CN104789938A - Surface coating cutting tool hard coating layer of which gives play to excellent anti-tipping performance - Google Patents
Surface coating cutting tool hard coating layer of which gives play to excellent anti-tipping performance Download PDFInfo
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Abstract
The subject of the invention is to provide a surface coating cutting tool a hard coating layer of which has excellent hardness and toughness and gives play to anti-tipping performance and defect-resistant performance. The hard coating layer contains a composite nitride represented by a compositional formula of (Ti<1-x-y>Al<x>Me<y>)(C<z>N<1-z>) or a layer of the composite nitride, wherein Me is an element selected from Si, Zr, B, V and Cr, the average contained proportion Xav of Al, the average contained proportion Yav of Me, the average contained proportion Zav of C meet 0.60<=Xav<=0.95, 0.005<=Yav<=0.10, 0<=Zav<=0.005 and Xav+Yav<=0955, the Xav, the Yav and the Zav are atomic ratios; and the layer at least contains cubic grains and has a granular structure the average particle width W of the cubic grains of which is 005-1.0[mu]m and the average aspect ratio A of which is lower than 5, and specified-period concentration changes of Ti, Al and Me exist in the cubic particles, so the subject is solved.
Description
Technical field
The present invention relates to a kind of steel alloy etc. occur with high heat and impact load acts in the high rate intermittent machining of cutting edge, possessed by hard coating layer and excellent resistance toly collapse cutter and in life-time service, play the surface-coated cutting tool (hereinafter referred to as coating tool) of excellent cutting ability.
Background technology
In the past, known general on the surface of the matrix (below these being referred to as matrix) be made up of wolfram varbide (representing with WC below) base cemented carbide, titanium carbonitride (representing with TiCN below) based ceramic metal or cubic boron nitride (representing with cBN below) base ultra-high pressure sintered compact, by the coated coating tool of composite nitride nitride layer as hard coating layer forming Ti-Al system of physical vapor deposition, and these coating tools known play excellent wear resistance.
But, although the coating tool wear resistance that described in the past coated is formed with the composite nitride nitride layer of Ti-Al system is more excellent, but easily collapse the abnormal wear such as cutter when using under high rate intermittent machining condition, therefore various scheme is proposed to the improvement of hard coating layer.
Such as, following coating tool is disclosed: in tool base in patent documentation 1, by physical vapor deposition be coated with more than one deck by comprising Ti, Al, the metallic element of Si or by a part of Ti by periodictable 4, 5, the metallic element that 6 race's elements replace, and be selected from B, C, N, the hard coating layer that the element more than at least one in O is formed, wherein, the Nitride Phase of Si is accompanied in hard coating layer, the dry type of the glass hard steel machining after thermal treatment can be tackled thus, high speed, even and if the hardness deterioration of hard coating layer at high temperature also can be suppressed.
And, following content is disclosed: on tool base surface successively coated 1st coating layer and there is columnar crystal structure and along the 2nd coating layer that grows with the direction of the angular slope of average 1 ~ 15 ° relative to the vertical line direction on tool base surface in patent documentation 2, even if impact thus and put on hard coating layer, also can disperse and impact to be difficult to be passed to the 1st coating layer from the power of the 2nd coating layer transmission, crackle is difficult to expansion, its result, that can suppress to occur in hard coating layer collapses cutter and larger defect.
In addition, following surface-coated cutting tool is disclosed: possess tool base and be formed at the hard coating layer on this matrix in patent documentation 3, wherein, hard coating layer comes tremendous the wear resistance and the oxidation-resistance that improve hard coating layer by inclusion compound and chlorine, this compound by any one in Al or Cr or two kinds of elements, be selected from least one element in periodictable 4a, 5a, 6a race's element and Si and at least one element be selected from carbon, nitrogen, oxygen and boron is formed.
On the other hand, when forming hard coating layer by all the time general physical vapor deposition evaporation, be difficult to the proportional x that contains of Al to be set to more than 0.6, expect to improve cutting ability further.
From this point of view, also proposed and contain by what utilize chemical vapor deposition method formation hard coating layer by Al the technology that proportional x is increased to about 0.9.
Such as, following content is recorded in patent documentation 4: at TiCl
4, AlCl
3, NH
3hybrid reaction gas in, carry out chemical vapor deposition the temperature ranges of 650 ~ 900 DEG C, thus can evaporation forms Al is (the Ti of 0.65 ~ 0.95 containing the value of proportional x
1-xal
x) N layer, in the document, at this (Ti
1-xal
x) also coated Al on N layer
2o
3layer, thus to improve for the purpose of insulation effect, therefore the value of x is increased to the (Ti of 0.65 ~ 0.95 by not open formation
1-xal
x) which kind of N layer has affect on cutting ability.
Further, such as, following content is proposed in patent documentation 5: by TiCN layer, Al
2o
3layer as internal layer, thereon by the coated cubic crystal structure of chemical vapor deposition method or the (Ti of cubic crystal structure comprising structure of hexagonal crystal
1-xal
x) N layer (wherein, x is 0.65 ~ 0.9) is as outer, and the stress under compression to this skin imparting 100 ~ 1100MPa, improve thermotolerance and the fatigue strength of coating tool thus.
Patent documentation 1: Japanese Patent Publication 2002-96205 publication
Patent documentation 2: Japanese Patent Publication 2008-105164 publication
Patent documentation 3: Japanese Patent Publication 2006-82207 publication
Patent documentation 4: Japanese Patent public affairs table 2011-516722 publication
Patent documentation 5: Japanese Patent public affairs table 2011-513594 publication
In recent years, saving labourization in machining and the requirement of energy-saving strong, machining has the trend of further high speed, high efficiency thereupon, collapse the resistance to Abnormal damages such as cutter, fracture resistance, peel resistance to coating tool requirement is further resistance to, and require in life-time service, play excellent wear resistance.
But, in the coating tool recorded in described patent documentation 1, by (Ti
1-xal
x) N layer form hard coating layer formed by physical vapor deposition evaporation, the Nitride Phase of Si etc. is accompanied in hard coating layer, nanocrystalline being scattered in has fcc structure and with in the TiAlN layer of columnar growth thus, this nanocrystalline generation lattice strain, and make the hardness of TiAlN increase by dispersion-strengthened mechanism, but this is nanocrystalline at grain boundary segregation, therefore such as when the high rate intermittent for steel alloy cuts, there is wear resistance, resistance toly collapse the insufficient problem of cutter.
Further, the coating tool recorded in patent documentation 2 and patent documentation 3 is intended to improve fracture resistance and wear resistance, anti-oxidation characteristics respectively, but in such as high rate intermittent cutting etc. with under the machining condition impacted, and exists resistance toly to collapse the insufficient problem of cutter.
On the other hand, about (the Ti that the chemical vapor deposition method evaporation by recording in described patent documentation 4 is formed
1-xal
x) N layer, Al can be improved containing proportional x, and, cubic crystal structure can be formed, therefore can obtain the hard coating layer with regulation hardness and excellent in abrasion resistance, but exist with the adhesion strength of matrix insufficient, and, the problem that toughness is poor.
In addition, although the coating tool recorded in described patent documentation 5 has regulation hardness and excellent in abrasion resistance, but toughness is poor, therefore when supplying the high rate intermittent machining etc. of steel alloy, exist and easily collapse the Abnormal damages such as cutter, defect, stripping, the problem of gratifying cutting ability cannot be played.
Summary of the invention
Therefore, even if technical task to be solved by this invention, namely the object of the present invention is to provide a kind of when the high rate intermittent cutting etc. for steel alloy, carbon steel, cast iron etc., also possess excellent toughness, and in life-time service, play the excellent resistance to coating tool collapsing cutter, wear resistance.
Therefore, the present inventors from the above point of view, is formed with by chemical vapor deposition evaporation the complex nitride that at least comprises Ti and Al or composite carbon nitride (below, uses " (Ti; Al) (C, N) " or " (Ti sometimes to realize improving
1-xal
x) (C
yn
1-y) " represent) and coating tool resistance to of hard coating layer collapse cutter, wear resistance and repeatedly conducting in-depth research, result obtains following opinion.
That is, in the past at least comprise one deck (Ti
1-xal
x) (C
yn
1-y) layer and the hard coating layer with the average thickness of regulation be as (Ti
1-xal
x) (C
yn
1-y) layer in tool base vertically in column formed time, there is higher wear resistance.On the other hand, (Ti
1-xal
x) (C
yn
1-y) higher (Ti of anisotropy of layer
1-xal
x) (C
yn
1-y) toughness of layer more declines, its result, resistance toly collapse cutter, fracture resistance declines, and cannot play sufficient wear resistance, and life tools can not be said in life-time service satisfactory.
Therefore, the present inventors is to (the Ti forming hard coating layer
1-xal
x) (C
yn
1-y) layer conducts in-depth research, a kind of element (representing with " Me " below) be selected from Si, Zr, B, V, Cr is contained in hard coating layer, thus forms (Ti mutually with hexagonal crystal by a cube crystalline phase
1-x-yal
xme
y) (C
zn
1-z) layer, and, the periodicity change in concentration of Ti, Al and Me is formed in cube crystalline phase, be conceived to this design completely newly, hardness and toughness is successfully improved by making cubic grain generation strain, its result, finds the resistance to brand-new opinion collapsing cutter, fracture resistance that can improve hard coating layer.
Specifically, find as follows: hard coating layer at least comprise by the average thickness of chemical vapor deposition method film forming be Ti, Al and Me of 1 ~ 20 μm (wherein, Me is a kind of element be selected from Si, Zr, B, V, Cr) complex nitride or the layer of composite carbon nitride, when with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) represent time, Al is at Ti, in the total amount of Al and Me shared average containing proportional Xav and Me at Ti, in the total amount of Al and Me shared average containing proportional Yav and C in the total amount of C and N shared average containing proportional Zav (wherein, Xav, Yav, Zav is atomic ratio) meet 0.60≤Xav≤0.95 respectively, 0.005≤Yav≤0.10, 0≤Zav≤0.005, Xav+Yav≤0.955, the layer of described complex nitride or composite carbon nitride comprises the crystal grain (or also comprising the crystal grain of the structure of hexagonal crystal with wurtzite-type) of the face-centred cubic structure with NaCl type, from the epithelium cross-section vertical with tool base surface, measure the particle width of each crystal grain and aspect ratio to obtain averaged particles width W, when Mean aspect size is than A, particle width when the direction parallel with tool base surface of the crystal grain of the face-centred cubic structure by having NaCl type is set to w, and the particle length in the direction vertical with tool base surface is set to l, the ratio l/w of this w and l is set to the aspect ratio a of each crystal grain, in addition, the mean value of the aspect ratio a obtained each crystal grain is set to Mean aspect size and compares A, when the mean value of the particle width w obtained each crystal grain is set to averaged particles width W, be that averaged particles width W is 0.05 ~ 1.0 μm and Mean aspect size is the granular structure of less than 5 than A, composition formula is there is: (Ti in the crystal grain of the face-centred cubic structure of described NaCl type
1-x-yal
xme
y) (C
zn
1-z) in Ti, Al and Me periodicity change in concentration (namely, x, y, z non-constant value, but periodically variable value), when the mean value of the maximum value of the x value containing proportional x generating period change by Al is set to Xmax and the minimizing mean value of the x value containing proportional x generating period change of Al is set to Xmin, the difference of Xmax and Xmin is 0.05 ~ 0.25, the crystal grain of the face-centred cubic structure with NaCl type can be made thus to strain, compared with hard coating layer in the past, (Ti
1-x-yal
xme
y) (C
zn
1-z) hardness of layer and toughness is improved, its result, resistance toly collapse cutter, fracture resistance is improved, thus play excellent wear resistance for a long time.
And, (the Ti of structure as above
1-x-yal
xme
y) (C
zn
1-z) layer is such as by containing trimethyl aluminium (Al (CH
3)
3) when carrying out film forming as the following chemical vapor deposition method of reactant gases composition, can by adding SiCl
4carry out film forming.
(a) film formation process
Reactant gases composition (capacity %) is set to TiCl
4: 1.5 ~ 2.5%, Al (CH
3)
3: 0 ~ 5%, AlCl
3: 6 ~ 10%, MeCl
n: 1 ~ 3%, NH
3: 10 ~ 12%, N
2: 6 ~ 7%, C
2h
4: 0 ~ 1%, H
2: residue, and is set to reaction atmosphere pressure: 2 ~ 3kPa, reaction atmosphere temperature: 700 ~ 900 DEG C of thermal cvd of carrying out the specified time, form (the Ti of define objective thickness thus on tool base surface
1-x-yal
xme
y) (C
zn
1-z) layer.
(b) etching work procedure
When the film formation process of described (a), carry out the specified time, stipulated number by TiCl
4: 2.0 ~ 5.0 capacity %, H
2: residue, reaction atmosphere pressure: 2 ~ 5kPa, reaction atmosphere temperature: the TiCl that the condition of 750 ~ 900 DEG C is formed
4etching work procedure.
In addition, as the reactant gases composition MeCl used in above-mentioned [(a) film formation process]
n, the kind according to Me composition such as uses SiCl respectively
4, ZrCl
4, BCl
3, VCl
4, CrCl
2.Or, also can use as SiH
2cl
2the reactant gases that the part of such chloro is replaced by hydrogen.
By carrying out TiCl as above in film formation process
4etching work procedure, finds as follows: the face-centred cubic structure of NaCl type with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) crystal grain that represents is by selective etch, the local composition forming Ti, Al and Me in crystal grain is poor, and it causes the rearrangement of atom to realize stable, thus produces the periodical change formed, and its result, toughness obtains tremendous raising.Its result, especially fracture resistance, the resistance to cutter that collapses are improved, even if act on when using in the high rate intermittent machining of the steel alloy of cutting edge etc. at interrupted impact load, hard coating layer also can play excellent cutting ability in life-time service.
The present invention completes in view of above-mentioned opinion, and it has following feature:
(1) surface-coated cutting tool, is being provided with hard coating layer by the surface of any one tool base formed in tungsten carbide base carbide alloy, base titanium carbonitride or cubic boron nitride base ultra-high pressure sintered compact, wherein,
(a) described hard coating layer at least comprise by the average thickness of chemical vapor deposition method film forming be Ti, Al and Me of 1 ~ 20 μm (wherein, Me is a kind of element be selected from Si, Zr, B, V, Cr) complex nitride or the layer of composite carbon nitride, when with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) represent time, Al in the total amount of Ti, Al and Me shared average containing proportional Xav and Me in the total amount of Ti, Al and Me shared average containing proportional Yav and C in the total amount of C and N shared average containing proportional Zav (wherein, Xav, Yav, Zav are atomic ratio) meet 0.60≤Xav≤0.95,0.005≤Yav≤0.10,0≤Zav≤0.005, Xav+Yav≤0.955 respectively
B the layer of () described complex nitride or composite carbon nitride at least comprises the complex nitride of the face-centred cubic structure with NaCl type or the phase of composite carbon nitride,
(c) and, when observing from the epithelium sectional side vertical with tool base surface, measuring, be that the averaged particles width W of the complex nitride of the face-centred cubic structure with NaCl type or the crystal grain of composite carbon nitride is 0.05 ~ 1.0 μm and Mean aspect size is the granular structure of less than 5 than A
In addition, in the complex nitride of face-centred cubic structure with described NaCl type or the crystal grain of composite carbon nitride, there is composition formula: (Ti in (d)
1-x-yal
xme
y) (C
zn
1-z) in the periodicity change in concentration of Ti, Al and Me, when the mean value of the maximum value of the x value containing proportional x generating period change by Al is set to Xmax and the minimizing mean value of the x value containing proportional x generating period change of Al is set to Xmin, the difference of Xmax and Xmin is 0.05 ~ 0.25.
(2) surface-coated cutting tool described in (1), wherein,
The periodicity change in concentration of Ti, Al and Me in the layer that there is described complex nitride or composite carbon nitride have in the crystal grain of the face-centred cubic structure of NaCl type, the periodicity change in concentration of Ti, Al and Me is there is along an orientation in the crystalline orientation of the equivalence represented with < 001 > of cubic grain, cycle along this orientation is 3 ~ 30nm, the Al in the face orthogonal with this orientation containing proportional x be changed to less than 0.01.
(3) surface-coated cutting tool described in (1), wherein,
The periodicity change in concentration of Ti, Al and Me in the layer that there is described complex nitride or composite carbon nitride have in the crystal grain of the face-centred cubic structure of NaCl type, following region A and region B is there is in crystal grain, border between described region A and region B is formed at { a face in the equivalent crystal that 110} represents
A () region A: the periodicity change in concentration that there is Ti, Al and Me along an orientation in the crystalline orientation of the equivalence represented with < 001 > of cubic grain, if be set to orientation d by this orientation
a, then along orientation d
acycle be 3 ~ 30nm, with orientation d
aal in orthogonal face containing proportional x be changed to less than 0.01;
(b) region B: along with orientation d
athere is the periodicity change in concentration of Ti, Al and Me in an orientation in the crystalline orientation of the equivalence represented with < 001 > of orthogonal cubic grain, if this orientation is set to orientation d
b, then along orientation d
bcycle be 3 ~ 30nm, with orientation d
bal in orthogonal face containing proportional x be changed to less than 0.01.
(4) surface-coated cutting tool according to any one of (1) to (3), wherein,
The layer of described complex nitride or composite carbon nitride is made up of the complex nitride of Ti, Al and Me of face-centred cubic structure or the single-phase of composite carbon nitride with NaCl type.
(5) surface-coated cutting tool according to any one of (1) to (3), wherein,
The layer of described complex nitride or composite carbon nitride is made up of two or more multiple mixed phase coexisted mutually, this mixed phase at least comprises the complex nitride of Ti, Al and Me of the face-centred cubic structure with NaCl type or the phase of composite carbon nitride, and other coexisting in mixed phase are respectively by with at least one element be selected from Ti, Al and Me be selected from the compound that at least one in C, N formed and formed.
(6) surface-coated cutting tool according to any one of (1) to (3), (5), wherein,
In the layer of described complex nitride or composite carbon nitride, there is the crystal grain with the structure of hexagonal crystal of wurtzite-type, when measuring from the epithelium sectional side vertical with tool base surface, the area ratio existing for crystal grain with the structure of hexagonal crystal of this wurtzite-type is 30 below area %.
(7) surface-coated cutting tool according to any one of (1) to (6), wherein,
Lower layer is there is by between the complex nitride of any one tool base formed in described tungsten carbide base carbide alloy, base titanium carbonitride or cubic boron nitride base ultra-high pressure sintered compact and described Ti, Al and Me or the layer of composite carbon nitride, described lower layer comprises Ti compound layer, and described Ti compound layer is by the one deck in the carbide lamella of Ti, nitride layer, carbonitride layer, oxycarbide layer and carbon nitrogen oxide layer or two-layerly form and have the average thickness of total of 0.1 ~ 20 μm above.
(8) surface-coated cutting tool according to any one of (1) to (7), wherein,
There is the upper layer comprising alumina layer on the top of the layer of described complex nitride or composite carbon nitride, described alumina layer at least has the average thickness of 1 ~ 25 μm.
(9) surface-coated cutting tool according to any one of (1) to (8), wherein,
The layer of described complex nitride or composite carbon nitride is by least containing the chemical vapor deposition method film forming of trimethyl aluminium as reactant gases composition.
In addition, hard coating layer in the present invention is using the structure of the layer of complex nitride as above or composite carbon nitride as its essence, in addition, use all the time known lower layer and upper layer etc., the effect that certainly can play with the layer of complex nitride or composite carbon nitride thus combines and creates characteristic excellent further simultaneously.
Below, the present invention is described in detail.
Form the average thickness of the complex nitride of hard coating layer or the layer of composite carbon nitride:
Hard coating layer of the present invention at least comprise by chemical vapor deposition with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) complex nitride of Ti, Al and Me that represents or the layer of composite carbon nitride.The layer hardness of this complex nitride or composite carbon nitride is higher and have excellent wear resistance, especially when average thickness is 1 ~ 20 μm, significantly plays its effect.Its reason is, when average thickness is less than 1 μm, thickness is thinner, therefore in life-time service, fully wear resistance cannot be guaranteed, on the other hand, if its average thickness is more than 20 μm, then the easy coarsening of crystal grain of the complex nitride of Ti, Al and Me or the layer of composite carbon nitride, thus easily collapse cutter.Therefore, its average thickness is decided to be 1 ~ 20 μm.
Form the composition of the complex nitride of hard coating layer or the layer of composite carbon nitride:
When the layer of the complex nitride or composite carbon nitride that form hard coating layer of the present invention is with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) represent time (wherein, Me is a kind of element be selected from Si, Zr, B, V, Cr), be controlled to average containing proportional Yav and C in the total amount of C and N shared on average the contain proportional Zav (wherein, Xav, Yav, Zav be atomic ratio) of Al average proportional Xav and Me of containing shared in the total amount of Ti, Al and Me shared by the total amount of Ti, Al and Me and meet 0.60≤Xav≤0.95,0.005≤Yav≤0.10,0≤Zav≤0.005, Xav+Yav≤0.955 respectively.
Its reason is, if the average of Al is less than 0.60 containing proportional Xav, then the hardness of the complex nitride of Ti, Al and Me or the layer of composite carbon nitride is poor, and therefore when the high rate intermittent for steel alloy etc. cuts, wear resistance is insufficient.On the other hand, if Al average containing proportional Xav more than 0.95, then Ti containing proportional relative minimizing, therefore cause embrittlement, the resistance to cutter that collapses declines.Therefore, the average of Al is set as 0.60≤Xav≤0.95 containing proportional Xav.
Further, if the average of Me is less than 0.005 containing proportional Yav, then the hardness of the complex nitride of Ti, Al and Me or the layer of composite carbon nitride is poor, and therefore when the high rate intermittent for steel alloy etc. cuts, wear resistance is insufficient.On the other hand, if more than 0.10, then because Me is to the segregation etc. of grain circle, the toughness of the complex nitride of Ti, Al and Me or the layer of composite carbon nitride declines, and when the high rate intermittent for steel alloy etc. cuts, resistance to collapse cutter insufficient.Therefore, the average of Me is set as 0.005≤Yav≤0.10 containing proportional Yav.
At this, use and be selected from the concrete composition of a kind of element in Si, Zr, B, V, Cr as Me.
When the mode becoming more than 0.005 using Yav uses Si composition or B component as Me, the hardness of the layer of complex nitride or composite carbon nitride is improved, therefore the raising of wear resistance can be realized, Zr composition has the effect of strengthening crystal boundary, further, V composition improves toughness, therefore can realize resistance to further raising of collapsing cutter, Cr composition improves oxidation-resistance, therefore can expect the further long lifetime of life tools.But, any composition is all when on average containing proportional Yav more than 0.10, Al composition, Ti composition average containing proportional relative minimizing, therefore can demonstrate wear resistance or resistance toly collapse cutter downward trend, therefore must avoid becoming as average containing proportional more than 0.10 of Yav.
And, when C contained in the layer of complex nitride or composite carbon nitride average is the scope of 0≤Zav≤0.005 micro-containing proportional (atomic ratio) Zav, adhesivity between the layer of complex nitride or composite carbon nitride and tool base or lower layer is improved, and oilness is improved, relax impact when cutting thus, as a result, the fracture resistance of the layer of complex nitride or composite carbon nitride and the resistance to cutter that collapses are improved.On the other hand, if the average scope departing from 0≤Zav≤0.005 containing proportional Zav of C, then the toughness of the layer of complex nitride or composite carbon nitride declines, and therefore fracture resistance and the resistance to cutter that collapses decline on the contrary, therefore not preferred.Therefore, the average of C is set as 0≤Zav≤0.005 containing proportional Zav.
Form the crystal grain of the face-centred cubic structure (being only called below " cubic crystal ") with NaCl type of the layer of complex nitride or composite carbon nitride:
When observing from the epithelium sectional side vertical with tool base surface, when measuring each cubic grain in the layer of described complex nitride or composite carbon nitride, the particle width in the direction parallel with tool base surface is set to w, and the particle length in the direction vertical with tool base surface is set to l, the ratio l/w of described w and l is set to the aspect ratio a of each crystal grain, in addition, the mean value of the aspect ratio a obtained each crystal grain is set to Mean aspect size and compares A, when the mean value of the particle width w obtained each crystal grain is set to averaged particles width W, be controlled to averaged particles width W and meet 0.05 ~ 1.0 μm, Mean aspect size is than A satisfied less than 5.
When meeting this condition, the cubic grain forming the layer of complex nitride or composite carbon nitride becomes granular structure, demonstrates the resistance to of excellence and collapse cutter, fracture resistance while keeping the wear resistance of excellence.On the other hand, if Mean aspect size than A more than 5; crystal grain becomes column crystal, resistance to collapse cutter, fracture resistance decline, therefore not preferred.
Further, if averaged particles width W is less than 0.05 μm, wear resistance declines, if more than 1.0 μm, toughness declines.Therefore, the averaged particles width W forming the cubic grain of the layer of complex nitride or composite carbon nitride is decided to be 0.05 ~ 1.0 μm.
Having the change in concentration of Ti, Al and Me of existing in the crystal grain of cubic crystal structure:
In addition, when with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) represent when there is the crystal of cubic crystal structure, when there is the periodicity change in concentration of Ti, Al and Me in crystal grain (that is, x, y, z non-constant value, but during periodically variable value), crystal grain strains, and hardness is improved.But, when the mean value of the maximum value of the x value containing proportional x generating period change of the Al in the index of the change in concentration size by Ti, Al and Me, i.e. described composition formula is set to Xmax and the minimizing mean value of the x value containing proportional x generating period change of Al is set to Xmin, if the difference of Xmax and Xmin is less than 0.05, then the strain of aforesaid crystal grain is less and cannot expect the abundant raising of hardness.On the other hand, if the difference of Xmax and Xmin is more than 0.25, then the strain of crystal grain is excessive, and lattice imperfection becomes large, thus hardness declines.Therefore, in the change in concentration with Ti, Al and Me of existing in the crystal grain of cubic crystal structure, the difference of Xmax and Xmin is set to 0.05 ~ 0.25.And, the periodicity change in concentration of Ti, Al and Me in the layer that there is described complex nitride or composite carbon nitride have in the crystal grain of cubic crystal structure, when there is the periodicity change in concentration of Ti, Al and Me along an orientation in the crystalline orientation of the equivalence represented with < 001 > of cubic grain, be difficult to the lattice imperfection produced because the strain of crystal grain causes, toughness is improved.And, in the face that the orientation that there is the periodicity change in concentration of Ti, Al and Me with described is orthogonal, in fact the concentration of Ti, Al and Me do not change, and the Al of the change in concentration of Ti, Al and Me in above-mentioned orthogonal face is shared in the total amount of Ti, Al and Me is changed to less than 0.01 containing proportional mean value Xo.
And, the cycle of the change in concentration of an orientation in the crystalline orientation of the equivalence represented with < 001 > along described cubic grain is when being less than 3nm, toughness declines, if more than 30nm, cannot give full play to the raising effect of hardness.Therefore, more preferably the cycle of described change in concentration is 3 ~ 30nm.
Further, for exist in orthogonal both direction Ti, Al and Me periodicity change in concentration, in crystal grain the crystal grain of domain of the existence A and region B, be present in crystal grain by making the strain of both direction and improve toughness.In addition, the border of region A and region B is formed at so that { face in the equivalent crystal that 110} represents, can not produce the mismatch on the border of region A and region B thus, therefore, it is possible to maintain higher toughness.
That is, when being formed: the periodicity change in concentration that there is Ti, Al and Me along an orientation in the crystalline orientation of the equivalence represented with < 001 > of cubic grain, when this orientation is set to orientation d
atime, along orientation d
acycle be 3 ~ 30nm, with orientation d
aal in orthogonal face containing proportional x be changed to less than 0.01 region A; And along with orientation d
athere is the periodicity change in concentration of Ti, Al and Me in an orientation in the crystalline orientation of the equivalence represented with < 001 > of orthogonal cubic grain, when this orientation is set to orientation d
btime, along orientation d
bcycle be 3 ~ 30nm, with orientation d
bal in orthogonal face containing proportional x be changed to the region B of less than 0.01 time, the strain of both direction is there is in crystal grain, toughness is improved thus, in addition, the border of region A and region B is formed at { a face in the equivalent crystal that 110} represents, the mismatch on the border of region A and region B can not be produced thus, therefore, it is possible to maintain higher toughness.
The area ratio shared by cube crystalline phase in crystal grain:
The layer of complex nitride of the present invention or composite carbon nitride can be made up of the single-phase of cube crystalline phase of the Electron Back-Scattered Diffraction image observing cubic(al)grating, but also can with the morphosis of two or more multiple mixed phase coexisted mutually.Now, other beyond cube crystalline phase coexisted in mixed phase are each mutually also can with at least one element be selected from Ti, Al and Me and the morphosis of compound being selected from least one in C, N.
As other phase, such as when using Electron Back-Scattered Diffraction device (EBSD) from the crystalline orientation of vertical section (the epithelium cross section vertical with tool base surface) each crystal grain of Orientation of the layer of the complex nitride of described Ti, Al and Me or composite carbon nitride, allow to there is the hexagonal crystal phase observing the Electron Back-Scattered Diffraction image of the hexagonal lattice of the structure of hexagonal crystal (being only called below " hexagonal crystal ") with wurtzite-type.
But when existing as the hexagonal crystal phase time of mixed phase, when measuring the shared mutually area ratio of this hexagonal crystal from the epithelium sectional side vertical with tool base surface, the area ratio of this hexagonal crystal shared by measuring in the area of visual field is preferably 30 below area %.This is because if the shared mutually area ratio of the hexagonal crystal in crystal grain is more than 30 area %, hardness declines, its result, and wear resistance declines.
And, the layer of complex nitride of the present invention or composite carbon nitride, even if comprising the carbide lamella by Ti, nitride layer, carbonitride layer, one deck in oxycarbide layer and carbon nitrogen oxide layer or two-layer above form and the Ti compound layer with the average thickness of total of 0.1 ~ 20 μm as lower layer time, and/or the alumina layer comprising the average thickness with 1 ~ 25 μm as upper layer time, aforesaid characteristic also can not be impaired, by using these known lower layer and upper layer etc. simultaneously, can combine with the effect that these layers play and create more excellent characteristic.When comprise by the one deck in the carbide lamella of Ti, nitride layer, carbonitride layer, oxycarbide layer and carbon nitrogen oxide layer or two-layer more than the Ti compound layer that forms as lower layer time, if the average thickness of the total of Ti compound layer is more than 20 μm, the then easy coarsening of crystal grain, thus easily collapse cutter.Further, when comprising alumina layer as upper layer, if the average thickness of the total of alumina layer is more than 25 μm, then the easy coarsening of crystal grain, thus easily collapse cutter.On the other hand, if lower layer is lower than 0.1 μm, then that cannot expect the layer of complex nitride of the present invention or composite carbon nitride improves effect with the adhesivity of lower layer, and, if upper layer is lower than 1 μm, then the wear resistance obtained based on formation upper layer improves effect can not be remarkable.
The schematic cross-section of the complex nitride of Ti, Al and Me of hard coating layer of the present invention or the layer of composite carbon nitride is formed shown in Fig. 1.
Of the present inventionly be provided with in the surface-coated cutting tool of hard coating layer by the surface of any one tool base formed in tungsten carbide base carbide alloy, base titanium carbonitride or cubic boron nitride base ultra-high pressure sintered compact, it is the complex nitride of Ti, Al and Me of 1 ~ 20 μm or the layer of composite carbon nitride that hard coating layer at least comprises by the average thickness of chemical vapor deposition method film forming, when with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) represent time, Al is at Ti, in the total amount of Al and Me shared average containing proportional Xav and Me at Ti, in the total amount of Al and Me shared average containing proportional Yav and C in the total amount of C and N shared average containing proportional Zav (wherein, Xav, Yav, Zav is atomic ratio) meet 0.60≤Xav≤0.95 respectively, 0.005≤Yav≤0.10, 0≤Zav≤0.005, Xav+Yav≤0.955, the layer of complex nitride or composite carbon nitride at least comprises the complex nitride of the face-centred cubic structure with NaCl type or the phase (cube crystalline phase) of composite carbon nitride, when observing from the epithelium sectional side vertical with tool base surface, during mensuration, be that the averaged particles width W of cubic grain is 0.05 ~ 1.0 μm and Mean aspect size is the granular structure of less than 5 than A, composition formula is there is: (Ti in the crystal grain with cubic crystal structure
1-x-yal
xme
y) (C
zn
1-z) in the periodicity change in concentration of Ti, Al and Me, when the mean value of the maximum value of the x value containing proportional x generating period change by Al is set to Xmax and the minimizing mean value of the x value containing proportional x generating period change of Al is set to Xmin, the difference of Xmax and Xmin is 0.05 ~ 0.25, strain in the crystal grain with cubic crystal structure of complex nitride or composite carbon nitride thus, therefore the hardness of crystal grain is improved, and improves toughness while keeping higher wear resistance.Its result, can play and improve the resistance to effect collapsing cutter, compared with hard coating layer in the past, plays excellent cutting ability, thus realize the long lifetime of coating tool in life-time service.
Accompanying drawing explanation
Fig. 1 is the membrane structure schematic diagram in the cross section schematically representing the complex nitride of Ti, Al and Me of forming hard coating layer of the present invention or the layer of composite carbon nitride.
Fig. 2 schematically represents to be equivalent on the composite nitride nitride layer of Ti, Al and Me of the hard coating layer of one embodiment of the present invention or the cross section of composite carbon nitride layer in formation, about the crystal grain with cubic crystal structure of periodicity change in concentration that there is Ti, Al and Me, the periodicity change in concentration of Ti, Al and Me is there is, the schematic diagram of the situation less containing the change of proportional x of the Al in the face orthogonal with this orientation along an orientation in the crystalline orientation of the equivalence represented with < 001 > of cubic grain.
Fig. 3 schematically represents to be equivalent on the composite nitride nitride layer of Ti, Al and Me of the hard coating layer of one embodiment of the present invention or the cross section of composite carbon nitride layer in formation, about the crystal grain with cubic crystal structure of periodicity change in concentration that there is Ti, Al and Me, the schematic diagram of the situation of domain of the existence A and region B in crystal grain.
Fig. 4 represents to be equivalent on the composite nitride nitride layer of Ti, Al and Me of the hard coating layer of one embodiment of the present invention or the cross section of composite carbon nitride layer in formation, for the crystal grain with cubic crystal structure of periodicity change in concentration that there is Ti, Al and Me, transmission electron microscope is used to carry out in the result after based on the line analysis of energy dispersion-type X-ray spectrography (EDS) Al relative to the figure of an example of the graphic representation of the periodicity change in concentration x of the total of Ti, Al and Me.
Embodiment
Of the present inventionly namely be provided with in the surface-coated cutting tool of hard coating layer by the surface of any one tool base formed in tungsten carbide base carbide alloy, base titanium carbonitride or cubic boron nitride base ultra-high pressure sintered compact in hard alloy tool base, it is the complex nitride of Ti, Al and Me of 1 ~ 20 μm or the layer of composite carbon nitride that hard coating layer at least comprises by the average thickness of chemical vapor deposition method film forming, when with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) represent time, Al is at Ti, in the total amount of Al and Me shared average containing proportional Xav and Me at Ti, in the total amount of Al and Me shared average containing proportional Yav and C in the total amount of C and N shared average containing proportional Zav (wherein, Xav, Yav, Zav is atomic ratio) meet 0.60≤Xav≤0.95 respectively, 0.005≤Yav≤0.10, 0≤Zav≤0.005, Xav+Yav≤0.955, the crystal grain forming the layer of complex nitride or composite carbon nitride at least comprises the crystal grain with cubic crystal structure, when observing from the epithelium sectional side vertical with tool base surface, during mensuration, be that the averaged particles width W of the crystal grain with cubic crystal structure is 0.05 ~ 1.0 μm and Mean aspect size is the granular structure of less than 5 than A, composition formula is there is: (Ti in the crystal grain with cubic crystal structure
1-x-yal
xme
y) (C
zn
1-z) in Ti, the periodicity change in concentration of Al and Me, when the mean value of the maximum value of the x value containing proportional x generating period change by Al is set to Xmax and the minimizing mean value of the x value containing proportional x generating period change of Al is set to Xmin, the difference of Xmax and Xmin is 0.05 ~ 0.25, by having this structure, the resistance to cutter that collapses is improved, compared with hard coating layer in the past, excellent cutting ability is played in life-time service, thus realize the long lifetime of coating tool, as long as this surface-coated cutting tool, then its embodiment can be arbitrary.
Then, the embodiment of embodiment to coating tool of the present invention is used to be specifically described.
[embodiment 1]
As raw material powder, prepare WC powder, TiC powder, TaC powder, NbC powder, the Cr all with the median size of 1 ~ 3 μm
3c
2powder and Co powder, these raw material powders are fitted in the cooperation composition shown in table 1, further interpolation paraffin, ball milling mixes 24 hours in acetone, after carrying out drying under reduced pressure, under the pressure of 98MPa, impact briquetting is the pressed compact of regulation shape, the condition that this pressed compact keeps 1 hour with the specified temperature within the scope of 1370 ~ 1470 DEG C in the vacuum of 5Pa is carried out vacuum sintering, after sintering, produce the tool base A ~ C of the WC base cemented carbide of the blade shapes with iso standard SEEN1203AFSN respectively.
Further, as raw material powder, TiCN (being TiC/TiN=50/50 by quality ratio) powder, the Mo all with the median size of 0.5 ~ 2 μm is prepared
2c powder, ZrC powder, NbC powder, WC powder, Co powder and Ni powder, these raw material powders are fitted in the cooperation composition shown in table 2, and utilize ball mill wet mixing 24 hours, after drying, under the pressure of 98MPa, impact briquetting is pressed compact, by this pressed compact in the nitrogen atmosphere of 1.3kPa with temperature: keep the condition of 1 hour to sinter at 1500 DEG C, after sintering, produce the tool base D of the TiCN based ceramic metal of the blade shapes with iso standard SEEN1203AFSN.
Then, on the surface of these tool base A ~ D, common chemical evaporation plating device is used,
A () the formation condition A shown in table 4 ~ V, that is, be set to TiCl by reactant gases composition (capacity %)
4: 1.5 ~ 2.5%, Al (CH
3)
3: 0 ~ 5%, AlCl
3: 6 ~ 10%, MeCl
n: 1 ~ 3%, NH
3: 10 ~ 12%, N
2: 6 ~ 7%, C
2h
4: 0 ~ 1%, H
2: residue, and is set to reaction atmosphere pressure: 2 ~ 3kPa, reaction atmosphere temperature: 700 ~ 900 DEG C of thermal cvd of carrying out the specified time, carries out the averaged particles width W shown in table 7,8 and the Mean aspect size (Ti than the granular structure of A thus
1-x-yal
xme
y) (C
zn
1-z) film forming (film formation process) of layer.
In addition, about above-mentioned MeCl
n, the classification according to Me (Si, Zr, B, V, Cr) uses SiCl respectively
4, ZrCl
4, BCl
3, VCl
4, CrCl
2.
B (), when the film formation process of described (a), carries out the formation condition a shown in the table 5 ~ j of specified time, stipulated number, that is, reactant gases composition (capacity %) is set to TiCl
4: 2.0 ~ 5.0%, H
2: residue, and be set to reaction atmosphere pressure: 2 ~ 5kPa, reaction atmosphere temperature: the TiCl of 750 ~ 900 DEG C
4etching work procedure (etching work procedure).
C () is in the film formation process of described (a), carry out the etching work procedure be made up of (b) of the specified time shown in table 7,8, stipulated number, formed thus by the (Ti at least comprising the granular structure of cubic crystal with the target thickness shown in table 7,8
1-x-yal
xme
y) (C
zn
1-z) hard coating layer that layer is formed, thus produce coating tool 1 ~ 27 of the present invention.
In addition, for coating tool 6 ~ 13,17,18,20,21,24,27 of the present invention, the lower layer shown in table 6 and/or the upper layer shown in table 7,8 under the formation condition shown in table 3, is formed.
For the complex nitride of Ti, Al and Me or the layer of composite carbon nitride of the hard coating layer of the described coating tool 1 ~ 27 of the present invention of formation, use the result that scanning electron microscope (multiplying power 5000 times and 20000 times) carries out observing throughout multiple visual field, shown in membrane structure schematic diagram as shown in Figure 1, confirm (the Ti of the granular structure of the mixed phase comprising cubic crystal or cubic crystal and hexagonal crystal
1-x-yal
xme
y) (C
zn
1-z) layer.Further, transmission electron microscope (multiplying power 200000 times) is used, by confirming based on the surface analysis of energy dispersion-type X-ray spectrography (EDS) periodic distribution that there is Ti, Al and Me in cubic grain.In addition, utilize the result by using the EDS of transmission electron microscope (multiplying power 200000 times) to carry out surface analysis, the mean value of the maximum value of the x in the cycle of the x of five cycle portions of the cubic grain existed in the layer of complex nitride in the present invention or composite carbon nitride is set to Xmax, and similarly the minimizing mean value of the x in the cycle of the x of five cycle portions is set to Xmin, obtain the result of its poor (=Xmax-Xmin), confirming its value is 0.05 ~ 0.25.
And, for the layer of described complex nitride or composite carbon nitride, use Electron Back-Scattered Diffraction device from Ti, the epithelium sectional side vertical with tool base surface of the complex nitride of Al and Me or the layer of composite carbon nitride is observed, measure, when analyzing the crystalline structure of each crystal grain, confirm and be made up of the single-phase of cube crystalline phase of the Electron Back-Scattered Diffraction image observing cubic(al)grating or cube crystalline phase mixed phase of hexagonal crystal phase with the Electron Back-Scattered Diffraction image observing hexagonal lattice, and the ratio of the area of hexagonal crystal phase shared by the mensuration visual field area observing Electron Back-Scattered Diffraction image is 30 below area %.
And, for the purpose of comparing, on the surface of tool base A ~ D, with the condition shown in table 3 and table 4 and with the target thickness (μm) shown in table 9,10, evaporation forms the hard coating layer of the layer of complex nitride or the composite carbon nitride at least comprising Ti, Al and Me in the same manner as coating tool 1 ~ 27 of the present invention.Now, at (Ti
1-x-yal
xme
y) (C
zn
1-z) layer film formation process in do not carry out etching work procedure and just form hard coating layer, thus produce and compare coating tool 1 ~ 13,16 ~ 27.
In addition, in the same manner as coating tool 6 ~ 13,17,18,20,21,24,27 of the present invention, for comparing coating tool 6 ~ 13,17,18,20,21,24,27 with the lower layer shown in the formation condition formation table 6 shown in table 3 and/or the upper layer shown in table 9,10.
In order to reference, on the surface of tool base B and tool base C, physical vapor deposition device is in the past used to be formed (the Ti of reference example with target thickness evaporation by arc ion plating
1-x-yal
xme
y) (C
zn
1-z) layer, thus produce the reference coating tool 14,15 shown in table 9.
In addition, the condition of the arc ion plating used in the evaporation of reference example is as follows.
A () carries out ultrasonic cleaning to described tool base B and C in acetone, and with the state of drying, the position of predetermined distance of being separated by from the central shaft on the turntable in arc ion plating apparatus along radial direction is installed along peripheral part, and, the Ti-Al-Me alloy of composition requirement is configured as cathode electrode (evaporation source)
(b) first, to being exhausted in device and keeping 10
-2the vacuum of below Pa, utilize well heater to be heated to after 500 DEG C in device simultaneously, the tool base rotated while rotation on described turntable is applied to the DC offset voltage of-1000V, and, what the electric current of 200A is flow through be made up of Ti-Al-Me alloy produces arc-over between cathode electrode and anode electrode, thus in device, produce Ti, Al and Me ion, thus Bombardment and cleaning is carried out to tool base surface
C () then, in device, importing oxide gas as reactant gases is set to the reaction atmosphere of 4Pa, and, the tool base rotated while rotation on described turntable is applied to the DC offset voltage of-50V, and, produce arc-over between the cathode electrode (evaporation source) electric current of 120A being flow through be made up of described Ti-Al-Me alloy and anode electrode, thus (the Ti of the target composition shown in table 9, target thickness is formed at the surperficial evaporation of described tool base, Al, Me) N layer, thus produce with reference to coating tool 14,15.
And, use scanning electron microscope (multiplying power 5000 times) to measure coating tool 1 ~ 27 of the present invention, compare the cross section in coating tool 1 ~ 13,16 ~ 27 and the direction vertical with tool base with reference to each constituting layer of coating tool 14,15, measure the thickness of 5 points observed in visual field and be averaged the result obtaining average thickness, all demonstrating the average thickness substantially the same with the target thickness shown in table 7 ~ 10.
And, about the average A l of the layer of complex nitride or composite carbon nitride containing proportional x, use electron rays microscopic analyzer (EPMA, Electron-Probe-Micro-Analyser), in the test portion of surface grinding, irradiate electron rays from test portion face side, contain proportional Yav by the average A l on average obtaining Al of 10 points of the analytical results of obtained characteristic X-ray containing the average of proportional Xav and Me.About average C containing proportional Zav, obtained by secondary ion mass spectrometry (SIMS, Secondary-Ion-Mass-Spectroscopy).From the range illumination ionic fluid of test portion surface lateral 70 μm × 70 μm, the composition discharged being acted on by sputtering carries out the concentration determination of depth direction.Average C represents the mean value of the depth direction for the complex nitride of Ti, Al and Me or the layer of composite carbon nitride containing proportional Zav.
And, for coating tool 1 ~ 27 of the present invention and compare coating tool 1 ~ 13,16 ~ 27 and with reference to coating tool 14,15, use scanning electron microscope (multiplying power 5000 times and 20000 times) from the cross-wise direction in the direction vertical with tool base, to along and the granular structure (Ti of layer of the formation complex nitride that exists in the scope of length 10 μm of the direction of tool base surface level or composite carbon nitride
1-x-yal
xme
y) (C
zn
1-z) each crystal grain in layer observes from the epithelium sectional side vertical with tool base surface, measure the particle width w in the direction parallel with matrix surface, the particle length l in the direction vertical with matrix surface, and calculate the aspect ratio a (=l/w) of each crystal grain, and to calculate the mean value of the aspect ratio a that each crystal grain is obtained as Mean aspect size than A, and calculate the mean value of the particle width w that each crystal grain is obtained as averaged particles width W.The results are shown in table 7 ~ 10.
And, use Electron Back-Scattered Diffraction device, with will by Ti, the cross section in the direction vertical with tool base surface of the hard coating layer that the layer of the complex nitride of Al and Me or composite carbon nitride is formed is as the state of abrasive surface, be fixed in the lens barrel of field emission type scanning electronic microscope, with become with described abrasive surface 70 degree incident angle and with the irradiation electric current of 1nA, each crystal grain existed in the measurement range of described cross section abrasive surface is irradiated to the electron rays of the acceleration voltage of 15kV, along the direction with tool base surface level throughout length 100 μm, to hard coating layer with the measuring space Electron Back-Scattered Diffraction image of 0.01 μm/step, and analyze the crystalline structure of each crystal grain, qualification is cubic crystal structure or structure of hexagonal crystal thus, and confirm Ti, the complex nitride of cubic crystal or the phase of composite carbon nitride whether is comprised in the complex nitride of Al and Me or the layer of composite carbon nitride, and, obtain the area ratio that hexagonal crystal that this layer comprise is shared mutually.Its result is shown in table 7 ~ 10 equally.
In addition, transmission electron microscope (multiplying power 200000 times) is used to observe the tiny area of the layer of complex nitride or composite carbon nitride, and use energy dispersion-type X-ray spectrography (EDS) to carry out the result of surface analysis from sectional side, confirm and there is composition formula in the crystal grain with described cubic crystal structure: (Ti
1-x-yal
xme
y) (C
zn
1-z) in the periodicity change in concentration of Ti, Al and Me.And, Ti is there is along an orientation in the crystalline orientation of the equivalence represented with < 001 > of cubic grain by carrying out electron rays diffraction to confirm to this crystal grain, the periodicity change in concentration of Al and Me, the line analysis based on EDS along this orientation is carried out at the section of five cycle portions, obtain Al relative to Ti, the mean value of the maximum value of the periodicity change in concentration of the total of Al and Me is as Xmax, and the Al obtaining this section is relative to Ti, the minimizing mean value of the periodicity change in concentration of the total of Al and Me is as Xmin, thus obtain its poor (=Xmax-Xmin).
And, carry out edge at the section of the distance being equivalent to described five cycle portions and there is Ti, the line analysis in the direction that an orientation in the crystalline orientation of the equivalence represented with < 001 > of the cubic grain of the periodicity change in concentration of Al and Me is orthogonal, the difference obtaining the maxima and minima containing proportional x of the Al of this section is used as and has Ti, the maximum value Δ Xo of the variable quantity in the face that an orientation in the crystalline orientation of the equivalence represented with < 001 > of the cubic grain of the periodicity change in concentration of Al and Me is orthogonal.
In addition, about the crystal grain of domain of the existence A and region B in crystal grain, Al is obtained in the same manner as aforementioned relative to Ti respectively for region A and region B, the mean value Xmax of the maximum value of the periodicity change in concentration of five cycle portions of the total of Al and Me and the difference (=Xmax-Xmin) of minimizing mean value Xmin, and obtain and there is Ti, in the face that an orientation in the crystalline orientation of the equivalence represented with < 001 > of the cubic grain of the periodicity change in concentration of Al and Me is orthogonal, Al is relative to Ti, the maximum value of difference as variable quantity containing the maxima and minima of proportional x of the total of Al and Me.
That is, along the periodicity change in concentration of Ti, Al and the Me of an orientation domain of the existence A in the crystalline orientation of the equivalence represented with < 001 > of cubic grain, this orientation is set to orientation d
atime, obtain along orientation d
acycle of change in concentration, and carry out edge and orientation d at the section of the distance being equivalent to described five cycle portions
athe line analysis in orthogonal direction, the difference of maxima and minima containing proportional x obtaining the Al of this section is used as the maximum value Δ Xoda of the variable quantity in the face orthogonal with an orientation in the crystalline orientation of the equivalence represented with < 001 > of the cubic grain of the periodicity change in concentration with Ti, Al and Me.
Further, along the periodicity change in concentration of Ti, Al and the Me of an orientation domain of the existence B in the crystalline orientation of the equivalence represented with < 001 > of cubic grain, this orientation is set to orientation d
btime, obtain along orientation d
bcycle of change in concentration, and carry out edge and orientation d at the section of the distance being equivalent to described five cycle portions
bthe line analysis in orthogonal direction, the difference of maxima and minima containing proportional x obtaining the Al of this section is used as the maximum value Δ Xodb of the variable quantity in the face orthogonal with an orientation in the crystalline orientation of the equivalence represented with < 001 > of the cubic grain of the periodicity change in concentration with Ti, Al and Me.
Further, d is confirmed
aand d
borthogonal, the border of region A and region B is formed at { a face in the crystal face of the equivalence that 110} represents.
The confirmation in this cycle is confirmed by minimum this crystal grain in the observation visual field of the tiny area of the layer of the complex nitride or composite carbon nitride that use transmission electron microscope (multiplying power 200000 times).And, for the crystal grain of domain of the existence A and region B in crystal grain, minimum this crystal grain on average obtaining respectively in the value of this region A and region B evaluation in the visual field of the tiny area of the complex nitride using transmission electron microscope (multiplying power 200000 times) to observe by calculating or the layer of composite carbon nitride.
[table 1]
[table 2]
[table 5]
[table 6]
Then, all described various coating tool to be clamped in the state in the instrument steel cutter front end portion that tool diameter is 125mm by stationary fixture, to coating tool 1 ~ 27 of the present invention, compare coating tool 1 ~ 13,16 ~ 27 and implement with reference to coating tool 14,15 a kind of dry type high speed front milling that the high rate intermittent as steel alloy shown below cuts, heart cutting formula machining tests, and measures the wear of the tool flank width of cutting edge.The results are shown in table 11.
Tool base: tungsten carbide base carbide alloy, base titanium carbonitride
Cutting test: the front milling of dry type high speed, heart cutting formula machining
Workpiece: the bulk of JISSCM440 width 100mm, length 400mm
Rotating speed: 943min
-1
Cutting speed: 370m/min
Depth of cut: 1.5mm
The single-blade amount of feed: 0.12mm/ sword
Cutting time: 8 minutes
[table 11]
[embodiment 2]
As raw material powder, prepare WC powder, TiC powder, ZrC powder, TaC powder, NbC powder, the Cr all with the median size of 1 ~ 3 μm
3c
2powder, TiN powder and Co powder, these raw material powders are fitted in the cooperation composition shown in table 12, further interpolation paraffin, ball milling mixes 24 hours in acetone, after drying under reduced pressure, under the pressure of 98MPa, impact briquetting is the pressed compact of regulation shape, this pressed compact is carried out vacuum sintering with the condition kept 1 hour under the specified temperature within the scope of 1370 ~ 1470 DEG C in the vacuum of 5Pa, after sintering, cutting edge portion is implemented to the cutting edge reconditioning processing of R:0.07mm, produce the tool base α ~ γ of the WC base cemented carbide of the blade shapes with iso standard CNMG120412 thus respectively.
And, as raw material powder, prepare TiCN (the being TiC/TiN=50/50 by quality ratio) powder all with the median size of 0.5 ~ 2 μm, NbC powder, WC powder, Co powder and Ni powder, these raw material powders are fitted in the cooperation composition shown in table 13, and utilize ball mill wet mixing 24 hours, after drying, under the pressure of 98MPa, impact briquetting is pressed compact, by this pressed compact in the nitrogen atmosphere of 1.3kPa with temperature: keep the condition of 1 hour to sinter at 1500 DEG C, after sintering, cutting edge part is implemented to the cutting edge reconditioning processing of R:0.09mm, form the tool base δ with the TiCN based ceramic metal of the blade shapes of iso standard CNMG120412 thus.
Then, on the surface of these tool base α ~ γ and tool base δ, common chemical evaporation plating device is used,
A () the formation condition A shown in table 4 ~ V, that is, be set to TiCl by reactant gases composition (capacity %)
4: 1.5 ~ 2.5%, Al (CH
3)
3: 0 ~ 5%, AlCl
3: 6 ~ 10%, MeCl
n: 1 ~ 3%, NH
3: 10 ~ 12%, N
2: 6 ~ 7%, C
2h
4: 0 ~ 1%, H
2: residue, and is set to reaction atmosphere pressure: 2 ~ 5kPa, reaction atmosphere temperature: 750 ~ 900 DEG C of thermal cvd of carrying out the specified time, carries out the averaged particles width W shown in table 15,16 and the Mean aspect size (Ti than the granular structure of A thus
1-x-yal
xme
y) (C
zn
1-z) film forming (film formation process) of layer.
In addition, for above-mentioned MeCl
n, use SiCl respectively according to the classification of Me (Si, Zr, B, V, Cr) similarly to Example 1
4, ZrCl
4, BCl
3, VCl
4, CrCl
2.
B (), when the film formation process of described (a), carries out the formation condition a shown in the table 5 ~ j of specified time, stipulated number, that is, reactant gases composition (capacity %) is set to TiCl
4: 2.0 ~ 5.0%, H
2: residue, and be set to reaction atmosphere pressure: 2 ~ 5kPa, reaction atmosphere temperature: the TiCl of 750 ~ 900 DEG C
4etching work procedure (etching work procedure).
C () is in the film formation process of described (a), carry out the etching work procedure be made up of (b) of the specified time shown in table 15,16, stipulated number, formed thus by the (Ti at least comprising the granular structure of cubic crystal with the target thickness shown in table 15,16
1-x-yal
xme
y) (C
zn
1-z) hard coating layer that layer is formed, thus produce coating tool 31 ~ 57 of the present invention.
In addition, for coating tool 34 ~ 43,47,48,50,51,54,57 of the present invention, the lower layer shown in table 14 and/or the upper layer shown in table 15,16 under the formation condition shown in table 3, is formed.
And, for the purpose of comparing, similarly on the surface of tool base α ~ γ and tool base δ, use common chemical evaporation plating device to form hard coating layer with the target thickness evaporation in the same manner as coating tool of the present invention shown in the condition shown in table 3 and table 4 and table 17,18, thus produce the comparison coating tool 31 ~ 43,46 ~ 57 shown in table 17,18.
In addition, in the same manner as coating tool 34 ~ 43,47,48,50,51,54,57 of the present invention, to comparing the lower layer shown in formation table 14 and/or the upper layer shown in table 17,18 under the formation condition of coating tool 34 ~ 43,47,48,50,51,54,57 shown in table 3.
In order to reference, on the surface of tool base β and tool base γ, physical vapor deposition device is in the past used to be formed (the Ti of reference example with target thickness evaporation by arc ion plating
1-x-yal
xme
y) (C
zn
1-z) layer, thus produce the reference coating tool 44,45 shown in table 17.
In addition, the condition of arc ion plating uses the condition identical with the condition shown in embodiment 1.
And, scanning electron microscope (multiplying power 5000 times) is used to measure coating tool 31 ~ 57 of the present invention, compare coating tool 31 ~ 43,46 ~ 57 and the cross section of each constituting layer with reference to coating tool 44,45, measure the thickness of 5 points observed in visual field and be averaged the result obtaining average thickness, all demonstrating the average thickness substantially the same with the target thickness shown in table 15 ~ 18.
And, for described coating tool 31 ~ 57 of the present invention, compare coating tool 31 ~ 43,46 ~ 57 and with reference to the hard coating layer of coating tool 44,45, use the method identical with the method shown in embodiment 1 to obtain average A l and contain proportional Zav containing proportional Xav, average Me containing proportional Yav, average C, form (the Ti of granular structure
1-x-yal
xme
y) (C
zn
1-z) the averaged particles width W of crystal grain of layer, the Mean aspect size area ratio more shared mutually than the hexagonal crystal in A, crystal grain.The results are shown in table 15 ~ 18.
For the complex nitride of Ti, Al and Me or the layer of composite carbon nitride of the hard coating layer of the described coating tool 31 ~ 57 of the present invention of formation, use the result that scanning electron microscope (multiplying power 5000 times and 20000 times) carries out observing throughout multiple visual field, shown in membrane structure schematic diagram as shown in Figure 1, confirm (the Ti of the granular structure that there is cubic crystal
1-x-yal
xme
y) (C
zn
1-z) layer.Further, transmission electron microscope (multiplying power 200000 times) is used, by confirming the periodicity concentration distribution that there is Ti, Al and Me in cubic grain based on the surface analysis of energy dispersion-type X-ray spectrography (EDS).The result of further detailed analysis, confirms the mean value Xmax of the maximum value of the x value containing the change of proportional x generating period of Al, is 0.05 ~ 0.25 with the difference (Xmax-Xmin) containing the minimizing mean value Xmin of the x value that proportional x generating period changes of Al.
And, for the layer of described complex nitride or composite carbon nitride, use Electron Back-Scattered Diffraction device, the epithelium sectional side vertical from the tool base surface with the complex nitride of Ti with Al or the layer of composite carbon nitride is observed, measure, when analyzing the crystalline structure of each crystal grain, confirm and be made up of the mixed phase of hexagonal crystal phase of the single-phase of cube crystalline phase of the Electron Back-Scattered Diffraction image observing cubic(al)grating or cube crystalline phase and the Electron Back-Scattered Diffraction image of observing hexagonal lattice, and the ratio of the area of hexagonal crystal phase shared by the mensuration visual field area observing Electron Back-Scattered Diffraction image is 30 below area %.
[table 12]
[table 13]
[table 14]
Then, all described various coating tool to be anchored on the state of the leading section of instrument steel lathe tool by stationary fixture, to coating tool 31 ~ 57 of the present invention, compare coating tool 31 ~ 43,46 ~ 57 and implement the dry type high rate intermittent cutting test of steel alloy, the wet type high rate intermittent cutting test of cast iron shown below with reference to coating tool 44,45, and all measure the wear of the tool flank width of cutting edge.
Machining condition 1:
The first-class gap-forming of length direction of workpiece: JISSCM435 has the pole of four pods
Cutting speed: 360m/min
Depth of cut: 1.5mm
The amount of feed: 0.2mm/rev
Cutting time: 5 minutes
(common cutting speed is 220m/min)
Machining condition 2:
The first-class gap-forming of length direction of workpiece: JISFCD450 has the pole of four pods
Cutting speed: 350m/min
Depth of cut: 1.2mm
The amount of feed: 0.4mm/rev
Cutting time: 5 minutes
(common cutting speed is 200m/min)
The result of described cutting test shown in table 19.
[embodiment 3]
As raw material powder, prepare the cBN powder of the median size all had in the scope of 0.5 ~ 4 μm, TiN powder, TiCN powder, TiC powder, Al powder and Al
2o
3powder, these raw material powders are fitted in the cooperation composition shown in table 20, and utilize ball mill wet mixing 80 hours, after drying, under the pressure of 120MPa, impact briquetting is for having diameter: the pressed compact of the size of 50mm × thickness: 1.5mm, then, by this pressed compact at pressure: carry out sintering with the condition kept 60 minutes under the specified temperature within the scope of 900 ~ 1300 DEG C in the vacuum atmosphere of 1Pa and be made into cutting blade presintering body, by this presintering body with prepare separately there is Co:8 quality %, WC: remaining composition, and diameter: the state of the WC base cemented carbide supporting slice coincidence of the size of 50mm × thickness: 2mm, load in common ultra-high pressure sintering device, at usual conditions and pressure: 4GPa, temperature: the specified temperature lower hold-time in the scope of 1200 ~ 1400 DEG C: carry out ultra-high pressure sintering under the condition of 0.8 hour, after sintering, use diamond wheel grinding upper and lower surface, the size of regulation is divided into by electric spark sutting machining device, in addition, to having Co:5 quality %, TaC:5 quality %, WC: remaining composition, and the brazed portion (bight) of the WC base cemented carbide vane body of the shape of JIS standard C NGA120412 (thickness: 80 ° of rhombuses of 4.76mm × inscribed circle diameter: 12.7mm), use and have in mass % by Zr:37.5%, Cu:25%, Ti: the solder of the Ti-Zr-Cu alloy of the composition that residue is formed carries out soldering, after specified dimension is processed in periphery, width: 0.13mm is implemented to cutting edge portion, angle: the cutting edge reconditioning processing of 25 °, further enforcement fine grinding, produce the tool base first of the blade shapes with iso standard CNGA120412 thus respectively, second.
[table 20]
Then, on the surface of these tool base first, second, use common chemical evaporation plating device, formed with target thickness evaporation under the condition shown in table 3 and table 4 by the method identical with embodiment 1 and at least comprise (Ti
1-x-yal
xme
y) (C
zn
1-z) hard coating layer of layer, thus produce the coating tool of the present invention 61 ~ 72 shown in table 22,23.
In addition, for coating tool 64 ~ 68,71 of the present invention, lower layer shown in table 21 and/or the upper layer as shown in table 22,23 under the formation condition shown in table 3, is formed.
Further, for the purpose of comparing, similarly on the surface of tool base first, second, use common chemical evaporation plating device to be formed with target thickness evaporation under the condition shown in table 3 and table 4 and at least comprise (Ti
1-x-yal
xme
y) (C
zn
1-z) hard coating layer of layer, thus produce the comparison coating tool 61 ~ 64,67 ~ 74 shown in table 24,25.
In addition, in the same manner as coating tool 64 ~ 68,71 of the present invention, under comparing the formation condition of coating tool 64,67,68 shown in table 3, form lower layer shown in table 21 and/or the upper layer as shown in table 24,25.
In order to reference, on the surface of tool base first, second, physical vapor deposition device is in the past used to form (Ti by arc ion plating with target thickness evaporation
1-x-yal
xme
y) (C
zn
1-z) layer, thus produce the reference coating tool 69,70 shown in table 24.
In addition, the condition of arc ion plating uses the condition identical with the condition shown in embodiment 1, forms (the Ti of the target composition shown in table 24, target thickness at the surperficial evaporation of described tool base
1-x-yal
xme
y) (C
zn
1-z) layer, thus produce with reference to coating tool 65,66.
And, use scanning electron microscope (multiplying power 5000 times) to measure coating tool 61 ~ 72 of the present invention, compare the cross section of coating tool 61 ~ 64,67 ~ 74 and each constituting layer with reference to coating tool 65,66, measure the thickness of 5 points observed in visual field and be averaged the result obtaining average thickness, all demonstrating the average thickness substantially the same with the target thickness shown in table 22 ~ 25.
And, for described coating tool 61 ~ 72 of the present invention, compare coating tool 61 ~ 64,67 ~ 74 and the hard coating layer with reference to coating tool 65,66, use the method identical with the method shown in embodiment 1 to obtain average A l and contain proportional Yav, average C containing proportional the Zav, (Ti forming granular structure containing proportional Xav, average Me
1-x-yal
xme
y) (C
zn
1-z) the averaged particles width W of crystal grain of layer, the Mean aspect size area ratio more shared mutually than the hexagonal crystal in A, crystal grain.The results are shown in table 22 ~ 25.
[table 21]
Then, all various coating tool to be anchored on the state of the leading section of instrument steel lathe tool by stationary fixture, to coating tool 61 ~ 72 of the present invention, compare coating tool 61 ~ 64,67 ~ 74 and implement the dry type high rate intermittent machining test of carburizing and quenching steel alloy shown below with reference to coating tool 65,66, and measure the wear of the tool flank width of cutting edge.
Cutting test: the dry type high rate intermittent machining of carburizing and quenching steel alloy
The first-class gap-forming of length direction of workpiece: JISSCr420 (hardness: HRC62) has the pole of four pods
Cutting speed: 260m/min
Depth of cut: 0.15mm
The amount of feed: 0.15mm/rev
Cutting time: 4 minutes
The result of described cutting test shown in table 26.
[table 26]
Clearly be known as below by the result shown in table 11, table 19 and table 26: coating tool of the present invention at least comprises in the hard coating layer of cubic grain the complex nitride of Ti, Al and Me or composite carbon nitride, the change in concentration of Ti, Al and Me is there is in this cubic grain, improve hardness by the strain of crystal grain thus, while keeping higher wear resistance, improve toughness.And, even if interrupted impact high loading act on use in the high rate intermittent machining of cutting edge time, resistance to cutter, the fracture resistance of collapsing is also excellent, its result, plays excellent wear resistance in life-time service.
Relative to this, about the Ti forming hard coating layer, the complex nitride of Al and Me or composite carbon nitride at least comprise in the hard coating layer of cubic grain, Ti is there is not in this cubic grain, the comparison coating tool 1 ~ 13 of the change in concentration of Al and Me, 16 ~ 27, 31 ~ 43, 46 ~ 57, 61 ~ 64, 67 ~ 74 and with reference to coating tool 14, 15, 44, 45, 65, 66 is clearly known, when occur with high heat and interrupted impact high loading act on use in the high rate intermittent machining of cutting edge time, because collapsing cutter, the generation of defect etc. and reach the life-span at short notice.
Utilizability in generation
As mentioned above, coating tool of the present invention can not only be used for the high rate intermittent machining of steel alloy, but also the coating tool of various workpiece can be used as, and play in life-time service and excellent resistance toly collapse cutter, wear resistance, therefore, it is possible to tackle the high performance of topping machanism, the saving labourization of machining and energy-saving, even cost degradation very satisfactorily.
Claims (9)
1. a surface-coated cutting tool, hard coating layer is being provided with by the surface of any one tool base formed in tungsten carbide base carbide alloy, base titanium carbonitride or cubic boron nitride base ultra-high pressure sintered compact, the feature of described surface-coated cutting tool is
A () described hard coating layer at least comprises by the average thickness of chemical vapor deposition method film forming is the complex nitride of Ti, Al and Me of 1 ~ 20 μm or the layer of composite carbon nitride, wherein, Me is a kind of element be selected from Si, Zr, B, V, Cr, when with composition formula: (Ti
1-x-yal
xme
y) (C
zn
1-z) represent time, on average contain proportional Xav and Me average contain proportional Yav and C in the total amount of Ti, Al and Me shared by average the contain proportional Zav in the total amount of C and N shared by of Al shared by the total amount of Ti, Al and Me meets 0.60≤Xav≤0.95,0.005≤Yav≤0.10,0≤Zav≤0.005, Xav+Yav≤0.955 respectively, wherein, Xav, Yav, Zav are atomic ratio
B the layer of () described complex nitride or composite carbon nitride at least comprises the complex nitride of the face-centred cubic structure with NaCl type or the phase of composite carbon nitride,
(c) and, when observing from the epithelium sectional side vertical with tool base surface, measuring, be that the averaged particles width W of the complex nitride of the face-centred cubic structure with NaCl type or the crystal grain of composite carbon nitride is 0.05 ~ 1.0 μm and Mean aspect size is the granular structure of less than 5 than A
In addition, in the complex nitride of face-centred cubic structure with described NaCl type or the crystal grain of composite carbon nitride, there is composition formula: (Ti in (d)
1-x-yal
xme
y) (C
zn
1-z) in the periodicity change in concentration of Ti, Al and Me, when the mean value of the maximum value of the x value containing proportional x generating period change by Al is set to Xmax and the minimizing mean value of the x value containing proportional x generating period change of Al is set to Xmin, the difference of Xmax and Xmin is 0.05 ~ 0.25.
2. surface-coated cutting tool according to claim 1, is characterized in that,
The periodicity change in concentration of Ti, Al and Me in the layer that there is described complex nitride or composite carbon nitride have in the crystal grain of the face-centred cubic structure of NaCl type, the periodicity change in concentration of Ti, Al and Me is there is along an orientation in the crystalline orientation of the equivalence represented with < 001 > of cubic grain, cycle along this orientation is 3 ~ 30nm, the Al in the face orthogonal with this orientation containing proportional x be changed to less than 0.01.
3. surface-coated cutting tool according to claim 1, is characterized in that,
The periodicity change in concentration of Ti, Al and Me in the layer that there is described complex nitride or composite carbon nitride have in the crystal grain of the face-centred cubic structure of NaCl type, following region A and region B is there is in crystal grain, border between described region A and region B is formed at { a face in the equivalent crystal that 110} represents
A () region A: the periodicity change in concentration that there is Ti, Al and Me along an orientation in the crystalline orientation of the equivalence represented with < 001 > of cubic grain, if be set to orientation d by this orientation
a, then along orientation d
acycle be 3 ~ 30nm, with orientation d
aal in orthogonal face containing proportional x be changed to less than 0.01;
(b) region B: along with orientation d
athere is the periodicity change in concentration of Ti, Al and Me in an orientation in the crystalline orientation of the equivalence represented with < 001 > of orthogonal cubic grain, if this orientation is set to orientation d
b, then along orientation d
bcycle be 3 ~ 30nm, with orientation d
bal in orthogonal face containing proportional x be changed to less than 0.01.
4. surface-coated cutting tool according to any one of claim 1 to 3, is characterized in that,
The layer of described complex nitride or composite carbon nitride is made up of the complex nitride of Ti, Al and Me of face-centred cubic structure or the single-phase of composite carbon nitride with NaCl type.
5. surface-coated cutting tool according to any one of claim 1 to 3, is characterized in that,
The layer of described complex nitride or composite carbon nitride is made up of two or more multiple mixed phase coexisted mutually, this mixed phase at least comprises the complex nitride of Ti, Al and Me of the face-centred cubic structure with NaCl type or the phase of composite carbon nitride, and other coexisting in mixed phase are respectively by with at least one element be selected from Ti, Al and Me be selected from the compound that at least one in C, N formed and formed.
6. the surface-coated cutting tool according to any one of claims 1 to 3 or 5, is characterized in that,
In the layer of described complex nitride or composite carbon nitride, there is the crystal grain with the structure of hexagonal crystal of wurtzite-type, when measuring from the epithelium sectional side vertical with tool base surface, the area ratio existing for crystal grain with the structure of hexagonal crystal of this wurtzite-type is 30 below area %.
7. surface-coated cutting tool according to any one of claim 1 to 6, is characterized in that,
Lower layer is there is by between the complex nitride of any one tool base formed in described tungsten carbide base carbide alloy, base titanium carbonitride or cubic boron nitride base ultra-high pressure sintered compact and described Ti, Al and Me or the layer of composite carbon nitride, described lower layer comprises Ti compound layer, and described Ti compound layer is by the one deck in the carbide lamella of Ti, nitride layer, carbonitride layer, oxycarbide layer and carbon nitrogen oxide layer or two-layerly form and have the average thickness of total of 0.1 ~ 20 μm above.
8. surface-coated cutting tool according to any one of claim 1 to 7, is characterized in that,
There is the upper layer comprising alumina layer on the top of the layer of described complex nitride or composite carbon nitride, described alumina layer at least has the average thickness of 1 ~ 25 μm.
9. surface-coated cutting tool according to any one of claim 1 to 8, is characterized in that,
The layer of described complex nitride or composite carbon nitride is by least containing the chemical vapor deposition method film forming of trimethyl aluminium as reactant gases composition.
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