chromium and consisting of vanadium, niobium, tantalum, molybdenum and tungsten Group selector. 3. The hard coating according to item 1 of the patent application scope, wherein the surface coating is a composite metal film doped with carbon, the composite metal film comprising chromium and consisting of vanadium, niobium, tantalum, molybdenum and tungsten. Group selector. 4. The hard coating according to item 3 of the patent application scope, further comprising an underlying coating layer sandwiched between the surface coating and a substrate, wherein the underlying coating is a composite metal film, the composite metal film comprising chromium and A group of vanadium, niobium, tantalum, molybdenum, and tungsten. 5. The hard coating according to item 4 of the patent application scope, wherein the composition of the composite metal film of the underlying coating is the same as the composition of the composite metal film of the surface coating. 6. A hard coating comprising: a surface mineral film substantially consisting of chromium, carbon, and by 鈒, sharp, 钽, platinum, and cranes 00596 Special CAl.ptc Page 17 .1248475 ... ___ Case No. 92112061_年月日日_魅_6. Patent application scope The group of selected members is composed. 7. The hard coating according to item 6 of the patent application scope, further comprising an underlying coating layer sandwiched between the surface coating and the substrate, the underlying coating substantially consisting of chromium and by hunger, sharp, group The group consisting of molybdenum and cranes. 8. The hard coating according to item 6 of the patent application scope, wherein the surface coating is a composite metal film doped with carbon, the composite metal film consists essentially of chromium and by 鈒, sharp, 钽, It consists of a group of molybdenum and tungsten. 9. The hard coating according to item 8 of the patent application scope further comprises an underlying coating sandwiched between the surface coating and the substrate, wherein the underlying coating is a composite metal film, and the composite metal film is substantially (consisting) Essentially of) chromium and consists of group selectors consisting of Syria, Sharp, Group, I and 嫣. 10. The hard coating according to item 9 of the patent application scope, wherein the composition of the composite metal film of the underlying coating is the same as the composition of the composite metal film of the surface coating. 00596-TW-CAl.ptc 18 I 1248475 __ Case No. 92112061_年月曰 _ _ _ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The material is placed in a physical vapor deposition system that uses both chromium and a group of sputum, sharp, group, turn, and crane as target sources; hydrocarbon gas is introduced into the physical vapor deposition system. And when the hydrocarbon gas is filled with the physical vapor deposition system, chromium and a group selected from vanadium, niobium, tantalum, molybdenum, and tungsten are simultaneously vapor-deposited on the surface of the substrate to form a surface coating. 1 . The method of forming a hard coating on a surface of a substrate according to the scope of claim 1 of the patent application, further comprising: introducing pure gas into the physical vapor deposition system before introducing the hydrocarbon; When the blunt gas is filled with the physical vapor deposition system, chromium and a group selected from vanadium, niobium, button, molybdenum and tungsten are simultaneously vapor-deposited on the surface of the substrate to form an underlying coating. 1 3. A method of forming a hard coating on a surface of a substrate according to the first aspect of the patent application, wherein the step of forming the underlying coating and forming the surface coating uses the same metal source. A method of forming a hard coating film according to claim 11 of the patent application form on a surface of a substrate, wherein the hydrocarbon gas system is acetylene. 00596-TW-CAl.ptc Page 19 1248475 _ Case No. 92112061_年月曰 曰 Amendment _ 6. Patent application scope 15. A method of forming a hard coating film on a surface of a substrate according to claim 11 of the patent application scope, wherein the carbon The hydrogen gas system is methane. 16. A hard coated article, comprising: a substrate selected from the group consisting of steel, inscription, titanium, ultra-thin alloy, and ceramics; and a hard coating comprising one The surface coating consists of chromium, carbon, and a group of vanadium, niobium, tantalum, molybdenum, and tungsten. 1 7. The object having a hard coating according to claim 16 of the patent application scope further comprises an underlying coating layer sandwiched between the surface coating film and the surface of the substrate, the underlying coating film comprising chromium and vanadium, niobium, tantalum, A group of molybdenum and tungsten selected. 18. The article having a hard coating according to the scope of the patent application, wherein the surface coating is a composite metal film doped with carbon, the composite metal film comprising chromium and by Kay, sharp, group, Gu And the group selection of the group. 1 . The article having a hard coating according to claim 18 of the patent application, further comprising an underlying coating layer sandwiched between the surface coating and the surface of the substrate, wherein the underlying coating is a composite metal film, the composite The metal film is composed of chromium and a group selected from vanadium, niobium, niobium, molybdenum and tungsten. 00596-TW-CAl.ptc Page 20 1248475 ___ Case No. 92112061_年月曰 _ Revision _ 6. Patent application scope 2 0. According to the patent application scope, item 19 has a hard coated object, wherein the underlying coating is The composition of the composite metal film is the same as that of the composite metal film of the surface coating. 21. A hard coating comprising: a surface coating comprising a group of titanium, zirconium and hafnium selected from the group consisting of nitrogen, carbon and chromium, vanadium, niobium, niobium, molybdenum and tungsten. a group of coatings; an underlying coating disposed on a substrate, the underlying coating comprising a group of titanium, hammer, and tantalum; and an intermediate coating sandwiched between the underlying coating and the surface coating The interlayer coating comprises a group of titanium, hammer, and crucible, nitrogen, and a group of chrome, hunger, sharp, bismuth, antimony, and tungsten. 2, according to the patent application scope of the second aspect of the hard coating, wherein the surface coating is a doped and nitrogen composite metal film, the composite metal film comprising a group consisting of titanium, erbium and strontium The selected person is selected from the group consisting of chrome, hunger, sharp, button, I, and for the group. 2 3. The hard coating according to item 22 of the patent application scope, wherein the underlying coating is a single metal film composed of a group of titanium, zirconium and hafnium, and the interlayer coating is a blend. A composite metal film mixed with nitrogen, comprising a group of titanium, erbium, and yttrium, and a group of chrome, vanadium, niobium, niobium, molybdenum, and tungsten. 00596-TW-CAl.ptc Page 21 1248475 _ Case No. 92112061_年月-曰_6. Patent application scope 24. Hard coating according to item 23 of the patent application scope, wherein the composite metal film of the intermediate layer mineral film The composition is the same as the composition of the composite metal film of the surface layer film. 25. A hard coating comprising: a surface coating, the surface coating is basically selected from the group consisting of titanium, ruthenium and ruthenium, nitrogen, carbon, and chromium, vanadium, and sharp. a group consisting of buttons, molybdenum, and tungsten; an underlying coating disposed on a substrate, the underlying coating being substantially formed by a group of constituents consisting essentially of titanium-germanium and tantalum And an intermediate layer coating between the underlying coating and the surface coating, the intermediate coating consisting essentially of a group consisting of titanium, zirconium and hafnium, nitrogen and chromium, vanadium The group consisting of 铌, 钽, 钼, molybdenum and tungsten is selected. 26. The hard bond film according to item 25 of the patent application scope, wherein the surface mineral film is a composite metal film doped with carbon and nitrogen, the composite metal film is basically consisting of titanium and a knot. And the group selection of 铪 and the group of chrome, signal, 铌, button, molybdenum and tungsten. 005%-TW-CAl_ptc Page 22 1248475 __ Case No. 92112061_年月曰 _ Revision _ 6. Patent application scope 27, according to the patent application scope of the 26th hard coating, wherein the underlying coating is basically (consisting essentially) a single metal film composed of a group of titanium, a junction, and a crucible, the intermediate layer coating being a composite metal film doped with nitrogen, the composite metal film substantially consisting of (consisting essentially Of) A group of titanium, erbium, and yttrium, and a group of chrome, vanadium, niobium, tantalum, molybdenum, and tungsten. 2 8. The hard coating according to item 27 of the patent application scope, wherein the composite metal film of the intermediate coating has the same composition as the composite metal film of the surface coating. 29. A method of forming a hard coating on a surface of a substrate, the method comprising the steps of: placing the substrate in a group selected from the group consisting of titanium, zirconium and hafnium and from chromium, vanadium, niobium, tantalum a group of molybdenum and tungsten selected as a target physical vapor deposition system; a hydrocarbon gas and nitrogen are introduced into the physical vapor deposition system; and when the hydrocarbon gas and nitrogen are filled with physical gas In the phase deposition system, a group of titanium, erroneous, and a group of selected ones, and a group of keels, samarium, knobs, molybdenum, and tungsten are vapor-deposited on the surface of the substrate to form a surface coating. 00596-TW-CAl.:otc 23 I 1248475, _ case number 92112061_年月日日_魅_6, the scope of application for patents 30, according to the scope of the patent application, the hard coating is formed on the surface of a substrate The method further comprising: introducing an blunt gas into the physical vapor deposition system before introducing the hydrocarbon; and grouping the titanium, zirconium, and thorium when the blunt gas is filled with the physical vapor deposition system The selected one is vapor-deposited on the surface of the substrate to form an underlying coating; and nitrogen is introduced into the physical vapor deposition system, and the group consisting of titanium, ruthenium and ruthenium is selected as well as chrome, ruthenium, ruthenium, iridium The group selectors of 锢, 锢 and crane are simultaneously evaporated on the surface of the underlying coating to form an intermediate layer of mineral film. 3 1. A method of forming a hard coating film on a surface of a substrate according to item 30 of the patent application scope, wherein the step of forming the intermediate layer coating film and forming the surface layer coating film uses the same metal target source. 3. A method of forming a hard coating film according to claim 29 of the patent application form on a surface of a substrate, wherein the hydrocarbon gas system is acetylene. 3 3. A method of forming a hard coating film according to claim 29 of the patent application form on a surface of a substrate, wherein the hydrocarbon gas system is decane. 34. An object having a hard coating comprising: a substrate made of steel, inscription, titanium, ultra-thin alloy, and ceramics 00596-TW-CAl.ptc 24th I 1248475 __Case No. 92112061_Yearly revision _ 6. Selected from the group consisting of patents; a hard coating containing a surface coating containing titanium and tantalum And a group selector selected from the group consisting of nitrogen, carbon, and a group of chrome, vanadium, niobium, tantalum, molybdenum, and tungsten; an underlying coating disposed on the substrate, the underlying coating comprising titanium a group of zirconium and hafnium; and an intermediate layer coating between the underlying coating and the surface coating, the intermediate layer of mineral film comprising titanium, zirconium and a group selected by the group, Nitrogen and a group of chrome, vanadium, niobium, tantalum, molybdenum and tungsten. 35. The article having a hard coating according to claim 34, wherein the surface coating is a composite metal film doped with carbon and nitrogen, the composite metal film comprising a group consisting of titanium, tantalum and niobium. The group is selected as well as the group of chrome, vanadium, niobium, button, molybdenum and tungsten. 3. The article having a hard coating according to Item 35 of the patent application, wherein the underlying coating is a single metal film composed of a group of titanium, zirconium and hafnium, the intermediate layer coating system It is a nitrogen-doped composite metal film comprising a group of titanium, zirconium and hafnium and a group of chrome, hunger, sputum, group, key and sputum. 3 7. The article having a hard coating according to the third aspect of the patent application, wherein the composition of the intermediate layer coated composite metal film is the same as the composition of the surface coated composite metal film. 00596-TW-CAl.ptc Page 25