CN1818125A - Hard coating, target for forming hard coating, and method for forming hard coating - Google Patents

Abstract

The present invention attempts to provide a hard coating which has excellent hardness and lubricity. Such attempt has been completed by providing a hard coating comprising (Al(1-a)Va) (C(1-X)NX), wherein 0.27 <= a <= 0.75, and 0.3 <= X <= 1, a and X respectively represent atom tatio.

Description

Hard coat forms hard coat target of using and the method that forms hard coat

Technical field

The present invention relates to a kind of cutting tool such as shovel, brill and end mill of being used for, forging die and anchor clamps, and such as the hard coat in the instrument of block stamp; A kind of target that is used to form this coating; And a kind of method that deposits hard coat.

Background technology

Cutting tool has wear resistance by the hard coat that forms TiN, TiCN, TiAlN etc. on the base material of rapid steel, Wimet, sintering metal etc.Particularly, forming under the situation of hard coat on the high speed cutting instrument or the Hardening Of Steel cutting tool that for example hardens, TiAlN is favourable selection.Along with the increase of the hardness of the material that recent cutting tool cut and the raising of cutting speed, highly need a kind of hard coat with wear resistance of improvement.For example, JP-A No.2003-71610 discloses and has used TiCrAlN to replace TiAlN improving the ratio that has the A1N of rock salt structure in the coating, thereby improves coating hardness when having oxidation-resistance.

Yet, comprise the hard coat of TiAlN or TiCrAlN, although improved the oxidation-resistance under the high temperature, oilness deficiency.Therefore, the cutting tool that is formed with such hard coat on it often runs into the part work piece and sticks to the lip-deep problem of cutting tool in the cutting operation process.The problem that anchor clamps and instrument such as forging die (forging dye) and block stamp also exist surface in contact place friction resistance excessively to increase, and forge and extrusion process in occur work material sometimes and cure situation on anchor clamps and instrument.

Summary of the invention

The present invention considers aforesaid situation and finishes, and an object of the present invention is to provide and a kind ofly have the excellent hardness and the hard coat of oilness, and correlation technique.

According to an aspect of the present invention, provide a kind of hard coat that overcomes above-mentioned situation.This hard coat is

(1) a kind of hard coat, it comprises (Al _1-aV _a) (C _1-XN _X), wherein

0.27≤a≤0.75, and

0.3≤X≤1，

Wherein a and X represent atom ratio independently; Perhaps

(2) a kind of hard coat, it comprises (Al _1-a-b-cV _aSi _bB _c) (C _1-XN _X), wherein

0.1≤a≤0.75，

0＜b+c≤0.20, and

0.3≤X≤1，

Wherein a, b, c and X represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c can be 0 simultaneously.

Hard coat can be the multilayer hard coat, and such multilayer hard coat can roughly be divided into following two embodiments.First embodiment of multilayer hard coat is a kind of multilayer hard coat of making by the repeated deposition thin layer, and described thin layer comprises the nitride or the carbonitride of at least a element that is selected from Al, V, Si and B.It periodically is no more than 80nm, and satisfies the composition of above-mentioned (1) or (2) the average composition, and described average composition is to multiply each other by composition and thickness with each layer, and the thickness of product summation divided by whole layers is calculated.Second embodiment of multilayer hard coat is by repeated deposition thin layer (a) and a kind of multilayer hard coat of (b) making, wherein (a) comprises the thin layer of the nitride of TiAl or carbonitride and/or comprises the nitride of CrAl or the thin layer of carbonitride, and (b) has and satisfy the thin layer of the composition of hard coat as mentioned above.It periodically is no more than 80nm.

Hard coat (comprising the multilayer hard coat) preferably has the NaCl-type crystal structure.The hardness of the existing excellence of hard coat of the present invention has excellent oilness again.

Hard coat (comprising the multilayer hard coat) can be that a kind of being coated with is deposited upon (the following lamination hard coat that is called sometimes) on the another kind of coating.In such lamination hard coat, the hard coat difference that each hard coat is adjacent.

Hard coat can be deposited on (comprising multilayer hard coat and lamination hard coat) one or two surface of (1) different hard coat or (2) metal level or alloy layer and go up (following be called sometimes compound hard coat).

(1) example of different hard coats comprises: the hard coat that comprises metal nitride, metal carbonate or carbonitride with NaCl-type crystal structure.

(2) example of metal level or alloy layer comprises: be selected from least a element among element, Al and the Si of periodic table of elements 4A, 5A and 6A family and the layer of alloy thereof.

Mo and/or W can also be contained in hard coat (1) and (2), that is, these coatings can be

(3) a kind of hard coat, it comprises (Al _1-a-d-eV _aMo _dW _e) (C _1-XN _X), wherein

0.2≤a≤0.75，

0＜d+e≤0.3, and

0.3≤X≤1，

Wherein a, d, e and X represent atom ratio independently, and precondition is that d and e are not 0 simultaneously, and among d and the e can be 0 simultaneously, perhaps

(4) a kind of hard coat, it comprises (Al _1-a-b-c-d-eV _aSi _bB _cMo _dW _e) (C _1-XN _X), wherein

0.2≤a≤0.75，

0＜b+c≤0.20，

0＜d+e≤0.3, and

0.3≤X≤1，

Wherein a, b, c, d, e and X represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0, and d and e be not 0 simultaneously, and among d and the e one can be 0.

The hard coat that contains Mo and/or W is when being used for cutting tool under 600 ℃ or higher hot conditions, excellent especially aspect oilness and weather resistance.

Zr and/or Hf can also be contained in hard coat (1) and (2), that is, these coatings can be

(5) a kind of hard coat, it comprises (Al _1-a-f-gV _aHf _fZr _g) (C _1-XN _X), wherein

0.01≤a≤0.75，

0＜f+g≤0.5, and

0.3≤X≤1，

Wherein a, f, g and X represent atom ratio independently, and precondition is that f and g are not 0 simultaneously, and among f and the g can be 0 simultaneously, perhaps

(6) a kind of hard coat, it comprises (Al _1-a-b-c-f-gV _aSi _bB _cHf _fZr _g) (C _1-XN _X), wherein

0.01≤a≤0.75，

0＜b+c≤0.20，

0＜f+g≤0.5, and

0.3≤X≤1，

Wherein a, b, c, f, g and X represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0, and f and g be not 0 simultaneously, and among f and the g one can be 0.

The hard coat that contains Zr and/or Hr under 600 ℃ or higher hot conditions excellent especially aspect the hardness.

Hard coat (3) to (6) can preferably have the NaCl-type crystal structure.

Further preferably a kind of lamination hard coat, it comprises the layer (below be called a layer A) of the hard coat that comprises above-mentioned (1) or (2) and comprises by selecting layer (below be called a layer B) of at least a compound that obtains among at least a and C and the N among Mo and the W.In this case, the thickness of layer A and layer B is preferably such: thickness≤200nm of thickness≤layer A of layer B.

Equally preferably a kind of lamination hard coat, it comprises the hard coat that comprises in above-mentioned (1) or (2) any (below be called a layer A) and comprises by selecting layer (below be called a layer C) of at least a compound that obtains among at least a and C and the N among Zr and the Hf.In this case, the thickness of layer A and layer C is preferably such: thickness≤200nm of thickness≤layer A of layer C.

According to a further aspect in the invention, provide a kind of hard coat by the arc ions electroplating deposition.This coating is to be sedimentary by the target below using in the gas of N of 30 to 100 atom % containing with respect to N and C summation: comprise (Al _1-aVa) target, 0.27≤a≤0.75 wherein, wherein a represents atom ratio, perhaps comprises (Al _1-a-b-cV _aSi _bB _c) target, 0.1≤a≤0.75 and 0＜b+c≤0.20 wherein, wherein a, b and c represent atom ratio independently, precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0.

In accordance with a further aspect of the present invention, provide a kind of target that is used to deposit hard coat.This target comprises following element (i) any in (iv):

(i) Al and V,

(ii) Al, V and Si,

(iii) Al, V and B and

(iv) Al, V, Si and B,

And the relative density of target is not less than 95%.

The present invention also provides a kind of target that is used to deposit hard coat, and it comprises

(Al _1-aV _a), wherein

0.27≤a≤0.75，

Wherein a represents atom ratio, and

A kind of target that is used to deposit hard coat, it comprises

(Al _1-a-b-cV _aSi _bB _c), wherein

0.1≤a≤0.75, and

0＜b+c≤0.20，

Wherein a, b and c represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0.

Hard coat can for example, be used for Ionized film forming atmosphere evaporated metal in order to the below manufactured, and promotes the plasma bodyization and the described ionization that is used for the metal of deposited coatings of film forming gas.

More specifically, constitute in the arc ions plating of metal of target by arc-over evaporation and ionization therein, be formed on the upwardly extending parallel or magnetic line of force dispersed in the side of the water surface of evaporation that is substantially perpendicular to target, and near target part, promote the plasma bodyization of film forming gas by these magnetic line of force that are used for deposited coatings.

In this stage, the magneticflux-density of surface that will apply the target part of hard coat is not less than 10 Gausses.In addition, preferably between target and target part, form magnetic field, make the angle that forms between magnetic line of force and the described target evaporation normal to a surface be no more than ± 30 °.

In hard coat of the present invention, the Al in Al nitride or the Al carbonitride hard coat is replaced by an amount of V, and therefore, it has excellent hardness and oilness.Can prolong the work-ing life with cutting tool of such hard coat, and have the anchor clamps and less the blocking of instrument meeting of such hard coat.

Description of drawings

Embodiment of the present invention will be described in detail based on the following drawings, wherein:

Fig. 1 is the synoptic diagram of the manufacturing installation that uses in the manufacture method of the present invention.

Fig. 2 is near the synoptic diagram that shows the distribution of the magnetic line of force that forms in the manufacture method of the present invention target part.

Fig. 3 is near the synoptic diagram that shows the distribution of the magnetic line of force that forms in the manufacture method of the present invention target part.

Fig. 4 is the synoptic diagram that is presented at the distribution of the magnetic line of force that forms in the conventional arc ions plating.

Fig. 5 is the synoptic diagram of the manufacturing installation that uses in the manufacture method of the present invention.

Embodiment

The present inventor has prepared various hard coats, and crystalline structure, hardness, surface friction drag and weather resistance to these coatings when they are deposited on the cutting tool are assessed, and be a kind of than TiAlN and the better coating of TiAlCN hard coat (the following TiAl-based hard coating that is commonly referred to as sometimes) to find out.So, the inventor finds, by V and Al are made up nitride and carbonitride (for example, VAlN and the VAlCN that replaces Ti to make, below, VAlN and VAlCN are commonly referred to as the VAl-based hard coating sometimes) have excellent hardness and an oilness (surface friction drag).The present invention is based on such discovery.

More specifically, when making the VAl-based hard coating, it is believed that the heat of friction that produces by boundary between target part or work piece and hard coat preferentially to form V oxide compound (V when replacing the Ti of TiAl-based hard coating with V ₂O ₅Deng), because V is the oxidation of phase commute, and, it is believed that the friction resistance at such boundary hard coat diminishes because this V oxide compound is softer relatively and fusing point is relatively low.In addition, under the situation of VAl-based hard coating, as long as keep the NaCl-type crystal structure (to be also referred to as rock salt structure, isometric system etc.), hardness improves along with the increase of Al ratio, and when the Al ratio was too high, the collapse of NaCl-type crystal structure produced hexagonal system (being also referred to as ZnS type etc.) and coating deliquescing.Under the situation of VAl-based hard coating, in an Al concentration range wideer, keep isometric system, thereby realize the remarkable improvement of coating hardness than TiAl-based hard coating.Therefore, the VAl-based hard coating has excellent hardness and excellent oilness simultaneously.

Such VAl-based hard coating can be expressed as (Al _1-aV _a) (C _1-XN _X), wherein " a " and " X " represents atom ratio independently." a " is not less than 0.27.When " a " too hour, the ratio of Al is with too high, coating will be taked hexagonal system structure, thereby cause hardness descend (frictional coefficient increase).Preferably " a " is not less than 0.3, particularly is not less than 0.35.Along with the increase of " a " value, hardness and oilness are improved.But when " a " is worth when too high, the Strain Accumulation of using Al to produce under the situation that V reduces causes hardness to descend and the frictional coefficient increase.Therefore, preferred " a " is not more than 0.75, preferably is not more than 0.6, more preferably no more than 0.5.

Although " X " can be 1 (that is, hard coat can be a nitride), the oilness of coating increases along with the decline (that is the increase of " C " amount) of " X " value., low excessively " X " causes the formation of unsettled AlC compound probably.Therefore, preferred " X " is not less than 0.3, preferably is not less than 0.4, and more preferably 0.5, and most preferably be not less than 0.6.

Can also be combined with Si and/or B in the VAl-based hard coating.Have the Si of adding and/or the VAl-based hard coating of B like this and can be expressed as (Al _1-a-b-cV _aSi _bB _c) (C _1-XN _X).Should be noted in the discussion above that (Al _1-a-b-cV _aSi _bB _c) (C _1-XN _X) not only comprise the wherein compound of B formation carbonitride, and (Al _1-a-b-cV _aSi _bB _c) (C _1-XN _X) typically refer to and comprise that wherein B and Al, V and Si form those compound of boride.In the formula, " a ", " b ", " c " and " X " represent atom ratio independently.The adding of Si and/or B causes in the VAl-based hard coating grain-size littler, thereby improves hardness.Accurately do not find at present the mechanism that crystal size reduces as yet.But, it is believed that grain growing has been subjected to the inhibition of the formation of Si-N key and B-N key in the crystal boundary.Have in the VAl hard coat of Si and/or B in adding, the value of " a " is not less than 0.1 (preferably be not less than 0.27, more preferably be not less than 0.3, and most preferably be not less than 0.35), and is not more than 0.75 (preferably be not more than 0.6, and more preferably 0.5).The add-on of Si and/or B (b+c) preferably is not less than 0.01 greater than 0, and more preferably is not less than 0.05.Should be noted in the discussion above that and any or two among Si and the B can be joined in the composition, and in " b " and " c " one can be 0.But it is more favourable than adding Si to add B, because B forms the B-N key, makes coating have oilness.Therefore, when needs improve oilness, recommend to add Si and B simultaneously, perhaps add B.On the other hand, it is hexagonal system that the excessive adding of Si and/or B causes the crystal structure transition of VAl-based hard coating, and this may cause the loss of hardness.Therefore, the add-on of Si and/or B (b+c) is not more than 0.20, preferably is not more than 0.15, more preferably is not less than 0.10, and in this case, the lower limit of the summation of " a " and " b+c " preferably is not less than 0.4, particularly is not less than 0.5.

Hard coat of the present invention is not limited to aforesaid hard coat with even composition, and comprise also in the hard coat of the present invention that those hard coats that have with the composition of VAl-based hard coating equivalence (comprise and add the VAl-based hard coating that Si or B are arranged, and in below this hard coat also is applied to), also be combined with the hard coat of Mo and/or W as will be described below, the hard coat that is combined with Zr and/or Hf that perhaps will be described below is as whole coating.For example, by repeat to deposit the coating that extremely thin layer makes (below be called the multilayer hard coat) with the periodicity that is not more than about 80nm, when it on average forms in the composition that falls into VAl-based hard coating (perhaps also being combined with the hard coat of Mo and/or W or Zr and/or Hf as will be described below), also in the scope of hard coat of the present invention.Because under the situation of such multilayer hard coat (following be called sometimes first kind of multilayer hard coat), the thickness owing to layer that constitutes each layer of this coating is extremely thinly lost its peculiar property, and coating is made the as a whole characteristic that demonstrates single-layer coating.Being also advantageous in that of such multilayer hard coat can be made coating by the combination of using known target (as AlN and AlVN), and do not needed to make the special target of forming coupling with coating.Term " the average composition " was meant by forming that the ratio that is present in the atomicity/unit surface in the laminate is represented, and this average composition can calculate with program for example as described below.About comprising the laminate of layer A and layer B, its middle level A comprises (V _aSi _b) (thickness, Xnm), layer B comprises (Al to N _cB _d) (thickness Ynm), for example, constitutes the lattice parameter (α) and the molecule number (Z)/10 of layer A and each structure cell of the compound of layer B to N ⁶Nm ²Measure by X-ray diffraction.The composition that layer A and layer B are every layer is by calculating such as AES, and film thickness is by calculating such as TEM.The numerical value that obtains is used for V atomicity/unit surface (Vm) of computation layer A, and the calculation formula of use is 10 ⁶X * Z * a/ (α ³)/(a+b), and the Si atomicity/unit surface (Sim) that is used for computation layer A Si, the calculation formula of use is 10 ⁶X * Z * b/ (α ³)/(a+b).Similarly, determine Al among the layer B and B atomicity/unit surface [(Alm) and (Bm)].The numerical value of the atomicity that so obtains is used to calculate the ratio [under the situation of V, (Vm/ (Vm+Sim+Alm+Bm))] of atomicity/unit surface, to determine average the composition.

The periodic upper limit is preferably 50nm, more preferably 30nm, and 15nm most preferably.The homogeneity of coating, hardness and oilness all improve along with reducing of the periodic upper limit.To periodically not setting limit.But, along with periodically reducing, multilayer hard coat and have difference between the hard coat of the even composition difficulty that becomes, thereby lower limit can be set in for example about 1nm (particularly, about 3nm).As long as periodically in such scope, then the stratified thickness of structure is not particularly limited.But, described layer can, for example be not more than 50nm, preferably be not more than in 30nm, the scope more preferably no more than 10nm.

The layer of multilayer VAl-based hard coating comprises the nitride of element of at least a Al of being selected from, V, Si and B and carbonitride [below, nitride and carbonitride can be called (carbon) nitride together] usually.Preferably the example of (carbon) nitride comprises Al-base (carbon) nitride such as Al (CN), AlSi (CN), AlB (CN) and AlSiB (CN), and wherein (CN) in the compound is the above-claimed cpd of (N); Si (CN) and B (CN).Combination to layer is not particularly limited, and its combination can be for example, to contain (carbon) nitride such as Al-base (carbon) nitride or AlV-base (carbon) nitride and the combination that does not contain (carbon) nitride such as V-base (carbon) nitride, Si (CN) or the B (CN) of Al of Al.The example of combination comprises Al (CN)/V (CN), Al (CN)/VSi (CN), AlSi (CN)/V (CN), AlSi (CN)/VB (CN), AlB (CN)/V (CN), AlB (CN)/VSi (CN), AlSiB (CN)/V (CN), AlV (CN)/Si (CN), AlV (CN)/B (CN), AlVSi (CN)/B (CN), AlVB (CN)/Si (CN) and AlVSiB (CN)/AlV (CN), in the above-mentioned exemplary combined, (CN) part can be (N).

The multilayer hard coat can also be a kind of like this multilayer hard coat, it comprises the hard coat that one deck is identical with VAl-based hard coating composition at least (comprise and add the hard coat that Si or B are arranged), perhaps also be combined with the hard coat of Mo and/or W as will be described below, perhaps be combined with the hard coat (comprising those hard coats that added Si or B) of Zr and/or Hf as will be described below; And rest layers (second kind of multilayer hard coat) with composition of this hard coat character of not obvious weakening.Under the situation of second kind of such multilayer hard coat, the character of whole coating is by the decision of the character of hard coat, therefore have excellent hardness and oilness, and such coating is also in the scope of hard coat of the present invention.

The example of remaining layer with composition of this hard coat character of not obvious weakening comprises the nitride that contains TiAl or the layer of carbonitride, and contains the nitride of CrAl or the layer of carbonitride.These layers have excellent oxidation-resistance, and when with such layer during with hard coat (VAl-based hard coating or added the VAl-based hard coating of Si and/or B) lamination, the lamination hard coat that obtains has the oxidation-resistance of improvement.At such rest layers and hard coat each other during lamination, to the quantity of rest layers without limits, and the lamination hard coat can comprise the rest layers that one or more layers is such.

The upper and lower bound of its periodic upper and lower bound and each layer can be identical with first kind of multilayer hard coat.

Typically, the thickness of hard coat is (when hard coat comprises multilayer, the total thickness of each layer) is not less than 0.5 times (preferably be not less than 0.8 times, and most preferably be not less than 1.0 times) of rest layers thickness, and is not more than 2.0 times (preferably being not more than 1.5 times) of rest layers thickness.When hard coat was higher with respect to the ratio of rest layers, hard formation may the less influence that is subjected to rest layers.The upper limit of hard formation with respect to the thickness of rest layers is not particularly limited, and higher ratio only means that such coating will be difficult to distinguish with the hard coat with even composition.But its upper limit can be about 10 times (particularly 5 times, and typically about 2 times).

Under the VAl-based hard coating situation of (comprising the VAl-based hard coating that has added Si and/or B), as mentioned above, the V oxide compound that fusing point is lower and softer preferentially is formed on boundary between the work piece (perhaps being cut part) by friction, it is believed that such hardness and oilness improved.But the fusing point of V oxide compound is about 600 ℃, and in the temperature condition lower slip higher than the temperature that can cause V component oxidation in the coating, thereby cause coating to be easy to degenerate.Consider such situation, the present inventor notices that the oxide compound that Mo and W form has the fusing point higher than V oxide compound, and by with Mo and W with (AlV) and (AlVSiB) component use, successfully formed the oxide compound [WO that fusing point is higher than V oxide compound fusing point ₂(fusing point, 1500 ℃), WO ₃(fusing point, 1470 ℃), MoO ₂(fusing point, 1100 ℃) and MoO ₃(fusing point, 795 to 801 ℃)].The inventor also finds, such hard coat (below be called the VAl-based hard coating that wherein is combined with Mo and/or W, perhaps abbreviate the hard coat that also contains Mo and/or W as, and this VAl-based hard coating that wherein is combined with Mo and/or W can also contain Si and/or B in addition), even under 600 ℃ or higher temperature condition, also can inhibited oxidation speed, and can improve wear resistance and frictional coefficient is suppressed at lower level.

When the content (atom ratio) of Mo and/or W (that is, as under the situation of aforesaid VAl-based hard coating, when compound is expressed as (Al _1-a-d-eV _aMo _dW _e) (C _1-XN _X) or (Al _1-a-b-c-d-eV _aSi _bB _cMo _dW _e) (C _1-XN _X) time, the numerical value of " d+e ") be typically greater than 0, preferably be not less than 0.05, and more preferably be not less than at 0.1 o'clock, frictional coefficient can be suppressed and wear resistance can be improved.But, when these elements with too high content in conjunction with the time, the crystalline structure of hard coat becomes and is easy to become softer hexagonal structure structure from hard NaCl type structural transformation, thereby has reduced wear resistance.Therefore, suitable being controlled to of the content of these elements (" d+e " numerical value) is not more than 0.3 (preferably being not more than 0.2).

Mention in passing, the lattice parameter of VN in the hard coat and AlN (pure with stable cubic crystal structure) is respectively 0.414nm and 0.412nm, the lattice parameter of ZrN and HfN is respectively 0.456nm and 0.452nm simultaneously, and these lattice parameters are greater than the lattice parameter of VN and AlN.Therefore, be formed with hard coat therein such as the compound of ZrN and HfN, described ZrN and HfN have the lattice parameter that is different from VN and AlN, (below be called the VAl-based hard coating that also is combined with Zr and/or Hf, perhaps abbreviate the hard coat that also contains Zr and/or Hf as, and this VAl-based hard coating that wherein is combined with Zr and/or Hf can also contain Si and/or B in addition), can promote sclerosis to improve hardness by lattice deformability.

When the content (atom ratio) of Zr and/or Hf (that is, under the situation of aforesaid VAl-based hard coating, when compound is expressed as (Al _1-a-f-gV _aHf _fZr _g) (C _1-XN _X) or (Al _1-a-b-c-f-gV _aSi _bB _cHf _fZr _g) (C _1-XN _X) time " f+g " value) be typically greater than 0, preferably be not less than 0.1, and more preferably be not less than at 0.2 o'clock, can improve hardness and wear resistance.But, when these elements with too high content in conjunction with the time, the crystalline structure of hard coat becomes and is easier to be transformed into hexagonal system structure, thereby has reduced wear resistance.Therefore, these elements are suitable to be not more than the content combination of 0.5 (preferably be not more than 0.4, and be not more than 0.3).

At the hard coat that also contains Mo and/or W or also contain in the hard coat of Zr and/or Hf, coating can have the content (that is, " a " in the above-mentioned chemical formula, " b+c " and " X " value) of V, the Si, B, C and the N that are similar to aforesaid VAl-based hard coating (comprise and add the hard coat that Si or B are arranged).But Mo, W, Hf and Zr have the aforesaid effect of improving wear resistance, and therefore, the lower limit of V content (" a " value) can be lower than the VAl-based hard coating or comprise " a " value lower limit of the VAl-based hard coating that adds the hard coat that Si or B are arranged.In the hard coat that also contains Mo and/or W, the lower limit of V content (" a " value) can be 0.2 (preferred 0.27, more preferably 0.3, and most preferably 0.35), and in the hard coat that also contains Zr and/or Hf, the lower limit of V content can be for 0.01 (preferred 0.2, more preferably 0.27, also more preferably 0.3, and most preferably 0.35).

Mo and/or W or Zr and/or Hf can be combined in hard coat, its combination not only can contain the individual layer hard coat of such element by being manufactured on its inside, but also can come combination by making the lamination hard coat, described lamination hard coat comprises the VAl-based hard coating and (comprises and add the hard coat that Si or B are arranged, and below be called a layer A) with by the layer of the compound of at least a and C among Mo and the W and at least a manufacturing among the N (below be called a layer B), perhaps by layer (below be called a layer C) of the compound of at least a and C among Zr and the Hf and at least a manufacturing among the N.

Metal such as Mo and/or W or Hf and/or Zr is being insufficient aspect the hardness, and will cause the loss of the wear resistance of whole lamination dura mater with the such metal of simple substance form deposition.Therefore, these metals should use with carbonitride-based compound form with C and/or N.But, even will be when the melts combine of Mo and/or W or Hf and/or Zr be in carbonitride-based compound, such compound still is inferior to VAl-based hard coating (comprising the hard coat of adding by Si or B) aspect hardness, therefore, if the layer of carbonitride-based compound of Mo, W, Hf or Zr is thicker than VAl-based hard coating, then the hardness of whole hard coat and wear resistance are with deficiency.So preferred settled layer B like this and layer C make them thinner than layer A.In addition, preferably the gauge control with each layer is being not more than 200nm (preferably being not more than 50nm, more preferably no more than 20nm), because when each layer thickness surpasses certain level, makes the advantage forfeiture of lamination coating.

As long as coating has the hardness and the oilness (frictional coefficient) of satisfactory level, hard coat of the present invention [VAl-based hard coating (comprise and add the hard coat that Si or B are arranged), also scribble the VAl-based hard coating (comprise and add the hard coat that Si or B are arranged) of Mo and/or W, also scribble the VAl-based hard coating (comprise and add the hard coat that Si or B are arranged), multilayer hard coat etc. of Zr and/or Hf] can have mixed-crystal structure, comprise cube and hexagonal system structure.Along with the ratio increase of cubic crystal structure, the hardness of coating will improve.

Whether crystalline structure is determined by X-ray diffraction method for the NaCl-type.More specifically, measure (111) of cubic system, the peak intensity on (200) and (220) surface and (100), (102) of hexagonal, the peak intensity on (110) surface, and calculate the ratio of cubic system by following formula (1).When the ratio of the cubic system of calculating like this is not less than 0.7, preferably be not less than 0.8, be not less than at 0.9 o'clock, the crystalline structure that can determine coating is the NaCl-type.In having the coating less than 0.7 mixed-crystal structure of this ratio wherein, preferably this ratio is not less than 0.4, particularly is not less than 0.5.

$\frac{\mathrm{IB}\left(111\right)+\mathrm{IB}\left(200\right)+\mathrm{IB}\left(220\right)}{\mathrm{IB}\left(111\right)+\mathrm{IB}\left(200\right)+\mathrm{IB}\left(220\right)+\mathrm{IH}\left(100\right)+\mathrm{IH}\left(102\right)+\mathrm{IH}\left(110\right)}---\left(1\right)$

Wherein IB (111), IB (200) and IB (220) represent the peak intensity on cubic system surface respectively, and IH (100), IH (102) and IH (110) represent the peak intensity on hexagonal surface respectively.

X-ray diffraction method is undertaken by θ-2 θ method.The X-ray diffraction method of cubic system is to use CuK α source to carry out, and respectively at for example about 2 θ=37.78 °, for example about 2 θ=43.9 °, about 2 θ=63.8 ° for example, measures the peak intensity on (111) surface, (200) surface and (220) surface.The X-ray diffraction method of hexagonal is to use CuK α source to carry out, and exist respectively, for example about 2 θ=32 ° to 33 °, for example about 2 θ=48 ° to 50 °, about 2 θ=57 ° to 58 ° for example measure the peak intensity on (100) surface, (102) surface and (110) surface.

Above-mentioned for cube and hexagonal shown in the peak position be according to those peak positions in the JCPDS card.When comprising Ti, V, Cr, Mo, Ta, W etc. in the crystal, crystal is each surperficial peak position of hexagonal (ZnS-N-type waferN) particularly, departs from the value shown in the JCPDS card sometimes.In this case, the target peak position can be determined with the relation of other peak position or with the relation at the peak of other compound by considering.

Can be at least one surface of hard coat with another hard coat, metal level or the deposition of alloy layers that are different from aforesaid hard coat, thus compound hard coat made.

More accurately, the hard coat that is different from aforesaid hard coat is the hard coat of metal nitride, metallic carbide or carbonitride with NaCl-type crystal structure, and it can be selected according to the purposes of coating.Typical example comprises: the Cr-based hard coating, and as Cr (CN) and CrAl (CN), and wherein (CN) part is (N) or those hard coats (C); The Ti-based hard coating, as Ti (CN), TiAl (CN) and TiSi (CN), and wherein (CN) part is (N) or those hard coats (C); With the TiCr-based hard coating, as TiAlCr (CN), and wherein (CN) part is (N) or those hard coats (C).

More accurately, metal level or alloy layer are to be selected from least a metal of element, Al and Si of 4A in the periodic table of elements, 5A and 6A family and the layer of their alloy, and because such layer hardness is lower than hard coat hardness of the present invention, (particularly comprise for example iron of rapid tool steel-Ji base material at insertion hard coat and target part, described rapid tool steel (for example SKH51 or SKD) has relative low sticking power with hard coat) this metal level or alloy layer on form hard coat, improved the sticking power between hard coat and the target part.Metal level or alloy layer comprise the layer of Cr, Ti, Nb or Ti-Al typically.

Hard coat can be deposited into (comprising lamination hard coat and compound hard coat) thickness of suitable selection according to purposes.But preferably its thickness is not less than 0.5 μ m (preferably being not less than 1 μ m) and is not more than 20 μ m (preferably be not more than 15 μ m, and more preferably no more than 10 μ m).

Example of the iron-based material of deposition hard coat comprises those that comprise rapid tool steel (SKH51, SKD11, SKD61 etc.) and Wimet on it.

Hard coat can form with methods known in the art, and described method is physical vapor deposition (PVD) or chemical vapor deposition (CVD) for example, considers sticking power etc., preferably adopts PVD, as sputter, vacuum moulding machine and ion plating.Preferably,, suitably form hard coat as sputter and ion plating (particularly arc ions plating) by vapour deposition process.

More specifically, VAl-based hard coating or wherein add the VAl-based hard coating that Si and/or B are arranged can be by the vapour deposition process manufacturing, and preferably adopts arc ions to electroplate, and in the presence of film forming gas, uses extremely (iv) manufacturing of following target (i):

(i) Al and V,

(ii) Al, V and Si,

(iii) Al, V and B, and

(iv) Al, V, Si and B.

More specifically,

When deposition is comprised (Al _1-aV _a) (C _1-XN _X) hard coat the time, can adopt to comprise (Al _1-aV _a) target, 0.27≤a≤0.75 (wherein a represents atom ratio) wherein, and

When deposition is comprised (Al _1-a-b-cV _aSi _bB _c) (C _1-XN _X) hard coat the time, can adopt to comprise (Al _1-a-b-cV _aSi _bB _c) target, wherein 0.1≤a≤0.75, and 0＜b+c≤0.20 (wherein a, b and c represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0).

The target that the target that uses when making the hard coat wherein also be combined with Mo and/or W or Zr and/or Hf can be above-mentioned (i) that also comprise Mo and/or W or Zr and/or Hf in (iv).

The present inventor has also studied the character of target, find that the low relatively target of density is associated with micropore probably, and the inhomogeneous evaporation of target causes the formation of inhomogeneous hard coat, and low density target local and consumption fast in the gap of target experience in being coated with layer deposition process, and the fast target rate of wear causes shorten the work-ing life of target.The inventor finds that also most space causes the generation in target strength reduction and crack etc. in the target.This problem can be increased to the degree that is not less than 95% (preferably being not less than 98%) by the relative density with target and be solved.Use the discharge condition of such target in can also steady-state evaporation or the ionization of the alloy compositions of the formation target by arc-over, thereby can make good hard coat.

Employed relative density is the numerical value of being determined by following formula: the [(1cm of the target of employing ³Weight)/(density (theoretical density)) * 100 with target of pure composition].Theoretical density can use methods known in the art to calculate.

Manufacture method to target is not particularly limited.The manufacturing process of target for example, raw material (V powder and the Al powder) uniform mixing that will have suitable component ratio of regulating and granularity in V mixing machine etc. to be making powder mixture, and makes target by methods such as isostatic cool pressing (CIP), hot isostatic pressing (HIP), hot-extrudable, ultra-high voltage hot pressing by this mixture.

The present inventor has also studied the device that is used for by arc ions electroplating deposition hard coat, and find, in the device that in conventional AIP, uses, target 106 is placed between the magnet 109 and work piece W that produces magnetic field, thereby schematically show as Fig. 4, the magnetic line of force 102 that magnet 109 produces is arranged essentially parallel to the target surface near the target evaporation surface, and magnetic line of force 102 less extend to work piece W near.Therefore, the plasma density of film forming gas is high near target, and reduces towards work piece W direction.The inventor finds, when the magnetic line of force that makes generation almost extends perpendicular to the water surface of evaporation of target, can deposit hard coat effectively, and the portions of electronics e of discharge generation will with N and/or the C collision in the gas, thereby be convenient to the plasma bodyization of N and/or C.More specifically, when magnet or be used for producing the device (the present invention is also referred to as magnetic field generation device) 8 or 9 in magnetic field, for example be equipped with coil and coil electro-magnet with power supply, when being placed between target 6 and the work piece W shown in Fig. 2 and 3, the angle that the normal of magnetic line of force and target 6 water surface of evaporation forms will be not less than ± 30 ° (preferably being not less than 20 °).Equally, when magneticflux-density is increased to the level that is higher than conventional AIP equipment near target and near the target part, can promote to have the generation of the AlN of rock salt crystalline structure, described rock salt crystalline structure is in nonequilibrium situations under standard temperature and standard pressure, thereby improves the hardness of coating.In addition, can promote the plasma bodyization of N in the plasma bodyization of the material that forms by evaporation and the atmosphere, thereby be convenient to form high energy particle, and the inventor believes that this has promoted to have the formation of the AlN of the rock salt structure that is in nonequilibrium state by the N of plasma bodyization.

As shown in Figure 2, the position of magnetic field generation device can be positioned at the side of the water surface of evaporation S of the top of target 6 and/or target 6, make target by magnetic field generation device 9 around or be clipped in the middle, perhaps as shown in Figure 3, magnetic field generation device 9 can be between the water surface of evaporation S and work piece W of target.Alternatively, as shown in Figure 2, can perhaps can provide around the special-purpose cylindrical anode of target periphery first half with the chamber as anode.

Can regulate the density in the magnetic field of generation, make the magneticflux-density of centre portions on the target part surface that will form hard coat on it be not less than 10 Gausses (preferably being not less than 30 Gausses).

Can select film forming gas according to the composition of required hard coat, and typically make N be not less than 0.3% (preferably be not less than 0.4%, more preferably be not less than 0.6%, and most preferably be not less than 0.8%) with respect to the ratio of N and C atom total amount.

Can suitably select the temperature of the target part in the hard coat deposition process according to the kind of target part.Cross when low when temperature, the unrelieved stress of hard coat may increase, and the too much unrelieved stress that acts on hard coat may have disadvantageous effect to the sticking power of hard coat and target part.Therefore, suitable temperature regulation with target part is to being not less than 300 ℃, and preferably is not less than 400 ℃.Although unrelieved stress will descend along with the rising of target part temperature, too high target part temperature will cause the decline of stress under compression simultaneously, and this may have a negative impact to the effect that coating is improved the target part resistance to bending.Such high temperature also may cause the distortion of target part.Therefore, suitable temperature regulation with target part is to being not more than 800 ℃, and preferably is not more than 700 ℃.When target part when being HSS (rapid tool steel) as the base material of SKH51 or hot working tool steel such as SKD11 or SKD61, preferably in manufacturing processed, keep the temperature of base material, make its tempering temperature that is no more than substrate material, thereby keep the mechanical properties of base material.Although can select tempering temperature according to substrate material, when SKH51 was used for base material, tempering temperature and when SKD11 is used for base material, was 500 to 530 ℃ usually in 550 to 570 ℃ of scopes.In this case, the preferred temperature of selecting to make base material makes it be lower than this tempering temperature, and typically, in the temperature that is no more than below the tempering temperature 50 ℃.

When in coating forming procedure when target part applies negative potential, can form hard coat effectively.The bias voltage that preferably applies is a negative voltage, and its absolute value is not less than 10V, particularly is not less than 30V, because higher bias voltage causes higher plasma body to change into the energy of film gas and metal ion, and is convenient to have the formation of the hard coat of cubic crystal structure.But the increase of bias voltage is relevant with the rapid decline of coating sedimentation velocity sometimes, because coating is by the film forming gas etching of plasma bodyization.Therefore, preferably bias voltage being remained on absolute value is not more than 200V, particularly is not more than the negative voltage of 150V.When Al content is low relatively, even bias voltage is low a little, aforesaid locking also will be effective, and be fit to the hard coat that deposition has cubic crystal structure.

When manufacturing comprises the hard coat of laminate form of multilayer hard coat, the manufacture method of such lamination coating can be, for example, use the equipment that has a plurality of target 6A and magnetic field generation device 8A as shown in Figure 5, and form each layer by aforesaid method.

Embodiment

Adopt following method to assess the physical properties of the hard coat that obtains in the following EXPERIMENTAL EXAMPLE:

[composition of hard coat]

Adopt EPMA to determine to form.In this method, confirm that also the content of the impurity except that metallic element and nitrogen, the content of oxygen and the content of carbon are no more than 5 atom % respectively.

[condition of using in the crystal structure analysis]

The X-ray diffractometer that uses Rigaku Electric to make carries out X-ray diffraction by θ-2 θ method, assesses the crystalline structure of hard coat.The X-ray diffraction method of cubic system is to use CuK α source to carry out, and respectively at about 2 θ=37.78 °, about 2 θ=43.9 ° and about 2 θ=63.8 ° of measurements (111) surface, (200) surface and (220) surperficial peak intensity.The X-ray diffraction method of hexagonal is to use CuK α source to carry out, and respectively at about 2 θ=32 ° to 33 °, about 2 θ=48 ° to 50 ° and about 2 θ=57 ° to 58 ° measurements (100) surface, (102) surface and (110) surperficial peak intensity.The value that obtains is used for following formula (1):

$\frac{\mathrm{IB}\left(111\right)+\mathrm{IB}\left(200\right)+\mathrm{IB}\left(220\right)}{\mathrm{IB}\left(111\right)+\mathrm{IB}\left(200\right)+\mathrm{IB}\left(220\right)+\mathrm{IH}\left(100\right)+\mathrm{IH}\left(102\right)+\mathrm{IH}\left(110\right)}---\left(1\right)$

Wherein IB (111), IB (200) and IB (220) represent the peak intensity on cubic system surface respectively, and IH (100), IH (102) and IH (110) represent the peak intensity on hexagonal surface respectively.When calculated value (" value of formula (1) " in the table 1) when being not less than 0.8, determine that coating has NaCl-type structure (being expressed as " B " in the table 1); When this value is 0, determine that coating has hexagonal system structure (being expressed as " H " in the table 1); And when this value greater than 0 and less than 0.8 the time, determine that coating has mixed structure (being expressed as " B+H " in the table 1).

[measurement of hardness]

Hardness is to measure under the retention time of the load of 0.25N and 15 seconds with the vickers microhardness tester.

[measurement of frictional coefficient]

Hard coat of the present invention is used in sliding test (to be made by SKD61 with test panel; Diameter 55mm; Thickness 5mm; A surface is by mirro finished) the surface on, and under following test conditions the assessment coating frictional coefficient.

The sliding test condition

Test method: ball on the dish

Ball: SUJ2 (diameter 9.54mm); Hardness, HRC60

Normal load: 5N

Sliding velocity: 1m/s

Atmosphere temperature: EXPERIMENTAL EXAMPLE 1 to 4 is 500 ℃, and EXPERIMENTAL EXAMPLE 5 to 8 is 800 ℃.

Sliding distance: 1000m

[observation of wearing and tearing width]

Hard coat of the present invention is deposited on end mill (the diameter 10mm of Wimet; 2 teeth) on, under following condition A (EXPERIMENTAL EXAMPLE 1 to 4) and following condition B (EXPERIMENTAL EXAMPLE 5 to 8), cut into predetermined length of cut, and under opticmicroscope, observe the tip of the end mill that is covered by hard coat.

-condition A

Work piece: SKD61 hardened steel (HRC50)

Cutting speed: 220m/ minute

Input speed: 0.06mm/ tooth

Axial depth of cut: 4.5mm

The radial cutting degree of depth: 1mm

Other (Misc.): only to incision, dried cutting, and blow air

Length of cut: 20m

-condition B

Work piece: SKD11 (HRC60)

Cutting speed: 150m/ minute

Input speed: 0.04mm/ tooth

Axial depth of cut: 4.5mm

The radial cutting degree of depth: 0.2mm

Other: is only to incision, dried cutting, and blow air

Length of cut: 50m

[being used to deposit the equipment of hard coat]

The AIP equipment that in EXPERIMENTAL EXAMPLE 1,2 and 4 to 6, uses Fig. 1 to schematically show.Among Fig. 1, expression chamber 1,2 expression arc evaporation sources, 3 expression carriers, 4 expression grid bias power supplies, 6 expression targets, 7 expression arc powers, 8 expressions are used to produce the device (magnet) in magnetic field, 11 expression pneumatic outlets, 12 expression gas feeds, and W represents target part.

In EXPERIMENTAL EXAMPLE 3,7 and 8, use the AIP equipment deposition hard coat that schematically shows among Fig. 5.The AIP equipment of Fig. 5 is the AIP equipment that also comprises with Fig. 1 of lower member: arc evaporation source 2A, grid bias power supply 4A, target 6A, arc power 7A and magnetic field generation device (magnet) 8A.

[kind of target part]

In EXPERIMENTAL EXAMPLE, use three kinds of target part.The target part of using is: the shovel that [1] Wimet is made (being used for determining crystalline structure and hardness), end mill (the diameter 10mm that [2] Wimet is made; 2 teeth) (be used for measure wearing and tearing width) and [3] sliding test (are made by SKD61 with coiling; 55mm (diameter) * 5mm (thickness); One side is by mirro finished; Be used to measure frictional coefficient).

EXPERIMENTAL EXAMPLE 1

[formation of hard coat]

The target 6 that uses is to have the target of forming shown in " composition ratio of target (atom ratio) " of table 1.

Evacuated chamber 1 is heated to 500 ℃ with the well heater (not shown) with target part.The single kind gas or the mixed gas that will have the composition of " composition ratio of film forming gas (atom ratio) " shown in the table 1 are fed to the chamber 1 from gas inlet 12, and the pressure until chamber 1 reaches 2.66Pa.Apply 20 to 100V voltage by grid bias power supply 4 to target part, making target part W is negative voltage with respect to ground voltage.By arc power 7 beginning arc-overs, evaporation and ionization target 6 are with the hard coat of deposition 3 μ m on target part W surface then.

[physical properties of hard coat]

The hard coat that obtains is carried out value, hardness, frictional coefficient and the assessment of wearing and tearing width of crystalline structure, formula (1).The results are shown in the table 1.

Table 1

	The composition ratio of target (atom ratio)		The composition ratio of film forming gas (atom ratio)		Crystalline structure [value of formula (1)]	Hardness	Frictional coefficient	The wearing and tearing width
										Al	V	C	N	(HV)	(μ)	(μm)
Comparative example
									1	Ti 0.4Al 0.6N				B[1]	2800	0.67	55.0
2	Cr 0.4Al 0.6N				B[1]	2750	0.56	54.0
									3	0.00	1.00	0.00	1.00	B[1]	2750	0.28	56.0
4	0.20	0.80	0.00	1.00	B[1]	2950	0.29	54.0
									5	0.75	0.25	0.00	1.00	B+H[0.2]	2700	0.58	37.0
6	0.85	0.15	0.00	1.00	H[0]	2200	0.62	60.0
									7	1.00	0.00	0.00	1.00	H[0]	2200	0.65	*
8	0.63	0.37	0.80	0.20	B[1]	2800	0.28	56.0
									Embodiment
1	0.25	0.75	0.00	1.00	B[1]	3100	0.29	33.0
									2	0.35	0.65	0.00	1.00	B[1]	3200	0.29	35.0
3	0.40	0.60	0.00	1.00	B[1]	3350	0.3	25.0
									4	0.60	0.40	0.00	1.00	B[1]	3400	0.3	22.0
5	0.63	0.37	0.00	1.00	B[1]	3450	0.34	18.0
									6	0.65	0.35	0.00	1.00	B[1]	3450	0.35	18.0
7	0.68	0.32	0.00	1.00	B[1]	3400	0.38	18.0
									8	0.70	0.30	0.00	1.00	B[1]	3000	0.39	20.0
9	0.73	0.27	0.00	1.00	B[1]	3300	0.34	20.0
									10	0.63	0.37	0.15	0.85	B[1]	3500	0.31	19.0
11	0.63	0.37	0.30	0.70	B[1]	3490	0.3	23.0
									12	0.63	0.37	0.42	0.58	B[1]	3300	0.3	25.0
13	0.63	0.37	0.55	0.45	B[1]	3150	0.29	29.0
									14	0.63	0.37	0.66	0.34	B[1]	2950	0.29	46.0

^*Become unavailable at the 50m place

With comprise TiAlN (comparative example 1), comprise CrAlN (comparative example 2) and compare with the conventional coating that comprises VN (comparative example 3), the hard coat (embodiment 1 to 14) that the present invention comprises Al, V, C and N all has more excellent hardness, lower frictional coefficient and narrower wearing and tearing width.Contain hexagonal system structure in the crystalline structure of the coating (comparative example 4 to 8) that the scope of the invention is outer, and these coatings or aspect hardness, frictional coefficient or wearing and tearing width inferior to conventional hard coat (comparative example 1 to 3).Use contains the film forming gas of C and coating deposited (embodiment 10 to 14) is compared with the coating (embodiment 5) of using the film forming gas preparation that does not contain C, and friction resistance is more bad and oilness is more excellent.

EXPERIMENTAL EXAMPLE 2

[formation of hard coat]

The program of repeated experiments embodiment 1 experimentizes, and difference is that the target 6 that uses is the targets with the composition of " composition ratio of target (atom ratio) " shown in the table 2.

[physical properties of hard coat]

The crystalline structure of the hard coat that assessment obtains, value, hardness, frictional coefficient and the wearing and tearing width of formula (1).The results are shown in the table 2.

Table 2

	The composition ratio of target (atom ratio)				The composition ratio of film forming gas (atom ratio)		Crystalline structure [value of formula (1)]	Crystal size	Hardness	Frictional coefficient	The wearing and tearing width
													Al	V	Si	B	C	N	(nm)	(HV)	(μ)	(μm)
Comparative example
												1	Ti 0.4Al 0.6N						B[1]	30	2800	0.67	55.0
2	Cr 0.4Al 0.6N						B[1]	35	2750	0.56	54.0
												9	0.51	0.25	0.00	0.24	0.00	1.00	H[0]	4	2650	0.21	43.0
10	0.53	0.20	0.27	0.00	0.15	0.85	H[0]	3	2700	0.4	53.0
												11	0.57	0.20	0.11	0.12	0.55	0.45	H[0]	3	2800	0.35	55.0
Embodiment
												15	0.60	0.40	0.00	0.00	0.10	0.90	B[1]	20	3300	0.3	22.0
16	0.59	0.40	0.00	0.01	1.00	0.00	B[1]	16	3450	0.28	18.0
												17	0.57	0.40	0.00	0.03	0.00	1.00	B[1]	15	3500	0.28	18.0
18	0.55	0.40	0.00	0.05	0.00	1.00	B[1]	12	3500	0.26	17.0
												19	0.59	0.34	0.00	0.07	0.00	1.00	B[1]	10	3450	0.25	17.0
20	0.55	0.30	0.00	0.15	0.00	1.00	B+H[0.5]	5	3100	0.23	20.0
												21	0.55	0.25	0.00	0.20	0.00	1.00	B+H[0.5]	5	3000	0.22	24.0
22	0.59	0.40	0.01	0.00	0.00	1.00	B[1]	10	3000	0.3	23.0
												23	0.58	0.40	0.02	0.00	0.00	1.00	B[1]	8	3300	0.32	22.0
24	0.63	0.35	0.02	0.00	0.00	1.00	B[1]	8	3350	0.31	21.0
												25	0.63	0.32	0.05	0.00	0.00	1.00	B[1]	6	3300	0.33	22.0
26	0.40	0.30	0.10	0.00	0.00	1.00	B[1]	5	3300	0.32	22.0
												27	0.59	0.30	0.11	0.00	0.00	1.00	B[1]	5	3250	0.33	25.0
28	0.55	0.30	0.15	0.00	0.00	1.00	B[1]	5	3200	0.33	26.0
												29	0.54	0.28	0.18	0.00	0.00	1.00	B+H[0.4]	3	3000	0.35	34.0
30	0.55	0.25	0.20	0.00	0.00	1.00	B+H[0.4]	3	3000	0.36	36.0
												31	0.60	0.35	0.03	0.02	0.30	0.70	B[1]	7	3450	0.29	19.0
32	0.52	0.40	0.03	0.05	0.42	0.58	B[1]	6	3300	0.31	23.0
												33	0.73	0.15	0.05	0.07	0.00	1.00	B+H[0.5]	5	2950	0.4	39.0

Compare with the conventional coating of CrAlN (comparative example 2) with comprising TiAlN (comparative example 1), hard coat of the present invention (embodiment 15 to 33) all has more excellent hardness, lower frictional coefficient and narrower wearing and tearing width.The hard coat (embodiment 15) that the hard coat (embodiment 16 to 33) that also comprises Si and B has with the present invention does not contain Si or B equates or more excellent character.But the outer coating (comparative example 9 to 11) of the scope of the invention contains the ZnS structure in their crystalline structure, and has to compare with conventional hard coat (comparative example 1 and 2) and equate or the more bad hardness and the width that weares and teares.

EXPERIMENTAL EXAMPLE 3

[formation of hard coat]

The equipment that uses is the equipment that schematically shows among Fig. 5.The target 2 that uses is to have the target of forming shown in " composition ratio of target (atom ratio) " of " layer A (row of going up) " in the table 3, and the target 2A that uses has the composition shown in " composition ratio of target (atom ratio) " of " layer B (row down) " in the table 3.Embodiment 39 and 41 coating are in the situation deposit of not using target 2.

The formation of-embodiment 34 to 38 and 40 hard coat:

Evacuated chamber 1 is heated to 500 ℃ with the well heater (not shown) with target part.Composition single that will have " composition ratio of film forming gas (atom ratio) " shown in the table 3 plants gas or mixed gas and 12 is fed to chamber 1 from the gas inlet, and the pressure until chamber 1 reaches 2.66Pa.Then by arc power 7 beginning arc-overs, thereby evaporation and ionization target 6, and apply 20 to 100V voltage by grid bias power supply 4 to target part, making target part W is negative voltage with respect to ground voltage, thereby deposits the layer A with thickness shown in the table 3 on the target part surface.Once more begin arc-over by arc power 7A this moment, with evaporation and ionization target 6A, and apply 20 to 100V voltage to target part by grid bias power supply 4, to make target part W be negative voltage with respect to ground voltage, thereby deposited the layer B that deposition on the target part W surface of layer A has thickness shown in the table 3 thereon.Aforesaid program is repeated the number of times shown in " precipitation number " of table 3, produce the hard coat that comprises laminate.

The formation of-embodiment 39 and 41 hard coat:

Use the target part of the hard coat of " layer A " that table 3 is arranged in its surface, and target part W is heated to 500 ℃ with the well heater (not shown).Composition single that will have " composition ratio of film forming gas (atom ratio) " shown in the table 3 plants gas or mixed gas and 12 is fed to chamber 1 from the gas inlet, and the pressure until chamber 1 reaches 2.66Pa.Once more begin arc-over by arc power 7A this moment, with evaporation and ionization target 6A, and apply 20 to 100V voltage by grid bias power supply 4 to target part W, making target part W is negative voltage with respect to ground voltage, thereby deposits the layer B with thickness shown in the table 3 on target part W surface.

[assessment of hard coat]

To their crystalline structure of hard coat assessment that obtains, value, hardness, frictional coefficient and the wearing and tearing width of formula (1).The results are shown in the table 3.

Table 3

	Layer A (row of going up)/layer B (row down)
																			The composition ratio of target (atom ratio)				Thickness	The average composition ratio (atom ratio) of the target that uses in the formation of layer A and layer B				Total thickness	The composition ratio of film forming gas (atom ratio)		Precipitation number	Crystalline structure [value of formula (1)]	Hardness	Frictional coefficient	The wearing and tearing width
	Al	V	Si	B	(nm)	Al	V	Si	B	(nm)	C	N		(HV)	(μ)	(μm)
																	Comparative example
1	Ti 0.4Al 0.6N												1	B[1]	2800	0.67																			55.0
																	2	Cr 0.4Al 0.6N												1	B[1]	2750	0.56	54.0
Embodiment
																		34	0.00	1.00	0.00	0.00	4	0.40	0.60	0.00	0.00	10.0	0.00	1.00	300	B[1]	3250	0.25	20.0
1.00	0.00	0.00	0.00	6
					35	0.00	0.96	0.04	0.00	3.7	0.63	0.36	0.01	0.00	10.0	0.00	1.00		300	B[1]	3300	0.31	21.0
1.00	0.00	0.00	0.00	6.3
						36	0.00	1.00	0.00	0.00								3.8						0.59	0.38	0.00	0.03	10.0	0.05	0.95	300	B[1]	3400	0.21	20.0
0.95	0.00	0.00	0.05	6.2
					37		0.00	1.00	0.00	0.00	30	0.60	0.40	0.00	0.00	75.0	0.00	1.00	40	B[1]	2850	0.5	48.0
1.00	0.00	0.00	0.00	45
						38	0.69	0.31	0.00	0.00	6													0.582	0.402	0.012	0.004	10.0	0.05	0.95	300	B[1]	3250	0.24	35.0
0.42	0.54	0.03	0.01	4
					39		TiN				500					3000			1	B[1]	3350	0.28	20.0
0.60	0.37	0.00	0.03	2500																							0.05	0.95
							40	Ti 0.4Al 0.6N				5						12											0.03	0.97	250	B[1]	3100	0.32	29.0
0.55	0.40	0.05	0.00	7
								41	V				200								3000			1	B[1]	3200	0.29	25.0
0.60	0.37	0.00	0.03	2800														0.05	0.95

Compare with the conventional coating of CrAlN (comparative example 2) with comprising TiAlN (comparative example 1), the hard coat (embodiment 34 to 41) that the present invention has a laminar structure all has more excellent hardness, lower frictional coefficient and narrower wearing and tearing width.

EXPERIMENTAL EXAMPLE 4

In the V mixing tank, mix V, Al, Si and B powder (granularity of every kind of powder all is not more than 100 orders), obtain the composition shown in the table 4.The powder that obtains is made target respectively under the condition of sintering (in reducing atmosphere and sintering temperature be 550 ℃), HIP (10,000atm, 480 ℃) and hot-cast (temperature after heating, 450 ℃).Target is placed in the AIP equipment shown in Figure 1, and on target part W surface, deposits hard coat.The discharge scenario of object observing spare W and the coating of formation.The results are shown in the table 4.Embodiment 42 and 43 film forming gas that use are 100% nitrogen, and embodiment 44 and 45 uses is the mixed gas (nitrogen: methane=80: 20 (atom ratio)) of nitrogen and methane.

Table 4

	The composition ratio of target (atom ratio)				The manufacture method of target	The relative density of target	Crystalline structure [value of formula (1)]	Hardness	The wearing and tearing width
											Al	V	Si	B	(HV)	(μm)
Comparative example
					14	0.60	0.35			0.03	0.02	Sintering	88	Because concentrating, discharge can not form film
15	0.50	0.50	0.00	0.00				Sintering	92								Because concentrating, discharge can not form film
					Embodiment
42	0.60	0.40	0.00	0.00											HIP	97	B[1]	3250	21.0
					43	0.57	0.40	0.00	0.03	HIP	99	B[1]	3100	28.0
44	0.59	0.34	0.00	0.07											Forge hot	100	B[1]	3300	21.0
					45	0.50	0.50	0.00	0.00	Forge hot	99	B[1]	3100	27.5

Use relative density fail, and when the use relative density is equal to or greater than 95% target (embodiment 42 to 45), can deposit hard coat less than the trial of 95% target deposition hard coat (comparative example 14 and 15).

EXPERIMENTAL EXAMPLE 5

[formation of hard coat]

The program of repeated experiments embodiment 1 experimentizes, and difference is that the target 6 that uses is the targets with the composition of " composition ratio of target (atom ratio) " shown in the table 5.

[physical properties of hard coat]

To their crystalline structure of hard coat assessment that obtains, value, hardness, frictional coefficient and the wearing and tearing width of formula (1).The results are shown in the table 5.

Table 5

	The composition ratio of target (atom ratio)						The composition ratio of film forming gas (atom ratio)		Crystalline structure [value of formula (1)]	Hardness	Frictional coefficient	The wearing and tearing width
														Al	V	W	Mo	Si	B	C	N	(HV)	(μ)	(μm)
Comparative example
													1	Ti 0.4Al 0.6N								B[1]	2800	0.85	100.0
2	Cr 0.4Al 0.6N								B[1]	2750	0.78	110.0
													16	0.45	0.16	0.39	0.00	0.00	0.00	0.00	1.00	B+H[0.4]	2800	0.35	53.0
Embodiment
													46	0.63	0.37	0.00	0.00	0.00	0.00	0.00	1.00	B[1]	3450	0.55	65.0
47	0.60	0.37	0.03	0.00	0.00	0.00	0.00	1.00	B[1]	3450	0.5	50.0
													48	0.55	0.37	0.08	0.00	0.00	0.00	0.00	1.00	B[1]	3550	0.45	45.0
49	0.50	0.35	0.15	0.00	0.00	0.00	0.00	1.00	B[1]	3550	0.4	41.0
													50	0.50	0.27	0.23	0.00	0.00	0.00	0.00	1.00	B[1]	3500	0.39	46.0
51	0.50	0.35	0.00	0.15	0.00	0.00	0.00	1.00	B[1]	3500	0.41	39.0
													52	0.50	0.35	0.07	0.08	0.00	0.00	0.00	1.00	B[1]	3500	0.39	39.0
53	0.65	0.20	0.10	0.05	0.00	0.00	0.00	1.00	B[1]	3000	0.4	45.0
													54	0.55	0.40	0.05	0.00	0.00	0.00	0.00	1.00	B[1]	3500	0.45	43.0
55	0.50	0.40	0.05	0.05	0.00	0.00	0.00	1.00	B[1]	3550	0.45	41.0
													56	0.40	0.30	0.15	0.15	0.00	0.00	0.00	1.00	B[1]	3400	0.46	47.0
57	0.50	0.35	0.10	0.00	0.05	0.00	0.00	1.00	B[1]	3480	0.4	36.0
													58	0.50	0.31	0.07	0.07	0.05	0.00	0.00	1.00	B[1]	3550	0.4	41.0
59	0.50	0.31	0.07	0.07	0.00	0.05	0.00	1.00	B[1]	3580	0.38	42.0

The result of hard coat that the hard coat of embodiment 47 to 59 and the present invention contain W and/or Mo is consistent, and is used for the comparison purpose and what show is hard coat (embodiment 46) and the conventional hard coat (comparative example 1 and 2) that the present invention does not contain W or Mo.Under 800 ℃ sliding condition, the hard coat (embodiment 47 to 59) that contains Mo and/or W all is better than conventional hard coat at hardness, frictional coefficient and wearing and tearing width aspect all.Particularly V content be 0.27 or the situation of higher hard coat under (embodiment 47 to 52 and 54 to 56), compare with the hard coat of embodiment 46, by in hard coat in conjunction with W and/or Mo, can improve hardness, frictional coefficient and all aspects of wearing and tearing width.But,,, find that hardness descends and the wearing and tearing width increases (comparative example 16) owing to the crystalline structure of hexagonal system structure type occurred when the total content of W and Mo is 0.39 or when higher.

EXPERIMENTAL EXAMPLE 6

[formation of hard coat]

The program of repeated experiments embodiment 1 experimentizes, and difference is that the target 6 that uses is the targets with the composition of " composition ratio of target (atom ratio) " shown in the table 6.

[physical properties of hard coat]

To their crystalline structure of hard coat assessment that obtains, value, hardness, frictional coefficient and the wearing and tearing width of formula (1).The results are shown in the table 6.

Table 6

	The composition ratio of target (atom ratio)						The composition ratio of film forming gas (atom ratio)		Crystalline structure [value of formula (1)]	Hardness	Frictional coefficient	The wearing and tearing width
														Al	V	Zr	Hf	Si	B	C	N	(HV)	(μ)	(μm)
Comparative example
													1	Ti 0.4Al 0.6N								B[1]	2800	0.85	100.0
2	Cr 0.4Al 0.6N								B[1]	2750	0.78	110.0
													Embodiment
46	0.63	0.37	0.00	0.00	0.00	0.00	0.00	1.00	B[1]	3450	0.55	65.0
													60	0.60	0.37	0.03	0.00	0.00	0.00	0.00	1.00	B[1]	3450	0.53	50.0
61	0.55	0.37	0.08	0.00	0.00	0.00	0.00	1.00	B[1]	3500	0.51	47.0
													62	0.50	0.35	0.15	0.00	0.00	0.00	0.00	1.00	B[1]	3560	0.53	39.0
63	0.50	0.27	0.23	0.00	0.00	0.00	0.00	1.00	B[1]	3500	0.55	47.0
													64	0.50	0.05	0.45	0.00	0.00	0.00	0.00	1.00	B+H[0.35]	3100	0.56	51.0
65	0.50	0.05	0.00	0.45	0.00	0.00	0.00	1.00	B+H[0.30]	3050	0.57	53.0
													66	0.50	0.35	0.00	0.15	0.00	0.00	0.00	1.00	B[1]	3550	0.54	38.0
67	0.50	0.35	0.07	0.08	0.00	0.00	0.00	1.00	B[1]	3520	0.54	38.0
													68	0.35	0.25	0.40	0.00	0.00	0.00	0.00	1.00	B[1]	3400	0.52	48.0
69	0.35	0.25	0.00	0.40	0.00	0.00	0.00	1.00	B[1]	3450	0.52	47.0
													70	0.35	0.25	0.25	0.15	0.00	0.00	0.00	1.00	B[1]	3450	0.5	48.0
70	0.50	0.40	0.10	0.00	0.00	0.00	0.00	1.00	B[1]	3500	0.53	45.0
													72	0.50	0.30	0.20	0.00	0.00	0.00	0.00	1.00	B[1]	3550	0.52	40.0
73	0.50	0.35	0.10	0.00	0.05	0.00	0.00	1.00	B[1]	3480	0.55	37.0
													74	0.50	0.31	0.07	0.07	0.05	0.00	0.00	1.00	B[1]	3570	0.52	39.0
75	0.50	0.31	0.07	0.07	0.00	0.05	0.00	1.00	B[1]	3580	0.48	41.0

The hard coat of embodiment 60 to 75 is consistent with the result of the hard coat of the present invention that contains Zr and/or Hf, and is used for the comparison purpose and what show is the present invention's hard coat (embodiment 46) that do not contain Zr or Hf and conventional hard coat (comparative example 1 and 2).Under 800 ℃ sliding condition, the hard coat of embodiment 60 to 75 all is better than conventional hard coat aspect all at hardness, frictional coefficient and wearing and tearing width.In the hard coat of embodiment 60 to 75,, can under the situation that frictional coefficient does not have obviously to change, increase hardness and reduce the width that weares and teares than embodiment 46 by in conjunction with Zr or Hf.But, when the total content of such element (Zr and Hf) is 0.45 or when higher, owing to the appearance of the crystalline structure of hexagonal system structure type begins to take place the decline of hardness and the increase (embodiment 64 and 65) of wearing and tearing width.Although as such decline and embodiment 64 and 65 when similar, hardness and wearing and tearing width will be no less than the hard coats (comparative example 1 and 2) of routine, the increase of Zr and Hf total content will cause the remarkable decline of hardness and the remarkable increase of wearing and tearing width.

EXPERIMENTAL EXAMPLE 7

[formation of hard coat]

The equipment that uses is the equipment that schematically shows among Fig. 5.In embodiment 77 to 87, the target 2 that uses is the targets with the composition shown in " composition ratio of target (atom ratio) " of " layer A (row of going up) " in the table 7, the target 2A that uses is the target with the composition shown in " composition ratio of target (atom ratio) " of " layer B (row down) " in the table 7, and uses these targets deposition hard coats.The coating of embodiment 76 is in the situation deposit of not using target 2.In addition, the program of repeated experiments embodiment 3.

[assessment of hard coat]

To hard coat assessment their hardness, frictional coefficient and the wearing and tearing width that obtains.The results are shown in the table 7.

Table 7

	Layer A (row of going up)/layer B (row down)
																The composition ratio of target (atom ratio)						Thickness	Total thickness	Film forming gas		Precipitation number	Hardness	Frictional coefficient	The wearing and tearing width
	Al	V	W	Mo	Si	B	(nm)	(nm)	C	N		(HV)	(μ)	(μm)
															Comparative example
1	Ti 0.4Al 0.6N						3000	3000	0.0	1.0	1	2800	0.85	100.0
															2	Cr 0.4Al 0.6N						3000	3000	0.0	1.0	1	2750	0.78	110.0
Embodiment
															46	0.65	0.35	0.00	0.00	0.00	0.00	3000	3000	0.0	1.0	1	3450	0.55	65.0
76	0.63	0.32	0.00	0.00	0.05	0.00	3000	3000	0.0	1.0	1	3300	0.57	55.0
															77	0.65	0.35	0.00	0.00	0.00	0.00	20	3000	0.0	1.0	143	3450	0.55	45.0
0.00	0.00	1.00	0.00	0.00	0.00	1
							78	0.65	0.35	0.00	0.00	0.00	0.00	20		3000	0.0	1.0	130	3500	0.51	34.0
0.00	0.00	1.00	0.00	0.00	0.00	3
								79	0.65	0.35	0.00	0.00	0.00	0.00	20								3000	0.0	1.0	103	3550	0.46	40.0
0.00	0.00	1.00	0.00	0.00	0.00	9
							80		0.65	0.35	0.00	0.00	0.00	0.00	20	3000	0.0	1.0	86	3500	0.43	41.0
0.00	0.00	1.00	0.00	0.00	0.00	15
								81	0.65	0.35	0.00	0.00	0.00	0.00	20								3000	0.0	1.0	55	3400	0.4	53.0
0.00	0.00	1.00	0.00	0.00	0.00	35
							82		0.65	0.35	0.00	0.00	0.00	0.00	20	3000	0.5	0.5	136	3500	0.41	34.0
0.00	0.00	1.00	0.00	0.00	0.00	2
								83	0.60	0.35	0.00	0.00	0.00	0.05	20								3000	0.0	1.0	136	3550	0.4	41.0
0.00	0.00	1.00	0.00	0.00	0.00	2
							84		0.63	0.32	0.00	0.00	0.05	0.00	55	3000	0.0	1.0	50	3550	0.43	40.0
0.00	0.00	0.00	1.00	0.00	0.00	5
								85	0.63	0.32	0.00	0.00	0.05	0.00	80								3000	0.0	1.0	35	3500	0.43	42.0
0.00	0.00	0.00	1.00	0.00	0.00	5
							86		0.63	0.32	0.00	0.00	0.05	0.00	150	3000	0.0	1.0	19	3450	0.53	53.0
0.00	0.00	0.00	1.00	0.00	0.00	10
								87	0.63	0.32	0.00	0.00	0.05	0.00	30								3000	0.0	1.0	94	3550	0.43	42.0
0.00	0.00	0.50	0.50	0.00	0.00	2

Lamination hard coat of the present invention (embodiment 77 to 87) is compared with conventional hard coat (comparative example 1 and 2), all has more excellent hardness, lower frictional coefficient and narrower wearing and tearing width.By deposition lamination hard coat (EXPERIMENTAL EXAMPLE 77 to 83), can also realize surpassing the frictional coefficient of individual layer hard coat (embodiment 46) and reducing of wearing and tearing width.The result of the lamination hard coat of the individual layer hard coat of embodiment 76 and embodiment 84 to 87 shows that also embodiment of the present invention are in full force and effect for the hard coat that contains Si.

EXPERIMENTAL EXAMPLE 8

[formation of hard coat]

The equipment that uses is the equipment that schematically shows among Fig. 5.In embodiment 88 to 98, the target 2 that uses is the targets with the composition shown in " composition ratio of target (atom ratio) " of " layer A (row of going up) " in the table 7, the target 2A that uses is the target with the composition shown in " composition ratio of target (atom ratio) " of " layer B (row down) " in the table 7, and uses these targets deposition hard coats.In addition, the program of repeated experiments embodiment 3.

[assessment of hard coat]

To hard coat assessment their hardness, frictional coefficient and the wearing and tearing width that obtains.The results are shown in the table 8.

Table 8

	Layer A (row of going up)/layer B (row down)
																The composition ratio of target (atom ratio)						Thickness	Total thickness	Film forming gas		Precipitation number	Hardness	Frictional coefficient	The wearing and tearing width
	Al	V	Zr	Hf	Si	B	(nm)	(nm)	C	N		(HV)	(μ)	(μm)
															Comparative example
1	Ti 0.4Al 0.6N						3000	3000	0.0	1.0	1	2800	0.85	100.0
															2	Cr 0.4Al 0.6N						3000	3000	0.0	1.0	1	2750	0.78	110.0
Embodiment
															46	0.65	0.35	0.00	0.00	0.00	0.00	3000	3000	0.0	1.0	1	3450	0.55	65.0
76	0.63	0.32	0.00	0.00	0.05	0.00	3000	3000	0.0	1.0	1	3300	0.57	55.0
															88	0.65	0.35	0.00	0.00	0.00	0.00	20	3000	0.0	1.0	143	3300	0.55	50.0
0.00	0.00	1.00	0.00	0.00	0.00	1
							89	0.65	0.35	0.00	0.00	0.00	0.00	20		3000	0.0	1.0	130	3500	0.55	44.0
0.00	0.00	1.00	0.00	0.00	0.00	3
								90	0.65	0.35	0.00	0.00	0.00	0.00	20								3000	0.0	1.0	103	3600	0.54	40.0
0.00	0.00	1.00	0.00	0.00	0.00	9
							91		0.65	0.35	0.00	0.00	0.00	0.00	20	3000	0.0	1.0	86	3550	0.56	35.0
0.00	0.00	1.00	0.00	0.00	0.00	15
								92	0.65	0.35	0.00	0.00	0.00	0.00	20								3000	0.0	1.0	55	3500	0.55	45.0
0.00	0.00	1.00	0.00	0.00	0.00	35
							93		0.65	0.35	0.00	0.00	0.00	0.00	20	3000	0.5	0.5	136	3500	0.54	34.0
0.00	0.00	1.00	0.00	0.00	0.00	2
								94	0.60	0.35	0.00	0.00	0.00	0.05	20								3000	0.0	1.0	136	3600	0.56	41.0
0.00	0.00	0.00	1.00	0.00	0.00	2
							95		0.63	0.32	0.00	0.00	0.05	0.00	55	3000	0.0	1.0	50	3450	0.5	40.0
0.00	0.00	0.00	1.00	0.00	0.00	5
								96	0.63	0.32	0.00	0.00	0.05	0.00	80								3000	0.0	1.0	35	3500	0.53	47.0
0.00	0.00	0.00	1.00	0.00	0.00	5
							97		0.63	0.32	0.00	0.00	0.05	0.00	150	3000	0.0	1.0	19	3600	0.56	55.0
0.00	0.00	0.00	1.00	0.00	0.00	10
								98	0.63	0.32	0.00	0.00	0.05	0.00	30								3000	0.0	1.0	94	3550	0.53	42.0
0.00	0.00	0.50	0.50	0.00	0.00	2

Lamination hard coat of the present invention (embodiment 88 to 98) is compared with conventional hard coat (comparative example 1 and 2), all has more excellent hardness, lower frictional coefficient and narrower wearing and tearing width.Under the situation of lamination hard coat (experimental example 87 to 93), can when frictional coefficient being remained essentially in the level identical, realize the raising of hardness and reducing of wearing and tearing width with individual layer hard coat (embodiment 46).Embodiment of the present invention also are (embodiment 95 to 98) in full force and effect for the hard coat that contains Si.

Hard coat of the present invention has fabulous hardness and oilness, therefore can be used for cutting tool (shovel, brill and end mill etc.) and anchor clamps and instrument (forging die (forging dye), block stamp etc.), and can be used in the various automobile sliding members.

Foregoing invention is described according to a preferred embodiment.But, those skilled in the art will recognize that there are many variants in such embodiment.Such variant is also in the scope of the present invention and appended claim.

Claims (24)

1, a kind of hard coat, it comprises (Al _1-aV _a) (C _1-XN _X), wherein

0.27≤a≤0.75, and

0.3≤X≤1，

Wherein a and X represent atom ratio independently.

2, a kind of hard coat, it comprises (Al _1-a-b-cV _aSi _bB _c) (C _1-XN _X), wherein

0.1≤a≤0.75，

0＜b+c≤0.20, and

0.3≤X≤1，

Wherein a, b, c and X represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0.

3, a kind of multilayer hard coat, it is made by the repeated deposition thin layer, and described thin layer comprises nitride or the carbonitride that is selected from least a element among Al, V, Si and the B, wherein periodically for being not more than 80nm, and

Satisfy the composition of claim 1 or 2 average the composition.

4, a kind of multilayer hard coat, wherein said coating is by making below the repeated deposition:

(1) comprise the thin layer of the nitride of TiAl or carbonitride and/or comprise the nitride of CrAl or the thin layer of carbonitride and

(2) the average thin layer of forming the composition that satisfies claim 1 or 2 is wherein periodically for being not more than 80nm.

5, according to any one hard coat of claim 1 to 4, wherein said hard coat has the NaCl-type crystal structure.

6, a kind of lamination hard coat, it comprises any one hard coat of multilayer claim 1 to 5, wherein the hard coat difference that is adjacent of each hard coat.

7, a kind of compound hard coat wherein deposits at least one surface of the hard coat of any one in claim 1 to 6:

(1) be different from the hard coat of the hard coat of any one in the claim 1 to 6, this hard coat comprises metal nitride, metal carbonate or the carbonitride with NaCl-type crystal structure, perhaps

(2) be selected from 4A in the periodic table of elements, 5A and at least a metal of 6A family element, Al and Si and the layer of alloy thereof.

8, a kind of hard coat, it comprises (Al _1-a-d-eV _aMo _dW _e) (C _1-XN _X), wherein

0.2≤a≤0.75，

0＜d+e≤0.3, and

0.3≤X≤1，

Wherein a, d, e and X represent atom ratio independently, and precondition is that d and e are not 0 simultaneously, and among d and the e one can be 0.

9, a kind of hard coat, it comprises (Al _1-a-b-c-d-eV _aSi _bB _cMo _dW _e) (C _1-XN _X), wherein

0.2≤a≤0.75，

0＜b+c≤0.20，

0＜d+e≤0.3, and

0.3≤X≤1，

Wherein a, b, c, d, e and X represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0, and d and e be not 0 simultaneously, and among d and the e one can be 0.

10, a kind of hard coat, it comprises (Al _1-a-f-gV _aHf _fZr _g) (C _1-XN _X), wherein

0.01≤a≤0.75，

0＜f+g≤0.5, and

0.3≤X≤1，

Wherein a, f, g and X represent atom ratio independently, and precondition is that f and g are not 0 simultaneously, and among f and the g one can be 0.

11, a kind of hard coat, it comprises (Al _1-a-b-c-f-gV _aSi _bB _cHf _fZr _g) (C _1-XN _X), wherein

0.01≤a≤0.75，

0＜b+c≤0.20，

0＜f+g≤0.5, and

0.3≤X≤1，

Wherein a, b, c, f, g and X represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0, and f and g be not 0 simultaneously, and among f and the g one can be 0.

12, according to Claim 8 to 11 any one hard coats, wherein said hard coat has the NaCl-type crystal structure.

13, a kind of lamination hard coat, it comprises

Comprise claim 1 and 2 any one hard coat layer (below be called a layer A) and

Comprise by selecting layer (below be called a layer B) of at least a compound that obtains among at least a and C and the N among Mo and the W.

14, according to the hard coat of claim 13, the thickness of wherein said layer A and described layer B is such: thickness≤200nm of thickness≤layer A of layer B.

15, a kind of lamination hard coat, it comprises

Comprise claim 1 and 2 any one hard coat layer (below be called a layer A) and

Comprise by selecting layer (below be called a layer C) of at least a compound that obtains among at least a and C and the N among Zr and the Hf.

16, according to the hard coat of claim 15, the thickness of wherein said layer A and described layer C is such: thickness≤200nm of thickness≤layer A of layer C.

17, a kind of hard coat, it is to use following target, contain with respect to N and C summation be in the gas of N of 30 to 100 atom % by the arc ions electroplating deposition,

Comprise (Al _1-aVa) target, 0.27≤a≤0.75 wherein, wherein a represents atom ratio, perhaps

Comprise (Al _1-a-b-cV _aSi _bB _c) target, wherein 0.1≤a≤0.75 and 0＜b+c≤0.20 wherein a, b and c represent atom ratio independently, precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0.

18, a kind of target that is used to deposit hard coat, it comprises following element (i) any in (iv):

(i) Al and V,

(ii) Al, V and Si,

(iii) Al, V and B and

(iv) Al, V, Si and B,

The relative density of described target is not less than 95%.

19, a kind of target that is used to deposit hard coat, it comprises

(Al _1-aV _a), wherein

0.27≤a≤0.75，

Wherein a represents atom ratio.

20, a kind of target that is used to deposit hard coat, it comprises (Al _1-a-b-cV _aSi _bB _c), wherein

0.1≤a≤0.75, and

0＜b+c≤0.20，

Wherein a, b and c represent atom ratio independently, and precondition is that b and c are not 0 simultaneously, and among b and the c one can be 0.

21, a kind ofly be used to deposit any one the method for hard coat of claim 1 to 16, this method is included in and is used for Ionized film forming atmosphere evaporated metal, and promotes the plasma bodyization of film forming gas and the Ionized step that is used for the described metal of deposited coatings.

22, a kind of method that is used to deposit the hard coat of claim 19, wherein the formation of film is electroplated by arc ions and is carried out, wherein constitute the metal of target by arc-over evaporation and ionization, be formed on the upwardly extending parallel or magnetic line of force dispersed in the side of the water surface of evaporation that is substantially perpendicular to target, and near target part, promote the plasma bodyization of film forming gas by these magnetic line of force that are used to deposit hard coat.

23, according to the method that is used to deposit hard coat of claim 21 or 22, wherein the magneticflux-density in the surface of the target part that will apply hard coat is not less than 10 Gausses.

24, according to any one the method that is used to deposit hard coat of claim 21 to 22, wherein between target and target part, form magnetic field, make the angle that forms between magnetic line of force and the described target evaporation normal to a surface be no more than ± 30 °.

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