CN101121309A - Hard film and hard film-coated material - Google Patents

Abstract

A hard film and a hard film-coated material having better wear resistance and sliding performance (due to lower friction coefficients) than conventional surface coating layers, wherein the hard film includes at least one covering layer A and at least one covering layer B stacked one over the other, both having a thickness of 5 to 100 nm. The covering layer has a composition represented by the formula M(BaCbN1-a-b), where M denotes one or more elements selected from W, V, Mo, and Nb, and a and b denote the atomic ratio of B and C, respectively, as defined below. 0<=a<=0.3 . . . (1A), and 0<=b<=0.5 . . . (2A). Covering layer B has a composition represented by the formula Ti1-x-yCrxAlySiz(C1-ANA) where x, y, z, and A denote the atomic ratio of Cr, Al, Si, and N, respectively, as defined below. 0<=1-x-y<=0.5 . . . (1B), 0<=x<=0.5 . . . (2B), 0.4<=y<=0.7 . . . (3B), 0<=z<=0.15 . . . (4B), and 0.5<=A<=1 . . . (5B).

Description

Hard film and hard film-coated material

Technical field

The invention belongs to the technical field that relates to hard film and hard film-coated material.

Background technology

At present, with regard to the metallurgical instrument of metals such as mould processing usefulness,, mar proof and sintering resistance are improved by nitrogen treatment.In recent years, just apply the mar proof bring and the improvement of sintering resistance, to replace nitrogen treatment in gas phases such as research and utilization PVD.For example, open in the 2000-144376 communique the spy, publicity based on the formation of the complex nitride more than 2 kinds that contains Cr, Al, Ti, V and sliding is improved.Open the 2002-307128 communique the spy, the spy opens in the 2002-307129 communique, publicity form Ti, V, Al, Cr, the nitride more than a kind of Si, carbide, carboritride, mould is carried out on the mar proof or the good surface of sintering resistance that form perhaps, and then on this basis the sulfurized layer that contains Ti, Cr and be made of remaining Mo.Open in the 2000-1768 communique the spy, publicity on the hard nitride, form MoS ₂Mar proof and the good finish materials of sintering resistance.

Patent documentation 1 spy opens the 2000-144376 communique

Patent documentation 2 spies open the 2002-307128 communique

Patent documentation 3 spies open the 2002-307129 communique

Patent documentation 4 spies open the 2000-1768 communique

Above-mentioned spy opens the complex nitride more than 2 kinds among Cr, Al, Ti, the V that contains of 2000-144376 communique institute publicity, has high rigidity, mar proof is good, but, sintering resistance is undesirable, when for example under higher surface pressing, carrying out Metal Forming etc., be not durable when under the rigorous environment condition, using.The spy opens nitride, the carbide more than a kind among Ti, V, Al, Cr, the Si of 2002-307128 communique publicity, carboritride has high rigidity too and sintering resistance is poor.In order to improve sintering resistance, under such situation that forms sulfide that Ru Te opens 2002-307129 communique and the publicity of Te Kai 2000-1768 communique institute, sulfide is soft, use initial stage sliding is good, but, wear and tear along with the prolongation of service time, long durability goes wrong.

Summary of the invention

The present invention be directed to above-mentioned situation and research and develop, its purpose is: provide a kind of and above-mentioned present surface-coated layer to compare, mar proof is good, simultaneously, and hard film that coefficient of friction is low, sliding is good and hard film-coated material.

The present inventor has carried out wholwe-hearted research to achieve these goals, and is final, finished the present invention.According to the present invention, can realize above-mentioned purpose.

The realized above-mentioned purpose the present invention who so finishes, relate to hard film and hard film-coated material, the hard film-coated material (hard film-coated material of the present invention the 3rd aspect) of the hard film (hard film of the present invention the 1st～2 aspect) of the first～the second invention and the 3rd invention, it is constructed as follows.

That is, the hard film of first invention, be add up to by following skin membrane A and skin membrane B stacked more than 2 layers and the hard film that forms, wherein, the thickness of described skin membrane A is 5～100nm, and simultaneously, the thickness of described skin membrane B is 5～100nm (the present invention the 1st aspect).

Skin membrane A:

A kind of by M (B _aC _bN _1-a-b) skin membrane that constitutes, it satisfies following formula (1A)～(2A).

0≤a≤0.3 ... ... ... ... ... ... ... ... ... formula (1A)

0≤b≤0.5 ... ... ... ... ... ... ... ... ... formula (2A)

Wherein, at above-mentioned M (B _aC _bN _1-a-b) in, M be among W, V, Mo, the Nb more than a kind; In following formula (1A)～(2A), a represents the atomic ratio of B, and b represents the atomic ratio of C.

Skin membrane B:

A kind of by Ti _1-x-yCr _xAl _ySi _z(C _1-AN _A) skin membrane that constitutes, it satisfies following formula (1B)～(5B).

0≤1-x-y≤0.5 ... ... ... ... ... ... ... ... ... formula (1B)

0≤x≤0.5 ... ... ... ... ... ... ... ... ... ... .. formula (2B)

0.4≤y≤0.7 ... ... ... ... ... ... ... ... ... ... formula (3B)

0≤z≤0.15 ... ... ... ... ... ... ... ... ... .. formula (4B)

0.5≤A≤1 ... ... ... ... ... ... ... ... ... ... formula (5B)

Wherein, in following formula (1B)～(5B), x represents the atomic ratio of Cr, and y represents the atomic ratio of Al, and z represents the atomic ratio of Si, and A represents the atomic ratio of N.

The hard film of second invention, as the described hard film of first invention, the M among the described skin membrane A is V, and a=0, described skin membrane B satisfies following formula (1C)～(5C) or (1D)～(5D) (the present invention the 2nd aspect).

0≤1-x-y≤0.3 ... ... ... ... ... ... .... formula (1C)

0.1≤x≤0.3 ... ... ... ... ... ... ... .. formula (2C)

0.5≤y≤0.7 ... ... ... ... ... ... ... .. formula (3C)

Z=0 ... ... ... ... ... ... ... ... ... formula (4C)

A=1 ... ... ... ... ... ... ... ... ... formula (5C)

0≤1-x-y≤0.3 ... ... ... ... ... ... ... formula (1D)

0.1≤x≤0.3 ... ... ... ... ... ... ... ... formula (2D)

0.5≤y≤0.65 ... ... ... ... ... ... ... .. formula (3D)

0.01≤z≤0.1 ... ... ... ... ... ... .... formula (4D)

A=1 ... ... ... ... ... ... ... ... ... formula (5D)

The hard film-coated material of the 3rd invention, at the following skin membrane C that forms on the substrate surface that constitutes by steel more than the thickness 5 μ m, and, have and form first invention or second and invent described hard film and form (the present invention the 3rd aspect).

Skin membrane C:

A kind of by (Cr _aM _1-a) (C _1-yN _y) skin membrane that constitutes, it satisfies following formula (1E)～(2E).

0.2≤a.................................................. formula (1E)

0≤y≤1................................................. formula (2E)

Wherein, at above-mentioned (Cr _aM _1-a) (C _1-yN _y) in, M be among Ti, Al, Nb, W, Mo, the Si more than a kind; In following formula (1E)～(2E), a represents the atomic ratio of Cr, and y represents the atomic ratio of N.

Hard film of the present invention is compared with existing surface-coated layer, and mar proof is good, and coefficient of friction is low, and sliding is good, applicable to hard films such as mould and metallurgical instruments, thereby can realize the raising of its durability.Hard film-coated material of the present invention applicable to mould material and metallurgical instrument material, thereby can be realized the raising of its durability.

The specific embodiment

The present inventor to achieve these goals, carried out research with keen determination, it found that, by forming by among W, Mo, V, the Nb more than a kind and the lit-par-lit structure of the compound that constitutes more than a kind among B, C, the N [(W, Mo, V, Nb) (BCN)] layer and TiCrAlSi (CN) layer, thereby obtain under higher surface pressing, having the epithelium of sliding, specifically have the epithelium of low friction and mar proof concurrently.That is, by using (W, Mo, V, Nb) (BCN) compound, the friction reaction takes place in the effect of frictional heat and surface pressing during owing to slip, and W, the Mo of melting point, the oxide of V, Nb are hanged down in formation, thereby obtain low coefficient of friction.But problem points is, carries out oxidation when these monomers particularly at high temperature use very soon, and wearing and tearing are increased., make up for this reason, promptly form lit-par-lit structure by the TiCrAlSi good (CN) with oxidative resistance, thereby, even at high temperature also can successfully suppress carrying out fast of oxidation, and, low coefficient of friction obtained.

At this, as (W, Mo, V, Nb) (BCN) W, Mo, V, the Nb in the layer, can use wherein any, also can several elements mix and use, since the kind difference of element, the also different (Nb of the melting point of the oxide that forms during slip ₂O ₅: 1460 ℃; WO ₃: 1400 ℃; MoO ₃: 800 ℃; V ₂O ₅: 685 ℃), therefore, high temperature side uses, the preferred element of selecting to form high melting point oxide.

From with W, Mo, V, Nb more than a kind (M hereinafter referred to as) combine and form this point of hard nitride, N is absolutely necessary.According to the ratio of B, C, the ratio of N (atomic ratio) [ratio (atomic ratio), hereinafter referred to as ratio] is preferably more than 0.2, and is further preferred more than 0.5.First purpose of adding B is to be combined in N to form B-N in the epithelium and combine, and improves lubricity, and in addition, its part combines with M, the formation hard borides.Therefore, because the interpolation of B improves mar proof, agglutinating property, for this reason, the ratio of B is preferably more than 0.05, more preferably more than 0.1.But excessive interpolation can make soft BN compound too much, and for this reason, the ratio of B need be set in below 0.3, preferably sets below 0.2.

C combines with M and forms hard carbide, can realize high rigidityization thus, and therefore, the ratio of C is preferably set to more than 0.05.But the excessive interpolation of C forms the free C that does not combine with M, and for this reason, the ratio of C need be set in below 0.5, preferably sets below 0.3, further preferably sets below 0.2.

In TiCrAlSi (CN) layer, it is very important making film have oxidative resistance, and therefore, Al is an indispensable element.From improving the viewpoint of oxidative resistance, can add Cr, still, add Cr and surpass ratio 0.5, the amount of Al is reduced, oxidative resistance reduces, and therefore, the ratio of Cr need be set 0.5 and be the upper limit.Preferred Cr ratio is 0.05～0.4, further preferred 0.2～0.4.It is low that the ratio of Al is lower than 0.4 o'clock oxidative resistance, surpasses at 0.7 o'clock and be converted into soft hexagoinal lattice compound, and therefore, the ratio of Al need be set at 0.4～0.7, is preferably set to 0.5～0.65.Ti is after the upper limit is added, can obtain the high rigidity epithelium with ratio 0.5, still, adds when surpassing ratio 0.5, and oxidative resistance is significantly reduced, and therefore, the ratio of Ti need be set 0.5 and be the upper limit.Add simultaneously under the situation of Cr, the ratio of Ti is preferably below 0.3, and is further preferred below 0.25.Ratio by adding Si can improve oxidative resistance below 0.15, still since Si be added with the tendency that reduces epithelium hardness, therefore, the ratio of Si need be set 0.15 and be the upper limit, preferably sets below 0.1.When the ratio of ratio+Si of Al surpassed 0.7, the crystal structure of epithelium changed to soft hexagoinal lattice, and therefore, the ratio of ratio+Si of Al is preferably below 0.7.N is essential, and the ratio of N need be set at more than 0.5.Utilize the interpolation of C can realize high rigidityization and improve lubrication property, still, when surpassing ratio 0.5 interpolation C, oxygen resistenceization significantly reduces, and therefore, the ratio of C need be set in below 0.5, is preferably below 0.3.

The present invention is based on this discovery and finishes.The hard film of so finishing of the present invention, it is stacked more than 2 layers and the hard film that constitutes to be that following skin membrane A and skin membrane B add up to, wherein, the thickness of described skin membrane A is 5～100nm, and the thickness of described skin membrane B is 5～100nm (the present invention the 1st aspect).Hard film of the present invention is carried out layer with existing surface and is compared, and mar proof is good, and coefficient of friction is low, and sliding is good, applicable to hard films such as mould and tools, thereby realizes the raising of its durability.

Skin membrane A:

A kind of by M (B _aC _bN _1-a-b) skin membrane that constitutes, it satisfies following formula (1A)～(2A).

0≤a≤0.3...................................... formula (1A)

0≤b≤0.5...................................... formula (2A)

Wherein, at above-mentioned M (B _aC _bN _1-a-b) in, M be among W, V, Mo, the Nb more than a kind; In following formula (1A)～(2A), a represents the atomic ratio of B, and b represents the atomic ratio of C.

Skin membrane B:

A kind of by Ti _1-x-yCr _xAl _ySi _z(C _1-AN _A) skin membrane that constituted, it satisfies following formula (1B)～(5B).

0≤1-x-y≤0.5........................................... formula (1B)

0≤x≤0.5.......................................... formula (2B)

0.4≤y≤0.7........................................ formula (3B)

0≤z≤0.15......................................... formula (4B)

0.5≤A≤1.......................................... formula (5B)

Wherein, in following formula (1B)～(5B), x represents the atomic ratio of Cr, and y represents the atomic ratio of Al, and z represents the atomic ratio of Si, and A represents the atomic ratio of N.

In hard film of the present invention, why the thickness of skin membrane A is set at 5～100nm, is that performance descends because when the thickness of skin membrane A surpasses 100nm, the characteristic that should surpass the epithelium of 100nm will play a decisive role, and stacked effect can not be brought into play; On the other hand, lepthymenia when being lower than 5nm, the action effect of skin membrane A can not be brought into play.Why the thickness of skin membrane B is set at 5～100nm, is that performance descends because when the thickness of skin membrane B surpasses 100nm, the characteristic that should surpass the epithelium of 100nm will play a decisive role, and stacked effect can not be brought into play; On the other hand, lepthymenia when being lower than 5nm, the action effect of skin membrane B can not be brought into play.In view of this, the thickness of skin membrane A preferably sets below 50nm, further preferably sets below 20nm.The thickness of skin membrane B preferably sets below 50nm, further preferably sets below 20nm.

In skin membrane A, why set 0≤a (atomic ratio of B)≤0.3, be owing to when a surpasses 0.3, make soft BN compound too much, thereby hardness descend, mar proof descends, and the result is undesirable.Why setting 0≤b (atomic ratio of C)≤0.5, is owing to when b surpasses 0.5, generate the free C that does not combine with M, thereby mar proof descends, and the result is undesirable.

In skin membrane B, why set 0≤1-x-y (atomic ratio of Ti)≤0.5, be because when 1-x-y surpasses 0.5, oxidative resistance decline and undesirable.Why set 0≤x (atomic ratio of Cr)≤0.5,, when x surpasses 0.5, the amount of Al is reduced, oxidative resistance decline and undesirable though be because Cr can make oxidative resistance improve.Why set 0.4≤y (atomic ratio of Al)≤0.7, be because: when y is lower than 0.4, oxidative resistance difference and undesirable; When y surpasses 0.7, change to soft hexagoinal lattice compound, thereby hardness descends, mar proof descends, and the result is also undesirable.Why setting 0≤z (atomic ratio of Si)≤0.15, is that the result is undesirable thereby mar proof descends because when z surpassed 0.15, hardness descended.Why set 0.5≤A (atomic ratio of N)≤1, be since when A is lower than 0.5 hardness low, thereby mar proof difference and undesirable.The atomic ratio of why setting C is below 0.5, is because it surpasses at 0.5 o'clock, oxidative resistance difference and undesirable.

When the M in described skin membrane A is V,, therefore, under about serviceability temperature below 600 ℃, has most preferred sliding properties because V and W and Mo relatively, form the oxide of low melting point.M in described skin membrane A is under the situation of V, and when not containing B (during a=0), owing to the lubricant effect of V oxide makes coefficient of friction minimum, sliding properties improves.This can be estimated as: because the compound of V and B is unsettled on thermodynamics, hardness is also low, and when not containing B, such V and the compound of B can not form.

1-x-y among the described skin membrane B (atomic ratio of Ti), x (atomic ratio of Cr), y (atomic ratio of Al), z (atomic ratio of Si), A (atomic ratio of N) are set at: when when 0.1≤1-x-y≤0.3,0.1≤x≤0.3,0.5≤y≤0.7, z=0, A=1 or 0.1≤1-x-y≤0.3,0.1≤x≤0.3,0.5≤y≤0.65,0.01≤z≤0.1, A=1, it is the highest that hardness reaches.Wherein,, increase epithelium hardness, improve mar proof by setting 0.1≤1-x-y (atomic ratio of Ti).

In view of the above, the hard film of the present invention the 2nd aspect may be defined as: in the hard film aspect the present invention the 1st, the M among the skin membrane A is V, and a=0, and skin membrane B satisfies following formula (1C)～(5C) or (1D)～(5D).The hard film of the present invention the 2nd aspect, particularly mar proof is good, and coefficient of friction is low, and sliding is good.

0.1≤1-x-y≤0.3...................................... formula (1C)

0.1≤x≤0.3.......................................... formula (2C)

0.5≤y≤0.7.......................................... formula (3C)

Z=0................................................. formula (4C)

A=1................................................. formula (5C)

0.1≤1-x-y≤0.3...................................... formula (1D)

0.1≤x≤0.3.......................................... formula (2D)

0.5≤y≤0.65......................................... formula (3D)

0.01≤z≤0.1......................................... formula (4D)

A=1................................................. formula (5D)

Hard film of the present invention is the stacked epithelium that skin membrane A and skin membrane B are laminated.This stacked epithelium integral body is composite, has the characteristic of skin membrane A and the characteristic of skin membrane B concurrently, can bring into play its composite effect, makes stacked epithelium have excellent characteristic on the whole.This effect is based on the stacked of skin membrane A and skin membrane B and produces, promptly stacked effect.

In hard film of the present invention, the stacked number (number of plies of the number of plies of skin membrane A+skin membrane B) with regard to skin membrane A and skin membrane B is not particularly limited, and still, in order more effectively to bring into play above-mentioned stacked effect etc., preferred stacked number is more.Promptly, under the certain condition of the thickness (integral thickness of stacked epithelium) of hard film, stacked number situation how and few situation are compared, under the few situation of stacked number (for example 2 layers time), even on macroscopic view, skin membrane A and skin membrane B are also obviously uneven respectively, and be poor as the homogenieity of hard film integral body on material, homogenieity on the characteristic is low, and stacked effect is little; Relative therewith, under the many situations of stacked number, from microcosmic, though skin membrane A and skin membrane B are obviously uneven respectively,, on macroscopic view, skin membrane A and skin membrane B become state mixed in together, as the homogenieity height of hard film integral body, the homogenieity on the characteristic is good on material, and stacked effect is good.Therefore, preferred stacked number is more.In addition, under the few situation of stacked number (for example 2 layers time), the thickness of hard film (thick entirely) can not be very big, relative therewith, under the many situations of stacked number, the thickness of hard film can be very big, even under the very big situation of needed thickness, also guarantee the regulation thickness easily, also preferred in this stacked number is more.In view of this,, for example, be preferably set to more than 10, more preferably set more than 20, further preferably set N (number of from surpass 20 number, selecting) again with regard to stacked number.

In the hard film in the present invention, thickness (thick entirely) with regard to hard film, be not particularly limited, but more than the preferred thickness 0.1 μ m (100nm), this is because when thickness is lower than 0.1 μ m, the action effect of mar proof can not brought into play fully, might produce the consequence of mar proof deficiency.On the other hand, when thickness surpasses 20 μ m and increase thickness and compare, the raising effect of mar proof and oxidative resistance is little, and, applying time lengthening, efficient reduces, and therefore, preferably sets below the 20 μ m.

Go up stacked order and indefinite with regard to skin membrane A and skin membrane B to base material (or forming basic epithelium on base material), any that can be from skin membrane A and skin membrane B begins stacked, also can finish stacked in any of skin membrane A and skin membrane B.But, under the few situation of stacked number (for example 2～3 layers time), preferably make the coefficient of friction skin membrane A lower become the superiors than skin membrane B.

As the pressure forming with high-tension heavy steel plate is representative, owing to produce bigger surface pressing when being shaped on the surface of mould, thereby produces sintering, in addition, also produce since foreign matter etc. be involved in the mould damage that causes.This tendency is particularly remarkable in the low steel based material of base material hardness.The present inventor finds, on the problem of hard film of the present invention and base material, following skin membrane C is formed more than the thickness 5 μ m (500nm), thus, can suppress this sintering and foreign matter and be involved in caused mould damage.According to this discovery, hard film-coated material of the present invention on the surface of the base material that is made of steel, forms the above following skin membrane C of thickness 5 μ m, thereby, form hard film of the present invention and constitute (the present invention the 3rd aspect).The hard film-coated material of the present invention the 3rd aspect, the hard film-coated material (material of no bottom) that constitutes with form hard film of the present invention on the surface of steel substrate is compared, sintering resistance is good, be difficult for producing sintering, in addition, also be difficult for producing because of foreign matter is involved in the damage that causes, applicable to mould material and metallurgical instrument material.

Skin membrane C:

A kind of by (Cr _aM _1-a) (C _1-yN _y) skin membrane that constitutes, it satisfies following formula (1E)～(2E).

0.2≤a........................................ formula (1E)

0≤y≤1....................................... formula (2E)

Wherein, at above-mentioned (Cr _aM _1-a) (C _1-yN _y) in, M be among Ti, Al, Nb, W, Mo, the Si more than a kind; In following formula (1E)～(2E), a represents the atomic ratio of Cr, and y represents the atomic ratio of N.

At this, the thickness of why setting skin membrane C is more than the 5 μ m (5000nm), is because when being lower than 5 μ m, can not realize the raising of sintering resistance, and when 5 μ m were above, sintering resistance improves fully.In skin membrane C, why set 0.2≤a (atomic ratio of Cr), be because when a is lower than 0.2, can not improve the adaptation of steel substrate epithelial membrane.That is,, the atomic ratio of Cr among the skin membrane C is contained more than 0.2 in order to improve the adaptation of hard film on the steel substrate; And be lower than at 0.2 o'clock at the atomic ratio of Cr, then can not improve the adaptation of steel substrate epithelial membrane.In order to make this adaptation reach higher level, preferably a is set at more than 0.5.

By adding M (among Ti, Al, Nb, W, Mo, the Si more than a kind), the hardness of skin membrane C is improved.Especially Al, W, Ti, Mo effect that hardness is improved is big, therefore, from improving the hardness aspect, recommend to add among Al, W, Ti, the Mo more than a kind.On the other hand, mold materials has the situation that the electrochemical method dissolving of use membrane removal applies again in case the use back takes place under the situation of part damage.At this moment, if contain W and/or Mo in the epithelium, then the enhanced dissolution rate of epithelium removes membrane efficiency and improves.From this point, recommend to add W and/or Mo.

From improving the viewpoint of mar proof, the wearing layer on skin membrane C upper strata is more than the preferred 3 μ m of thickness of hard film of the present invention (the stacked epithelium of skin membrane A and skin membrane B), further more than the preferred 5 μ m.The thickness total of the thickness of skin membrane C and the wearing layer on upper strata (the stacked epithelium of skin membrane A and skin membrane B) is preferably more than the 10 μ m.

Below, embodiments of the invention and comparative example are described.In addition, the present invention is defined in this embodiment, can be fit in the scope of purport of the present invention, also can suitably be changed and implement, but these all is included in the technical scope of the present invention.

Example A

In film formation device with arc evaporation source and sputter vaporization source, use contains M (among W, V, the Mo more than a kind) or further contains the target of B and contain the target more than a kind among Ti, Cr, Al, the Si, forms the epithelium (stacked film) of the composition shown in table 1～2, stacked number, thickness.

At this moment, with regard to base material, the superhard alloy substrate that uses mirror ultrafinish to cross when the composition of epithelium, epithelium that hardness test is used form when the epithelium that sliding test is at high temperature used forms, uses SKD11 substrate (hardness HRC60).Under the situation that forms any epithelium, all be that substrate is imported in the chamber of film formation device, (be vented to 1 * 10 with vacuumizing in the chamber ^-3Pa is following) after, base material is heated to about 400 ℃, then, utilize the Ar ion to implement sputter clean.Afterwards, utilizing arc evaporation source to carry out under the situation of film forming, using the target of  100mm, the setting arc current is 150A, at the N of total pressure 4Pa ₂Atmosphere or N ₂+ CH ₄Mist in carry out film forming.In addition, when on base material, carrying out skin membrane A and skin membrane B stacked, begin stackedly from skin membrane B, on skin membrane A, finish stacked.That is, skin membrane B is above base material is direct, and skin membrane A is the superiors.

So forming in the test of epithelium, carry out the composition of epithelium, the investigation of hardness, carry out the sliding test under the high temperature again, mar proof and coefficient of friction are examined or check.

At this moment, the composition of epithelium utilizes EPMA to measure.About the hardness of epithelium, utilize micro Vickers, examine or check by under measuring load 0.25N, 15 seconds condition of minute, measuring.Sliding test under the high temperature is carried out under following high temperature sliding test condition.

High temperature sliding test condition:

Device: blade connection collar plate shape sliding test device

Blade: SKD 61 steel (HRC50)

Disk: go up the formation epithelium at SKD 11 steel (HRC60)

Sliding speed: 0.1m/ second

Load: 500N

Sliding distance: 500m

Test temperature: 500 ℃

The result of above-mentioned test is shown in table 3～4.In addition, in table 1～2, the value of forming in the hurdle is the value of atomic ratio, stacked number is the number of plies of the number of plies+layer B of layer A, total film thickness is thick entirely (down together) of stacked film, by table 1～2, table 3～4 as can be known, the hard film that satisfies the present invention's the 1st aspect necessary condition is the present invention the 1st aspect example (No.7～12,14～24,26～28,30～32,35～37,39～43,45～46,48～50), what invent the 1st aspect necessary condition with discontented unabridged version is comparative example (No.1～5,6,13,25,29,33,34,38,44,47) compare, coefficient of friction is little and sliding is good, and film specific wear amount is few and mar proof is good.

Example B

The same method of situation of utilization and above-mentioned routine A, the epithelium (stacked film) of the composition shown in the formation table 8, stacked number, thickness uses the same method and carries out same test.The result of this test is as shown in table 9.By table 8, table 9 as can be known, the hard film that satisfies the present invention's the 1st aspect necessary condition is the present invention's the 1st aspect example (No.2d～5d, 8d～9d, 11d), (No.1d, 6d, 7d, the 10d) that invent the 1st aspect necessary condition with discontented unabridged version compares, coefficient of friction is little and sliding is good, and film specific wear amount is few and mar proof is good.In addition, comparative example (No.1～5,6,13,25,29,33,34,38,44,47 in table 1～2, table 3～4) among this present invention's the 1st aspect example (No.2d～5d, 8d～9d, 11d) and the above-mentioned routine A compares, coefficient of friction is little and sliding is good, and film specific wear amount is few and mar proof is good.

Example C

The same method of situation of utilization and above-mentioned routine A, the epithelium (stacked film) of the composition shown in the formation table 5, stacked number, thickness uses the same method and carries out same test.The result of this test is as shown in table 6.By table 5, table 6 as can be known, the hard film that satisfies the present invention's the 2nd aspect necessary condition is the present invention's the 2nd aspect example (No.7a, 8a, 12a, 15a～21a), compare with the present invention's the 2nd aspect necessary condition and the present invention's the 1st aspect necessary condition all ungratified (No.1a～4a, 9a, 10a), coefficient of friction is little and sliding is good, and film specific wear amount is few and mar proof is good; Even compare, also be that coefficient of friction is little and sliding is good, and film specific wear amount is few and mar proof is good with (No.6a, 11a, 13a, the 14a) that only satisfy the present invention's the 1st aspect necessary condition (discontented unabridged version invent the 2nd aspect necessary condition).

Example D

The same method of situation of utilization and above-mentioned routine A forms the composition shown in the table 7, the bottom (skin membrane C) of thickness, and then forms the composition shown in the table 7, the epithelium (stacked film) of stacked number.In addition, carry out when stacked, begin stackedly from skin membrane B, on skin membrane A, finish stacked at skin membrane A and skin membrane B.

So forming in the test of epithelium, the same method of situation of utilization and above-mentioned routine A is examined or check composition, the hardness of epithelium.In addition, carry out the sliding test under the high temperature, examine or check its sintering resistance.Sliding test under this high temperature is carried out under following high temperature sliding test condition.

High temperature sliding test condition:

Device: blade connection collar plate shape sliding test device

Blade: SKD 61 steel (HRC50)

Disk: go up the formation epithelium at SKD 11 steel (HRC11)

Sliding speed: 0.1m/ second

Load: 500N-1000N increases load with the rate of change tilting ground of 100N/100m, and examination is from the load to sintering damaged of epithelium.

Test temperature: 500 ℃

The result of above-mentioned test is as shown in table 7.As shown in Table 7, have every hard film (stacked film of skin membrane A and skin membrane B) that all satisfies the necessary condition of the present invention the 1st aspect, the composition of this hard film, thickness, stacked number are identical.Have in the below of this hard film (stacked film) skin membrane C more than the thickness 5 μ m that satisfy the necessary condition aspect the present invention the 3rd as bottom (No.3c～12c), compare with (No.1c) that do not have bottom, sintering load is big so sintering resistance is good.In the example of No.3c～12c, the identical example of composition of bottom (skin membrane C) is compared as can be known, its thickness is thick more, thus the big more sintering resistance of sintering load is good more.In addition, the example of No.2c has the bottom of the composition necessary condition of the skin membrane C that satisfies the present invention the 3rd aspect, but this thickness is 3000nm (3 μ m), does not satisfy more than the 5 μ m, and its sintering load is same level with (No.1c) that do not have bottom.

Table 1

SP: sputter * A, the B layer was on base material when B was stacked, and the A layer is the superiors

AIP: electric arc

Table 2

No.	Film build method	Layer A								Layer B							Stacked number	Total thickness of slab nm
																			Form							Thickness nm	Form						Thickness nm
		V	W	Mo	Nb	B	C	N	Ti	Cr	Al	Si	C	N
															26	SP			0.3	0	0.7	0	0	0.2	0.80		30	0.2	0.2	0.55	0.05	0		1.00	30	50	3000
27	SP	0.3	0	0.7	0	0	0.3	0.70	30	0.2	0.2	0.55	0.05	0			1.00	30								50							3000
															28	SP			0.3	0	0.7	0	0	0.5	0.50		30	0.2	0.2	0.55	0.05	0		1.00	30	50	3000
29	SP	0.3	0	0.7	0	0	0.7	0.30	30	0.2	0.2	0.55	0.05	0			1.0	30								50							3000
															30	AIP			0.8	0.2	0	0	0	0	1.00		30	0	0.4	0.6	0	0		1.00	30	50	3000
31	AIP	0.8	0.2	0	0	0	0	0	30	0.2	0.2	0.6	0	0			1.00	30								50							3000
															32	AIP			0.8	0.2	0	0	0	0	1.00		30	0.3	0.1	0.6	0	0		1.00	30	50	3000
33	AIP	0.8	0.2	0	0	0	0	1.00	30	0.4	0.1	0.5	0	0			1.00	30								50							3000
															34	SP			0.4	0.2	0.4	0	0	0	1.00		40	0.2	0	0.8	0	0		1.00	40	37	3000
35	SP	0.4	0.2	0.4	0	0	0	1.00	40	0.3	0.05	0.65	0	0			1.00	40								37							3000
															36	SP			0.4	0.2	0.4	0	0	0	1.00		40	0.2	0.25	0.55	0	0		1.00	40	37	300O
37	SP	0.4	0.2	0.4	0	0	0	1.00	40	0.1	0.5	0.4	0	0			1.00	40								37							300
															38	SP			0.4	0.2	0.4	0	0	0	1.00		40	0.1	0.7	0.2	0	0		1.00	40	37	3000
39	SP	0.4	0.2	0.4	0	0	0	1.00	40	0.1	0.2	0.7	0	0			1.00	40								37							3000
															40	AIP			0.9	0	0.1	0	0	0	1.00		35	0.2	0.2	0.6	0	0		1.00	40	40	3000
41	AIP	0.9	0	0.1	0	0	0	1.00	35	0.2	0.2	0.55	0.05	0			1.00	40								40							3000
															42	AIP			0.9	0	0.1	0	0	0	1.00		35	0.2	0.2	0.5	0	0		1.00	40	40	3000
43	AIP	0.9	0	0.1	0	0	0	1.00	35	0.15	0.2	0.5	0.15	0			1.00	40								40							300O
															44	AIP			0.9	0	0.1	0	0	0	1.00		35	0.1	0.2	0.5	0.2	0		1.00	40	40	3000
45	SP	0	0.2	0.8	0	0	0	1.00	30	0.2	0.2	0.55	0.05	0.2			0.80	30								50							3000
															46	SP			0	0.2	0.8	0	0	0	0.8		30	0.2	0.2	0.55	0.05	0.5		0.50	30	50	3000
47	SP	0	0.2	0.8	0	0	0	1.00	30	0.2	0.2	0.55	0.05	0.7			3000	30								50							3000
															48	AIP			0	0	0	1	0	0	1.00		25	0.2	0.2	0.55	0.05	0		1.00	20	66	3000
49	AIP	0.5	0	0	0.5	0	0	1.00	26	0.2	0.2	0.55	0.05	0			1.00	20								66							3000
															50	AIP			0	0.5	0	0.5	0	0	1.00		25	0.2	0.2	0.55	0.05	0		1.00	20	66	3000

SP: sputter * A, when B is stacked on the B layer base for post material, the A layer is the superiors

AIP: electric arc

Table 3

No.	Hardness Gpa	Behind the coefficient of friction 300m	Film specific wear amount * 10E-10mm3/Nm
				6	31	0.45	11.00
7	33	0.35	6.00
				8	35	0.3	5.00
9	35	0.3	4.80
				10	33	0.3	5.00
11	33	0.4	7.00
				12	32	0.5	7.50
13	29	0.58	12.00
				14	32	0.3	5.50
15	32	0.3	6.00
				16	36	0.3	4.40
17	36	0.3	6.50
				18	35	0.3	7.30
19	34	0.34	5.60
				20	35	0.37	4.70
21	35	0.36	4.80
				22	36	0.3	5.00
23	33	0.27	4.50
				24	31	0.3	8.00
25	28	0.3	15.00
				4	25	0.35	15.00
5	29	0.6	10.00
				1	25	0.7	20.00
2	28	0.6	15.00
				3	20	0.5	12.00

Table 4

No.	Hardness GPa	Behind the coefficient of friction 300m	Film specific wear amount * 10E-10mm3/Nm
				26	36	0.38	4.40
27	35	0.4	4.20
				28	32	0.45	7.50
29	29	0.58	13.00
				30	33	0.34	4.50
31	35	0.37	5.20
				32	33	0.39	6.40
33	31	0.45	15.00
				34	28	0.4	17.00
35	31	0.42	7.50
				36	35	0.34	4.50
37	30	0.4	6.00
				38	27	0.45	13.00
39	36	0.37	4.10
				40	33	0.4	5.50
41	36	0.37	3.90
				42	34	0.37	3.70
43	33	0.4	6.50
				44	29	0.45	14.00
45	36	0.35	3.00
				46	33	0.33	5.00
47	27	0.32	11.00
				48	35	0.45	4.20
49	33	0.4	4.50
				50	33	0.47	5.10

Table 5

No.	Film build method	Layer A							Layer B							Stacked number	Total thickness of slab nm
																		Form						Thickness nm	Form						Thickness nm
		V	W	Mo	B	C	N	Ti	Cr	Al	Si	C	N
														6a	AIP			1	0	0	0	0	1.00		30	0	0.4	0.6	0	0		1.00	30	50	3000
7a	AIP	1	0	0	0	0	1.00	30	0.2	0.2	0.6	0	0			1.00	30							50							3000
														8a	AIP			1	0	0	0	0	1.00		30	0.3	0.1	0.6	0	0		1.00	30	50	3000
9a	AIP	1	0	0	0	0	1.00	30	0.4	0.1	0.5	0	0			1.00	30							50							3000
														10a	AIP			1	0	0	0	0	1.00		30	0.2	0	0.8	0	0		1.00	30	50	3000
11a	AIP	1	0	0	0	0	1.00	30	0.3	0.05	0.65	0	0			1.00	30							50							3000
														12a	AIP			1	0	0	0	0	1.00		30	0.2	0.25	0.55	0	0		1.00	30	50	3000
13a	AIP	1	0	0	0	0	1.00	30	0.1	0.5	0.4	0	0			1.00	30							50							3000
														14a	AIP			1	0	0	0	0	1.00		30	0.3	0.3	0.4	0	0		1.00	30	50	3000
15a	AIP	1	0	0	0	0	1.00	30	0.25	0.25	0.5	0	0			1.00	30							50							3000
														16a	AIP			1	0	0	0	0	1.00		30	0.2	0.2	0.6	0	0		1.00	30	50	3000
17a	AIP	1	0	0	0	0	1.00	30	0.1	0.2	0.7	0	0			1.00	30							50							3000
														18a	AIP			1	0	0	0	0	1.00		30	0.2	0.2	0.6	0	0		1.00	30	50	3000
19a	AIP	1	0	0	0	0	1.00	30	0.2	0.2	0.55	0.05	0			1.00	30							50							3000
														20a	AIP			1	0	0	0	0	1.00		30	0.2	0.2	0.5	0.1	0		1.00	30	50	3000
21a	AIP	1	0	0	0	0	1.00	30	0.15	0.2	0.5	0.15	0			1.00	30							50							3000
														4a				1	0	0	0	0	1.00		3000	Do not have.						0		3000
1a		(Ti0.5Al0.5)N																						3000
															2a				(Ti0.1Cr0.4Al0.5)N															3000
3a		(Ti0.5Al0.5)N+MoS2																																	3000

SP: sputter * A, the B layer was on base material when B was stacked, and the A layer is the superiors

AIP: electric arc

Table 6

No.	Hardness Gpa	Behind the coefficient of friction 300m	Film specific wear amount * 10E-10mm3/Nm
				6a	31	0.34	7.50
7a	35	0.37	5.20
				8a	33	0.39	4.50
9a	31	0.45	15.00
				10a	28	0.4	17.00
11a	31	0.34	5.50
				12a	35	0.34	4.00
13a	30	0.4	6.00
				14a	31	0.4	6.50
15a	34	0.42	4.00
				16a	36	0.37	2.50
17a	36	0.37	3.50
				18a	33	0.4	5.50
19a	36	0.37	2.70
				20a	34	0.37	3.70
21a	33	0.4	6.50
				4a	25	0.35	15.00
1a	25	0.7	20.00
				2a	28	0.6	15.00
3a	20	0.6	12.00

Table 7

No.	Bottom		Layer A		Layer B		Stacked number	Sintering load N
									Form	Thickness nm	Form	Thickness nm	Form	Thickness nm
	1c	Do not have	0	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N									30	50	600
2c							(Cr0.8W0.2)N	3000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N	30	50	600
	3c	(Cr0.8W0.2)N	5000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N									30	50	800
4c							(Cr0.8W0.2)N	7000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N	30	50	900
	5c	(Cr0.8W0.2)N	10000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N									30	50	＞1000
6c							(Cr0.8W0.2)N	15000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N	30	50	＞1000
	7c	CrN	10000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N									30	50	900
8c							(Cr0.8Al0.2)N	10000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N	30	50	＞1000
	9c	(Cr0.8Ti0.2)N	10000	VN	30	(T0.2Cr0.2Al0.55Si0.05)N									30	50	＞1000
10c							(Cr0.8Mo0.2)N	10000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N	30	50	＞1000
	11c	(Cr0.8Nb0.2)N	10000	VN	30	(Ti0.2C0.2Al0.55Si0.05)N									30	50	900
12c							(Cr0.8Si0.2)N	10000	VN	30	(Ti0.2Cr0.2Al0.55Si0.05)N	30	50	900

Table 8

No.	Film build method	Layer A								Layer B							Stacked number	Total film thickness nm
																			Form							Thickness nm	Form						Thickness nm
		V	W	Mo	Nb	B	C	N	Ti	Cr	Al	Si	C	N
															1d	AIP			0	0	0	1	0	0	1		1	0.2	0.2	0.55	0.05	0		1.00	1	1500	3000
2d	AIP	0	0	0	1	0	0	1	10	0.2	0.2	0.55	0.05	0			1.00	10								150							3000
															3d	AIP			0	0	0	1	0	0	1		25	0.2	0.2	0.55	0.05	0		1.00	25	60	3000
4d	AIP	0	0	0	1	0	0	1	80	0.2	0.2	0.55	0.05	0			1.00	80								18							3000
															5d	AIP			0	0	0	1	0	0	1		100	0.2	0.2	0.55	0.05	0		1.00	100	15	3000
6d	AIP	0	0	0	1	0	0	1	150	0.2	0.2	0.55	0.05	0			1.00	150								10							3000
															7d	AIP			1	0	0	0	0	0	1		25	0.2	0	0.8	0	0		1.00	25	60	3000
8d	AIP	1	0	0	0	0	0	1	25	0.3	0	0.7	0	0			1.00	25								60							3000
															9d	AIP			1	0	0	0	0	0	1		25	0.5	0	0.5	0	0		1.00	25	60	3000
10d	AIP	1	0	0	0	0	0	1	25	0.6	0	0.4	0	0			1.00	25								60							3000
															11d	AIP			1	0	0	0	0	0	1		25	0.4	0	0.55	0.05	0		1.00	25	60	3000

Table 9

No.	Hardness GPa	Behind the coefficient of friction 300m	Film specific wear amount * 10E-10mm3/Nm
				1d	29	0.4	11
2d	36	0.4	5.3
				3d	37	0.4	3
4d	35	0.4	4.3
				5d	34	0.45	6.7
6d	28	0.5	12.5
				7d	28	0.55	13
8d	33	0.37	5.6
				9d	34	0.35	6.1
10d	29	0.51	11
				11d	35	0.35	4.3

In addition, in above routine A～routine D, carry out when stacked at skin membrane A and skin membrane B, all be to begin stacked from skin membrane B, finish at skin membrane A stacked, skin membrane B base material directly above (situation of routine C be the bottom on the base material directly above), skin membrane A is the superiors; As replace, begin stackedly from skin membrane B, finish stacked at skin membrane B, or begin stackedly from skin membrane A, and finish stackedly at skin membrane B, or begin stacked from skin membrane A, stacked in skin membrane A end, all can obtain under wherein arbitrary situation and routine A～same result of routine D.

Hard film of the present invention is compared with existing surface-coated layer, and mar proof is good, and simultaneously, coefficient of friction is low and sliding is good, and the applicable hard film of making mould and tool etc. is effective to the raising that realizes its durability.

Claims (4)

1. hard film, it is laminated by following skin membrane A and skin membrane B, and the total number of plies of described skin membrane A and skin membrane B is more than 2 layers, it is characterized in that the thickness of described skin membrane A is 5～100nm, and, the thickness of described skin membrane B is 5～100nm

Skin membrane A:

Be by M (B _aC _bN _1-a-b) skin membrane that constitutes, satisfy following formula (1A)～(2A),

0≤a≤0.3 ... formula (1A)

0≤b≤0.5 ... formula (2A)

Wherein, at above-mentioned M (B _aC _bN _1-a-b) in, M be among W, V, Mo, the Nb more than a kind, in following formula (1A)～(2A), a represents the atomic ratio of B, b represents the atomic ratio of C;

Skin membrane B:

Be by Ti _1-x-yCr _xAl _ySi _z(C _1-AN _A) skin membrane that constitutes, satisfy following formula (1B)～(5B),

0≤1-x-y≤0.5 ... formula (1B)

0≤x≤0.5 ... formula (2B)

0.4≤y≤0.7 ... formula (3B)

0≤z≤0.15 ... formula (4B)

0.5≤A≤1 ... formula (5B)

Wherein, in following formula (1B)～(5B), x represents the atomic ratio of Cr, and y represents the atomic ratio of Al, and z represents the atomic ratio of Si, and A represents the atomic ratio of N.

2. hard film as claimed in claim 1 is characterized in that, the M among the described skin membrane A is V, and a=0, and described skin membrane B satisfies following formula (1C)～(5C) or following formula (1D)～(5D),

0.1≤1-x-y≤0.3 ... formula (1C)

0.1≤x≤0.3 ... formula (2C)

0.5≤y≤0.7 ... formula (3C)

Z=0 ... formula (4C)

A=1 ... formula (5C)

0.1≤1-x-y≤0.3 ... formula (1D)

0.1≤x≤0.3 ... formula (2D)

0.5≤y≤0.65 ... formula (3D)

0.0 1≤z≤0.1 ... formula (4D)

A=1 ... formula (5D).

3. a hard film-coated material is characterized in that, it is at the following skin membrane C that forms on the substrate surface that is made of steel more than the thickness 5 μ m, and forms the described hard film of claim 1 and constitute on skin membrane C,

Skin membrane C:

Be by (Cr _aM _1-a) (C _1-yN _y) skin membrane that constitutes, satisfy following formula (1E)～(2E),

0.2≤a ... formula (1E)

0≤y≤1 ... formula (2E)

Wherein, at above-mentioned (Cr _aM _1-a) (C _1-yN _y) in, M be among Ti, Al, Nb, W, Mo, the Si more than a kind, in following formula (1E)～(2E), a represents the atomic ratio of Cr, y represents the atomic ratio of N.

4. a hard film-coated material is characterized in that, at the following skin membrane C that forms on the substrate surface that constitutes by steel more than the thickness 5 μ m, and on skin membrane C, form the described hard film of claim 2 and constitute,

Skin membrane C:

Be by (Cr _aM _1-a) (C _1-yN _y) skin membrane that constitutes, satisfy following formula (1E)～(2E),

0.2≤a ... formula (1E)

0≤y≤1 ... formula (2E)

Wherein, at above-mentioned (Cr _aM _1-a) (C _1-yN _y) in, M be among Ti, Al, Nb, W, Mo, the Si more than a kind, in following formula (1E)～(2E), a represents the atomic ratio of Cr, y represents the atomic ratio of N.