CN102978618A - Making method for surface coating cutting tool with excellent wear resistance property - Google Patents
Making method for surface coating cutting tool with excellent wear resistance property Download PDFInfo
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- CN102978618A CN102978618A CN2012102783079A CN201210278307A CN102978618A CN 102978618 A CN102978618 A CN 102978618A CN 2012102783079 A CN2012102783079 A CN 2012102783079A CN 201210278307 A CN201210278307 A CN 201210278307A CN 102978618 A CN102978618 A CN 102978618A
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Abstract
The invention provides a making method for surface coating cutting tool with excellent wear resistance property. At least top surface of a tool body is coated with film of 0.05-5um and is provided with an alumina layer of [alpha] alumina composition with corundum crystal structure, and the alumina layer is formed by following sol-gel method: adding ethanol in aluminum alkoxide (preferably selecting ethanol with [alpha]alumina particle of 10-300um ), further adding acid (for example diluted hydrochloric acid), stirring and generating sol under temperature lower than 10 DEG C, adding water in the sol so that molar ratio between aluminum and water contained in the sol becomes 1:30-1:150, carrying out high crystallization process of heating and stirring under 15-80 DEG C, coating the highly crystallized sol on the surface of the tool body or on a top surface of a hard film formed on the surface of the tool body, repeatly carrying out drying process more than once under 100-400 DEG C, and finally carrying out burning process in a temperature scope of 500-1000 DEG C.
Description
Technical field
The present invention relates to a kind of manufacture method of surface-coated cutting tool of excellent in abrasion resistance, relate in particular to a kind of manufacture method of surface-coated cutting tool of excellent in abrasion resistance of following feature, its by sol-gel method on the surface of the tool base that comprises tungsten carbide base carbide alloy, base titanium carbonitride, rapid steel or cubic boron nitride base ultra-high pressure sintered compact (the following tool base that only is called) or the most surperficial formation alumina layer of the hard film that forms on this tool base surface.
Background technology
As everyone knows, all the time, comprise that by coating on tool base surface to form the hard film of the carbide, nitride, carbonitride etc. of element more than at least a kind in the 4a, the 5a that are selected from periodictable, the 6a family seeks to improve the wear resistance of cutting tool.
And, especially the excellent heat stability of alpha-type aluminum oxide layer in the hard film, reactivity is lower, and be high rigidity, because this point, mostly coat and form the alpha-type aluminum oxide layer as the upper layer of the hard film of the carbide, nitride, carbonitride etc. of element more than at least a kind that comprises in the 4a, the 5a that are selected from above-mentioned periodictable, the 6a family.
As the coating formation method of alumina layer, generally adopt chemical vapor deposition (CVD) method, but in addition, also known to physical vapor deposition (PVD) method, sol-gel method formation alumina layer.
For example, shown in patent documentation 1, for fear of tool base, the deterioration in characteristics of hard film, distortion, proposed a kind of under cold condition (below 1000 ℃) form the method for alpha-type aluminum oxide layer, as the method, form on tool base surface by physical vapor deposition (PVD) method and to comprise with Al and to be selected from and comprise 4a family, 5a family, at least a kind of element in the group of 6a family and Si is the nitride of essential composition, carbide, carbonitride, boride, oxynitride, behind the hard film of carbon nitrogen oxide, this hard film is carried out oxidation form the oxycompound layer, and carrying out physical vapor deposition (PVD) at this oxycompound layer, evaporation forms wear resistance and excellent heat resistance and the alumina layer as upper layer take alpha type crystal structure as main body thus.
In addition, shown in patent documentation 2, propose a kind of surface-coated cutting tool by physical vapor deposition (PVD) method evaporation formation hard coating layer, wherein, consisted of the 1st layer by (Ti, Al) N layer, and, by alumina layer
(preferred γ type alumina layer) consists of the 2nd layer.
In addition, shown in patent documentation 3, a kind of manufacture method with alumina-coated structure of mechanical characteristic and weather resistance has been proposed, as the method, utilize sol-gel method after mother metal comprises 1st alumina layer of crystalline structure for the aluminum oxide of non-crystal structure or γ type or their mixture, coat the 2nd alumina layer that forms take the γ type as main body by sputter.
Patent documentation 1: Japanese Patent Publication 2004-124246 communique
Patent documentation 2: Japanese Patent Publication 2007-75990 communique
Patent documentation 3: Japanese Patent Publication 2006-205558 communique
Coat to form the above-mentioned in the past surface-coated cutting tool that comprises hard film and be formed on the hard coating layer of its most surperficial aluminum oxide (below, only be called coating tool) in, the most surperficial alumina layer has for example improved the wear resistance in the rake face at coating tool when machining steel etc., this especially because the thermostability of alpha-type aluminum oxide, non-reacted higher due to.
Proposed in the above-mentioned patent documentation 1 under cold condition, to form the alpha-type aluminum oxide layer by physical vapor deposition (PVD) method, but there are the following problems when evaporation forms alumina layer, at first, although need to make the hard film oxidation and form the oxycompound layer on its surface, but the adhesivity of oxycompound layer and alumina layer is insufficient, and, as aluminum oxide, not only there is alpha-type aluminum oxide, but also there is γ type aluminum oxide, therefore can't obtain sufficient thermotolerance, its result can't bring into play gratifying cutting ability through life-time service.
In addition, in above-mentioned patent documentation 2,3, there are the following problems: because formed aluminum oxide is γ type aluminum oxide, therefore lack the stability in the high temperature, and, in High Speed Machining, can't bring into play gratifying cutting ability.
Summary of the invention
Therefore, the inventor etc. are to utilizing physical vapor deposition (PVD) method to form to coat behind the hard film sol-gel method that forms its upper layer to further investigate rear discovery on the tool base surface, in aluminium-alcohol salt, add pure and mild acid, and under cold condition, be hydrolyzed for a long time, ripening at low temperature processes, then, implement high crystallization and process the alumina sol that prepare and be coated with, burn till after the drying as upper layer by adding water, thereby can coat the alumina layer that formation has alpha type crystal structure.
Namely, discovery is when the preparation alumina sol, process as ripening at low temperature, by carrying out than the stirring under the usually lower temperature and keeping for a long time suppressing being hydrolyzed and the speed of response of polycondensation, and after closely formation comprises the aluminum oxide precursor of Al-O key, process as high crystallization, adding water makes the aluminium amount in the aluminium-alcohol salt become predetermined concentration, and the heating under the enforcement preset temperature, at this moment, can more promote hydrolysis and the polycondensation of aluminium-alcohol salt, and form more octahedra AlO near corundum type structure
6If, therefore be coated with this alumina sol as the upper layer of hard film, and carry out drying, burn till, then can form the upper layer of the hard film that comprises the α-aluminum oxide layer with the higher corundum type crystalline structure of densification and crystallinity.
In addition, the hard film that will contact with the alumina layer of upper layer form in the metal ingredient of Al in this hard film shared contain proportional when being nitride epithelium more than the 40 atom %, owing to uprise with the adhesion strength of the alumina layer of upper layer, therefore the peeling off of the alumina layer that causes such as the impact when suppressing to produce because of machining, the viewpoint such as damaged consider it is preferred.
And, in the surface-coated cutting tool of finding to make by manufacture method of the present invention, the surface smoothing of the most surperficial alumina layer, excellent for the deposit resistance property of smear metal, bring into play thus excellent wear resistance through life-time service.
This invention is finished according to above-mentioned opinion, and it has following feature:
(1) a kind of manufacture method of surface-coated cutting tool of excellent in abrasion resistance, form the alumina layer of α-aluminum oxide structure in the most surperficial coating of the tool base that comprises tungsten carbide base carbide alloy, base titanium carbonitride, rapid steel or cubic boron nitride base ultra-high pressure sintered compact, this alumina layer has the thickness of 0.05～5 μ m and has the corundum type crystalline structure, wherein
Above-mentioned alumina layer coats by following sol-gel method and forms: add alcohol in aluminium-alcohol salt, and after further adding acid, in the temperature range below 10 ℃, stir and generate colloidal sol, after interpolation water makes the mol ratio of aluminium contained in this colloidal sol and water become 1:30～1:150 in colloidal sol, be implemented under 15～80 ℃ the temperature and heat, the high crystallization that stirs is processed, to implement that colloidal sol that this high crystallization processes is coated above-mentioned tool base surface or the hard film that forms on the tool base surface the most surperficial, then, repeatedly carrying out drying treatment more than 1 time under 100～400 ℃, then, in 500～1000 ℃ temperature range, burn till processing.
(2) such as the manufacture method of the surface-coated cutting tool of above-mentioned (1) described excellent in abrasion resistance, wherein, by physical vapor deposition, chemical vapor deposition method or sol-gel method coat on the surface of above-mentioned tool base contain at least a above element among the 4a, the 5a that are selected from periodictable, 6a family, Al, the Si nitride as hard film, and at the above-mentioned alumina layer of the most surperficial formation of this hard film.
(3) such as the manufacture method of the surface-coated cutting tool of above-mentioned (1) described excellent in abrasion resistance, it is characterized in that, implement nitriding treatment on the surface of above-mentioned tool base in advance.
(4) such as the manufacture method of the surface-coated cutting tool of each described excellent in abrasion resistance in above-mentioned (1) to (3), it is characterized in that, when in above-mentioned aluminium-alcohol salt, adding alcohol, add and contain the alcohol that median size is the alpha alumina particles of 10～300nm.
Below, be elaborated for the present invention.
In the manufacture method of the surface-coated cutting tool of this invention, directly coat the alumina layer that forms the α-aluminum oxide structure with corundum type crystalline structure on the surface of the tool base that comprises tungsten carbide base carbide alloy, base titanium carbonitride, rapid steel or cubic boron nitride base ultra-high pressure sintered compact by sol-gel method.
In addition, in the manufacture method of the surface-coated cutting tool of this invention, also can form hard film well known by persons skilled in the art on the surface of above-mentioned tool base by physical vapor deposition (PVD) method, namely comprise the element more than at least a kind that contains among 4a, 5a, 6a family and the Si that is selected from periodictable and Al nitride hard film more than at least 1 layer (for example, TiAlN film, CrAlN film etc.) after, the alumina layer of the α-aluminum oxide structure with corundum type crystalline structure formed in the most surperficial coating of this hard film by sol-gel method.
In addition, when forming hard film by above-mentioned physical vapor deposition (PVD) method, consider that from improving adhering viewpoint the hard film that preferably contacts with alumina layer forms that shared in the metal ingredient of Al in this hard film to contain proportional be nitride epithelium more than the 40 atom %.
Its reason is: if shared in the metal ingredient of Al in hard film to contain proportional be nitride epithelium more than the 40 atom %, then nitride epithelium and aluminum oxide epithelium form at the interface the higher oxide compound of aluminum concentration, this oxide compound has the effect of firmly bond nitride epithelium and aluminum oxide epithelium.
Coating the operation that forms alumina layer based on sol-gel method of the present invention is specially as follows.
The preparation of alumina sol:
At first, at aluminium-alcohol salt (for example, aluminium secondary butylate, aluminum isopropylate) the middle alcohol (for example ethanol, n-butyl alcohol) that adds, and after further adding acid (for example hydrochloric acid, nitric acid) (also can add simultaneously the alpha alumina particles that median size is 10～300nm), in the temperature range below 10 ℃, stir and carry out for example maturation process more than 12 hours, thereby form alumina sol.
In addition, consider from the viewpoint of making uniform colloidal sol, preferably when adding alcohol, contain in advance the alcohol that median size is the alpha alumina particles of 10～300nm in order to improve film formation at low temp and the crystallinity by promoting that nucleus generates to realize when forming alumina layer, to add.This be because, alpha alumina particles becomes the nuclear of crystal growth starting point during coating, therefore the early effect of stage crystallization at firing process is arranged, but add when containing alpha alumina particles pure, if the median size of alpha alumina particles is less than 10nm, then do not reach the critical nucleus size that can become crystal growth starting point, therefore do not occur from the crystal growth of the alumina sol around the alpha alumina particles and cause isolating, burn till the rear position weak with the linkage force of on every side crystal grain that become easily.On the other hand, if median size surpasses 300nm, then can cause the nucleus hypertrophy take alpha alumina particles as starting point to be big particle, cause that film hardness descends and film in damaged, therefore, the median size of the alpha alumina particles that adds is made as 10～300nm.
In addition, if the alpha alumina particles content in the alcohol with respect to aluminium-alcohol salt less than 0.5 quality %, then can't satisfy for making nucleus to be uniformly distributed in karyogenesis number required in the film more than certain density, cause crystallinity in the film along with the place becomes inhomogeneous, cause easily inordinate wear when therefore cutting.If surpass 5 quality % with respect to aluminium-alcohol salt, the cohesion of alpha alumina particles then occurs in alumina sol easily, should cohesion section when forming alumina layer form the big particle in the film, and cause in the film damaged, considered that by above reason the addition of preferred alpha alumina particles is made as in 0.5～5 quality % scope with respect to aluminium-alcohol salt.
In addition, the concentration of the preferred acid of adding is 0.01～4.0N, and preferred acid is 0.5～5 times (capacity) with respect to the addition of alcohol.
In the preparation of the alumina sol that usually carries out, carry out under 40～80 ℃ stirring and in the maturation process of this whipping temp about lower a few hours, but in this invention, stirring and for example long-time ripening at low temperature more than 12 hours of carrying out in the low temperature range below 10 ℃ are processed.
At this, if the temperature when stirring surpasses 10 ℃, then cause hydrolysis to be carried out fast, therefore can not form densely precursor, in the firing process of rear operation, can not form α-aluminum oxide, therefore, the temperature during with stirring is made as the cryogenic temperature scope below 10 ℃.
In addition, will be made as the curing time more than 12 hours is for slow facilitation of hydrolysis at low temperatures for a long time, and generates densely the aluminum oxide precursor.
Then, in this invention, the above-mentioned alumina sol of processing carrying out above-mentioned ripening at low temperature adds water so that after the mol ratio of contained aluminium and water becomes 1:30～1:150 in this colloidal sol in colloidal sol, be implemented in the high crystallization processing of heating, stirring under 15～80 ℃ the temperature.
In colloidal sol, add water so that carried out that the mol ratio of aluminium contained in the above-mentioned alumina sol that ripening at low temperature processes and water becomes the technical reason of 1:30～1:150 and the technical reason that heats, stir is as follows under 15～80 ℃ temperature: to process the aluminum oxide precursor of densely formation as starting point by ripening at low temperature, interpolation and heating by above-mentioned water promote the bonding of Al-O more, thereby can more firmly form more octahedra AlO near the α-aluminum oxide corundum
6If the final mol ratio of the water yield is less than 30 after adding, then the supply of contained O is insufficient in the water, and therefore, the hydrolysis of aluminium-alcohol salt and polycondensation are carried out insufficiently, does not satisfy for forming more octahedra AlO near the α-aluminum oxide corundum
6And realization improves the bonding number of the required Al-O of crystallinity.On the other hand, if surpass 150, then cause the bonding number of Al-O of the per unit volume of alumina sol to tail off, can not become fine and close pellumina during coating, therefore the mol ratio with aluminium and water is defined as 1:30～1:150.In addition, if the heating that high crystallization is processed, whipping temp less than 15 ℃, then can fully not promote hydrolysis and the polycondensation of aluminium-alcohol salt, therefore can not form the octahedra AlO near the α-aluminum oxide corundum of quantity sufficient
6, and can't form the higher alumina layer of crystallinity.On the other hand, if heating, whipping temp surpass 80 ℃, then can carry out the volatilization of solvent, it is destroyed to cause processing the aluminum oxide precursor that forms densely by ripening at low temperature, can't the higher alumina layer of film forming crystallinity.Therefore, heating, the whipping temp of high crystallization processing are defined as 15～80 ℃.
Dry, burn till:
The alumina sol of above-mentioned preparation directly coated tool base surface or coat by physical vapor deposition (PVD) method be formed on the most surperficial of the lip-deep hard film of tool base, then, repeatedly carry out more than 1 time 100～400 ℃, the drying treatment under 250～350 ℃ more preferably, then, 500～1000 ℃, more preferably burn till processing in 600～900 ℃ the temperature range, form alumina layer thereby coat.
By the desiccant gel of above-mentioned drying treatment formation aluminum oxide, coat the alumina layer that forms the α-aluminum oxide structure with corundum type crystalline structure by the processing of burning till of then carrying out on the hard film surface.
The thickness of above-mentioned alumina layer exists with ... coating thickness and the coating number of times of alumina sol, if but the thickness of the above-mentioned alumina layer that coating forms is less than 0.05 μ m, then can't bring into play through long-time use the wear resistance as surperficial coating tool excellence, on the other hand, if thickness surpasses 5 μ m, then alumina layer easily produces and peels off, and therefore the thickness of above-mentioned alumina layer is defined as 0.05～5 μ m.
In addition, the temperature range of drying treatment is defined as 100～400 ℃, more preferably be set as 250～350 ℃, the temperature range of burning till processing is defined as 500～1000 ℃, more preferably is set as 600～900 ℃, its reason is respectively as follows: for drying temperature, if less than 100 ℃, then can't carry out sufficient drying, if above 400 ℃, then burn till simultaneously and produce be full of cracks etc. at film, epithelium easily produces to be peeled off etc.; For firing temperature, if less than 500 ℃, then can't form for cutting and have sufficient crystalline alumina layer, when under surpassing 1000 ℃ temperature, burning till, although do not have too large problem, can produce decomposition or oxidation as hard films such as substrate film forming (Ti, Al) N, perhaps produce the oxidation of Wimet or sintering metal matrix etc., can not present the profitability of film formation at low temp.
Nitriding treatment:
Although above-mentioned alumina layer direct formation of film at surface also can be brought into play its performance on tool base, but especially take Wimet or base titanium carbonitride, rapid steel during as matrix, by making the tool base surface produce surface hardening according to the metal bound phase of nitriding treatment nitrogenize tool base near surface in advance, and form alumina layer on this surface, thereby can improve the adhesion strength of alumina layer and tool base, and prolong life tools.
Manufacture method according to the surface-coated cutting tool of this invention, directly on the surface of tool base or the hard film through forming by physical vapor deposition (PVD) method the most surperficially coat the alumina layer that formation has the α-aluminum oxide structure of corundum type crystalline structure by sol-gel method at it, formed above-mentioned alumina layer has excellent deposit resistance property and wear resistance, in addition, be formed at the most surperficial above-mentioned alumina layer and hard film by hard film and have excellent adhesion strength, therefore the surface-coated cutting tool of making by the manufacture method of this invention is brought into play excellent cutting ability through life-time service, and can seek the long lifetime of life tools.
Description of drawings
Fig. 1 represents the X-ray diffraction figure that the alumina layer for instrument 4 of the present invention and comparative example instrument 4 obtains.
Embodiment
Then, by embodiment this invention is specifically described.
[embodiment 1]
(a1) as raw material powder, prepare the WC powder, TiC powder, ZrC powder, VC powder, TaC powder, NbC powder, the Cr that all have 1～3 μ m median size
3C
2Powder, the TiN powder, TaN powder and Co powder, these raw material powders are fitted in predetermined mix proportion, adding paraffin ball milling in acetone mixed 24 hours again, behind the drying under reduced pressure, impact briquetting is the pressed compact of predetermined shape under 98MPa pressure, in the vacuum of 5Pa, with this pressed compact of condition vacuum sintering of 1 hour of maintenance under the preset temperature in 1370～1470 ℃ of scopes, behind the sintering, the cutting blade is implemented the cutting edge reconditioning processing of R:0.07mm, thereby produce the WC base cemented carbide tool base A processed with blade shapes of stipulating among the ISOCNMG120408, B, C, D(is called hard substrate A, B, C, D).
(b1) then, be in the arc ion plating apparatus with above-mentioned hard substrate A a kind of of physical vapor deposition device that pack into, coat by physical vapor deposition and form thickness and be 2.0 μ m and comprise Ti
0.5Al
0.5The hard film of N layer.
In addition, pack into too in the arc ion plating apparatus for above-mentioned hard substrate B, coat by physical vapor deposition and form thickness and be 2.0 μ m and comprise Al
0.7Cr
0.3The hard film of N layer.
In addition, for above-mentioned hard substrate C, in the plasma nitridation process of packing into the device, be 600 ℃ with base plate heating, and in the air-flow of ammonia and hydrogen (throughput ratio is made as 1:4), under the pressure of 200Pa, substrate is added the volts DS of ﹣ 300V, carry out about 1 hour plasma nitridation process.
(c1) on the other hand, following carrying out be used to utilizing sol-gel method to form the preparation of the alumina sol of alumina layer in the most surperficial coating of hard film.
Aluminium-alcohol salt at the predetermined amount shown in the table 1 is in the aluminium secondary butylate, adds the ethanol of the predetermined amount that is shown in equally table 1 as alcohol, stirs with 0 ℃ in thermostatic bath, again the hydrochloric acid that adds predetermined water gaging is spent interpolation in 1 hour in the dropping mode.
(d1) under the state that in thermostatic bath, holds it in below 10 ℃ as shown in table 1, continue to stir more than 12 hours, carry out 24 hours ripening at low temperature with 3 ℃ again and process, thus the preparation alumina sol.
In addition, the water yield that makes an addition in this colloidal sol is 1:20～1:100 with respect to the ratio of aluminium contained in the above-mentioned alumina sol.
(e1) mol ratio of aluminium and water becomes in the scope of 1:30～1:150 in the alumina sol for preparing in above-mentioned operation in order to make, the high crystallization processing of implementing the water of the predetermined amount shown in the interpolation table 1 and heating, stirs under predetermined condition.
(f1) then, at the described Ti that comprises that is formed on above-mentioned hard substrate A, the B
0.5Al
0.5N layer, Al
0.7Cr
0.3On the hard film of N layer, at the hard substrate C that carries out plasma nitridation process and do not implement the above-mentioned alumina sol of special surface-treated hard substrate D coating.
(g1) then, in atmosphere with 300 ℃ of drying treatment of the alumina sol of above-mentioned coating being carried out 0.5 hour, after repeatedly adding up to again 5 coatings and drying, in atmosphere with 600 ℃ of processing of burning till of carrying out 1 hour, forming thickness in the most surperficial coating is 1 μ m and alumina layer with α-aluminum oxide structure of corundum type crystalline structure, thus produce surface-coated cutting tool 1 of the present invention, 2,3,4(is called instrument 1 of the present invention, 2,3,4).
For the invention described above instrument 1～4, utilize the X-ray diffraction device to the result that alumina layer carries out structural analysis, confirmed that alumina layer possesses the α-aluminum oxide structure with corundum type crystalline structure.
As an example X-ray diffraction figure that the alumina layer for instrument 4 of the present invention obtains is shown among Fig. 1, can confirms that from Fig. 1 the alumina layer of instrument of the present invention is the α-aluminum oxide structure with corundum type crystalline structure.
[comparative example 1]
For relatively, made surface-coated cutting tool with following manufacture method.
That is, to tool base A, B, C, the D of described (a1), utilize described (b1) operation to form hard film, and utilize described (c1) operation (reference table 1) preparation alumina sol.
Then, replace described (d1) operation, in thermostatic bath, remain under 40 ℃ the state, continue to stir 12 hours, carry out 24 hours maturation process with 40 ℃ again, thus the preparation alumina sol.
Then, with described (f1) in the same manner, at the Ti that comprises that is formed on hard substrate A, the B
0.5Al
0.5N layer, Al
0.7Cr
0.3Reach on the hard film of N layer, at the hard substrate C that implements plasma nitridation process and do not implement to be coated with above-mentioned alumina sol on the special surface-treated hard substrate D.
Then, with described (g1) in the same manner, in atmosphere with 300 ℃ of drying treatment of the alumina sol of above-mentioned coating being carried out 0.5 hour, after repeatedly adding up to again 5 coatings and drying treatment, in atmosphere with 600 ℃ of processing of burning till of carrying out 1 hour, forming thickness in the most surperficial coating is the alumina layer of 1 μ m, thereby the surface-coated cutting tool 1,2,3, the 4(that produce comparative example are called comparative example instrument 1,2,3,4).
[reference example 1]
For reference, made surface-coated cutting tool with following manufacture method.
That is, to tool base A, B, C, the D of described (a1), utilize described (b1) operation to form hard film, utilize described (c1) operation (reference table 1) preparation alumina sol, and utilize described (d1) operation
After (reference table 1) implemented ripening at low temperature and processed, utilize described (f1) operation on hard substrate A, B, C, the D respectively coating do not implement colloidal sol that high crystallization of the present invention processes and under the condition different from high crystallization process range of the present invention, utilize described (e1) operation to implement the colloidal sol that high crystallization is processed.
Then, with described (g1) in the same manner, in atmosphere with 300 ℃ of drying treatment of the alumina sol of above-mentioned coating being carried out 0.5 hour, after repeatedly adding up to again 5 coatings and drying treatment, in atmosphere with 600 ℃ of processing of burning till of carrying out 1 hour, forming thickness in the most surperficial coating is the alumina layer of 1 μ m, thereby the surface-coated cutting tool 1～4(that produces reference example is called reference example instrument 1～4).
For above-mentioned comparative example instrument 1～4, reference example instrument 1～4, the result who utilizes the X-ray diffraction device that alumina layer is carried out structural analysis does not detect clear and definite peak value, confirmed alumina layer have crystallinity lower near amorphous crystalline structure.
Then, to the invention described above instrument 1～4, comparative example instrument 1～4 and reference example instrument 1～4, carry out under the following conditions the machining test of chromemolybdenum steel.
The pole of workpiece: JISSCM415
Cutting speed: 180m/min
Cutting-in amount: 1.5mm
Speed of feed: 0.3mm/rev
Cutting time: 5 minutes
State of wear to each instrument after the machining test is observed, and carries out the mensuration of tool flank wear.
These be the results are shown in table 2.
[table 1]
[table 2]
[embodiment 2]
(a2) as raw material powder, the TiCN(for preparing all to have 0.5～2 μ m median size is TiC/TiN=50/50 by quality ratio) powder, Mo
2The C powder, the ZrC powder, the NbC powder, the TaC powder, WC powder, Co powder and Ni powder, these raw material powders are fitted in predetermined mix proportion, after ball mill wet mixing 24 hours and drying, impact briquetting is pressed compact under the pressure of 98MPa, in the nitrogen atmosphere of 1.3kPa, with in temperature: 1540 ℃ of lower these pressed compacts of condition sintering that keep 1 hour, behind the sintering, cutting edge is partly implemented the cutting edge reconditioning processing of R:0.07mm, thereby produce the TiCN based ceramic metal tool base E processed of the blade shapes with iso standard CNMG190612, F(is called sintering metal matrix E, F).
(b2) then, be in the arc ion plating apparatus with above-mentioned sintering metal matrix E a kind of of physical vapor deposition device that pack into, coat by physical vapor deposition and form thickness and be 2.0 μ m and comprise Ti
0.5Al
0.5The hard film of N layer.
In addition, pack into too in the arc ion plating apparatus for above-mentioned sintering metal matrix F, coat by physical vapor deposition and form thickness and be 2.0 μ m and comprise Al
0.7Cr
0.3The hard film of N layer.
(c2) on the other hand, following carrying out be used to utilizing sol-gel method to form the preparation of the alumina sol of alumina layer in the most surperficial coating of hard film.
Aluminium-alcohol salt at the predetermined amount shown in the table 3 is in the aluminum isopropylate, the predetermined amount n-butyl alcohol of the alpha alumina particles that contains predetermined mean particle diameter shown in the interpolation table 3 is as alcohol, and when in thermostatic bath, stirring with 0 ℃, spend the water-reducible nitric acid that added with predetermined amount in 1 hour in the dropping mode.
(d2) in thermostatic bath, hold it under 0 ℃ the state, continue to stir 12 hours, process with 3 ℃ of ripening at low temperature of carrying out 24 hours again, thus the preparation alumina sol.
In addition, the water yield that makes an addition in this colloidal sol is 1:20～1:100 with respect to the ratio of aluminium contained in the above-mentioned alumina sol.
(e2) for the mol ratio that makes aluminium contained in the alumina sol for preparing and water in above-mentioned operation becomes 1:30～1:150, the high crystallization processing of implementing the water of the predetermined amount shown in the interpolation table 3 and under predetermined condition, heating, stir.
(f2) then, at the described Ti that comprises that is formed on above-mentioned sintering metal matrix E, the F
0.5Al
0.5N layer, Al
0.7Cr
0.3The above-mentioned alumina sol of coating on the hard film of N layer.
(g2) then, in atmosphere with 300 ℃ of drying treatment of the alumina sol of above-mentioned coating being carried out 0.5 hour, after repeatedly adding up to again 4 coatings and drying, in atmosphere, carry out burning till in 1 hour processing with 600 ℃, forming thickness in the most surperficial coating is 1 μ m and alumina layer with α-aluminum oxide structure of corundum type crystalline structure, thus produce surface-coated cutting tool 5 of the present invention, 6(is called instrument 5 of the present invention, 6).
(a3) in addition, as raw material powder, prepare all to have TiN powder, TiC powder, TiCN powder, the TiAl of the median size in 0.3～0.9 mu m range
3Powder, Al
2O
3Powder, WC powder and cBN powder, these raw material powders are fitted in predetermined mix proportion, after in ball mill, utilizing acetone wet mixing 48 hours and drying, it is diameter with hydraulic punch impact briquetting under the forming pressure of 1MPa: the size of 50mm * thickness: 1.5mm, then in the vacuum atmosphere of pressure: 1Pa, keep under the preset temperature in 1000～1300 ℃ of scopes this formed body being heat-treated in 30～60 minutes, the composition of removing volatile component and being adsorbed in powder surface is used as the cutting edge sheet with the preparation sintered compact, will prepare sintered compact with prepare in addition have a Co:8 quality %, WC: in the common ultra-high pressure sintering device of packing under the overlapping state of the WC base cemented carbide supporting slice processed of the size of remaining composition and diameter: 50mm * thickness: 2mm, be pressure in usual conditions: 5GPa, temperature: 1500 ℃, hold-time: carry out the high pressure high temperature sintering under 30 minutes the condition, obtain the cBN agglomerated material.With spark coil cutting processor cBN agglomerated material plectane is cut to predetermined size, with have take quality % Cu as 26%, Ti as 5%, Ag as the solder brazing of the Ag alloy of the composition of remainder in having Co as 5 quality %, the TaC composition as 5 quality %, WC as remainder and the soldering section (bight) of the WC base cemented carbide vane body processed of the blade shapes of iso standard CNGA120408, and implement top and bottom and periphery is ground, the cutting edge reconditioning is processed, thereby produce cBN sintering system tool base G, H, the I of the blade shapes with iso standard CNGA120408.
For cBN sintering system tool base G, H, I, by above-mentioned operation (b2)～(g2) after forming hard film respectively on tool base G, the H, for tool base I, then form pellumina with untreated state on each surface, produce surface-coated cutting tool 7 of the present invention, 8,9(is called instrument 7 of the present invention, 8,9).
For the invention described above instrument 5～9, utilize the X-ray diffraction device to the result that alumina layer carries out structural analysis, confirmed that alumina layer possesses the α-aluminum oxide structure with corundum type crystalline structure.
[comparative example 2]
For relatively, utilize above-mentioned tool base E～I, the surface-coated cutting tool 5～9(that makes comparative example is called comparative example instrument 5～9).
That is, utilize above-mentioned (b2) operation, comprise Ti in sintering metal matrix E formation
0.5Al
0.5The hard film of N layer comprises Al in sintering metal matrix F formation
0.7Cr
0.3The hard film of N layer comprises Ti in cBN sintering system tool base G formation
0.5Al
0.5The hard film of N layer comprises Al in cBN sintering system tool base H formation
0.7Cr
0.3The hard film of N layer, in addition, I keeps untreated state for cBN sintering system tool base, utilizes above-mentioned (c2) operation to prepare alumina sol.
Then, in described (d2) operation, in thermostatic bath, remain under 40 ℃ the state, continue to stir 12 hours, again with 40 ℃ of maturation process of carrying out 24 hours, thus the preparation alumina sol.
Then, on the hard film that is formed on sintering metal matrix E, F, cBN sintering system tool base G, the H and the above-mentioned alumina sol of untreated cBN sintering system tool base I coating.
Then, with above-mentioned (g2) in the same manner in atmosphere with 300 ℃ of drying treatment of the alumina sol of above-mentioned coating being carried out 0.5 hour, after repeatedly adding up to again 5 coatings and drying treatment, in atmosphere with 600 ℃ of processing of burning till of carrying out 1 hour, forming thickness in the most surperficial coating is the alumina layer of 1 μ m, thereby the surface-coated cutting tool 5～9(that produces comparative example is called comparative example instrument 5～9).
[reference example 2]
For reference, made surface-coated cutting tool with following manufacture method.
Namely, for the tool base G of the tool base E of described (a2)～F, described (a3)～I, utilize described (b2) operation to form hard film, utilize described (c2) operation to prepare alumina sol, after utilizing described (d2) operation to implement ripening at low temperature to process, utilize described (f2) operation not implement colloidal sol that high crystallization of the present invention processes and under the different condition of the scope of processing from high crystallization of the present invention, utilize described (e2) operation to implement the colloidal sol that high crystallization is processed in tool base E～I coating.
Then, with described (g2) in the same manner in atmosphere with 300 ℃ of drying treatment of the alumina sol of above-mentioned coating being carried out 0.5 hour, after repeatedly adding up to again 5 coatings and drying treatment, in atmosphere with 600 ℃ of processing of burning till of carrying out 1 hour, forming thickness in the most surperficial coating is the alumina layer of 1 μ m, thereby the surface-coated cutting tool 5～9(that produces reference example is called reference example instrument 5～9).
For above-mentioned comparative example instrument 5～9, above-mentioned reference example instrument 5～9, utilize the X-ray diffraction device alumina layer to be carried out the result of structural analysis, do not detect clear and definite peak value, and confirmed alumina layer have crystallinity lower near amorphous crystalline structure.
Then, under the following conditions to the invention described above instrument 5,6, comparative example instrument 5,6 and reference example instrument 5,6 carry out the machining test of carbon steel.
The pole of workpiece: JISS45C
Cutting speed: 220m/min
Cutting-in amount: 0.5mm
Speed of feed: 2.0mm/rev
Cutting time: 5 minutes
State of wear to each instrument after the machining test is observed, and carries out the mensuration of tool flank wear.
In addition, under the following conditions the invention described above instrument 7～9, comparative example instrument 7～9 and reference example instrument 7～9 are carried out the machining test of hardened steel.
The pole of workpiece: JISSCr415
Cutting speed: 180m/min
Cutting-in amount: 0.5mm
Speed of feed: 2.0mm/rev
Cutting time: 5 minutes
State of wear to each instrument after the machining test is observed, and carries out the mensuration of tool flank wear.
The observations of the abrasive conditions of each instrument after will testing for machining is shown in table 4.
[table 3]
[table 4]
By the result shown in the table 2,4 as can be known, in the surface-coated cutting tool 1～9 made from the manufacture method of this invention, it is 0.05～5 μ m and alumina layer with α-aluminum oxide structure of corundum type crystalline structure that the most surperficial alumina layer constitutes smoothness excellence, thickness, therefore neither produce depositedly etc., and bring into play excellent wear resistance through life-time service.
Relative therewith, be in the surface-coated cutting tool 1～9 of comparative example of the lower non-crystal structure of crystallinity at the most surperficial alumina layer, owing to produce damagedly because of rake face midway in cutting, perhaps produce violent rake wear etc., therefore wear no resistance, reach work-ing life in the short period of time.
In addition, although the most surperficial alumina layer comprises the α-aluminum oxide structure with corundum type crystalline structure, but having omitted the high crystallization that comprises operation (e1) or operation (e2) in the preparation section of alumina sol processes, perhaps in the surface-coated cutting tool 1～9 of the reference example of having implemented the processing outside the scope of the invention, there is crescent hollow abrasion, although can not produce damagedly because of this crescent hollow abrasion, wearing no resistance of rear knife face have reached work-ing life in the short period of time.
Utilizability on the industry
Manufacture method according to surface-coated cutting tool of the present invention, can be by the sol-gel method of preparation alumina sol in lower low-temperature region, form the alumina layer of the α-aluminum oxide structure with corundum type crystalline structure of thermostability, excellent in abrasion resistance with simple operation, therefore, not only can seek the long lifetime of life tools, but also can help joint source, energy-conservation in the manufacturing process, practical function is large.
Claims (4)
1. the manufacture method of the surface-coated cutting tool of an excellent in abrasion resistance, form the alumina layer of α-aluminum oxide structure in the most surperficial coating of the tool base that comprises tungsten carbide base carbide alloy, base titanium carbonitride, rapid steel or cubic boron nitride base ultra-high pressure sintered compact, this alumina layer has the thickness of 0.05～5 μ m and has the corundum type crystalline structure, it is characterized in that
Above-mentioned alumina layer coats by following sol-gel method and forms: add alcohol in aluminium-alcohol salt, and after further adding acid, in the temperature range below 10 ℃, stir and generate colloidal sol, after interpolation water makes the mol ratio of aluminium contained in this colloidal sol and water become 1:30～1:150 in colloidal sol, be implemented under 15～80 ℃ the temperature and heat, the high crystallization that stirs is processed, to implement that colloidal sol that this high crystallization processes is coated above-mentioned tool base surface or the hard film that forms on the tool base surface the most surperficial, then, repeatedly carry out the drying treatment under 100～400 ℃ more than 1 time, then, in 500～1000 ℃ temperature range, burn till processing.
2. the manufacture method of the surface-coated cutting tool of excellent in abrasion resistance as claimed in claim 1 is characterized in that,
By physical vapor deposition, chemical vapor deposition method or sol-gel method coat on the surface of above-mentioned tool base contain at least a above element among the 4a, the 5a that are selected from periodictable, 6a family, Al, the Si nitride as hard film, and at the above-mentioned alumina layer of the most surperficial formation of this hard film.
3. the manufacture method of the surface-coated cutting tool of excellent in abrasion resistance as claimed in claim 1 is characterized in that, implements nitriding treatment on the surface of above-mentioned tool base in advance.
4. such as the manufacture method of the surface-coated cutting tool of each described excellent in abrasion resistance in the claims 1 to 3, it is characterized in that,
When in above-mentioned aluminium-alcohol salt, adding alcohol, add and contain the alcohol that median size is the alpha alumina particles of 10～300nm.
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| JP2011192437A JP5771483B2 (en) | 2011-09-05 | 2011-09-05 | Method for producing surface-coated cutting tool with excellent wear resistance |
| JP2011-192437 | 2011-09-05 |
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| CN107405695A (en) * | 2015-03-13 | 2017-11-28 | 三菱综合材料株式会社 | Hard coating layer plays the excellent resistance to surface-coated cutting tool for collapsing knife |
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| JP6115824B2 (en) * | 2013-09-06 | 2017-04-19 | 三菱マテリアル株式会社 | Metal nitride material for thermistor, method for producing the same, and thermistor sensor |
| JP6364195B2 (en) * | 2014-01-30 | 2018-07-25 | 三菱マテリアル株式会社 | Surface-coated cutting tool with excellent chipping resistance in high-speed intermittent cutting |
| JP6488106B2 (en) * | 2014-10-30 | 2019-03-20 | 三菱マテリアル株式会社 | Surface-coated cutting tool with excellent chipping resistance in high-speed intermittent cutting |
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| JP5771483B2 (en) | 2015-09-02 |
| JP2013053344A (en) | 2013-03-21 |
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