CN105586572B - (Ti, Al, Zr) N multicomponents composite coating, the gradient ultra-fine cemented carbide cutter with the composite coating and preparation method thereof - Google Patents
(Ti, Al, Zr) N multicomponents composite coating, the gradient ultra-fine cemented carbide cutter with the composite coating and preparation method thereof Download PDFInfo
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- CN105586572B CN105586572B CN201610083506.2A CN201610083506A CN105586572B CN 105586572 B CN105586572 B CN 105586572B CN 201610083506 A CN201610083506 A CN 201610083506A CN 105586572 B CN105586572 B CN 105586572B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
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Abstract
A kind of (Ti, Al, Zr) N multicomponents composite coating, the gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings and preparation method thereof.Alloy cutter is made of tool matrix and (Ti, Al, Zr) N multicomponents composite coating.Tool matrix is provided with normal structure layer, rich cobalt transition zone and poor cobalt richness cubic layer.(Ti, Al, Zr) N multicomponents composite coating includes N layers of the TiAlN layers as transition zone, (Ti, Al, Zr) as functional layer.The present invention has the gradient ultra-fine cemented carbide cutter for being somebody's turn to do (Ti, Al, Zr) N multicomponent composite coatings, its tool matrix and (Ti, Al, Zr) N multicomponent composite coating associativities are good, solid tool has good abrasion-proof and temperature-resistant performance, and intensity is high, shock resistance is excellent.(Ti, Al, Zr) N multicomponent composite coatings, good with tool matrix associativity, adhesive force is good between the coating of composite coating, and heat-resisting quantity, corrosion resistance, wearability are good.
Description
Technical field
The present invention relates to hard alloy cutter technical field, more particularly to a kind of compound painting of (Ti, Al, Zr) N multicomponents
Layer, the gradient ultra-fine cemented carbide cutter with the composite coating and preparation method thereof.
Background technology
The appearance of cutting tool coated with hard alloy is an important milestone in cutter development history.It is in intensity and toughness
On preferable hard alloy substrate, the good refractory metal of a thin layer wearability or nonmetallic chemical combination are coated using vapor deposition method
Object and formed.
Coating reduces diffusion and chemical reaction between cutter and workpiece as a chemical barrier and thermodynamic barrier, so as to
Reduce crescent hollow abrasion.Coating has very high hardness and heat resistance, and reduces the friction coefficient between cutter and workpiece, because
This coated cutting tool can significantly increase service life than non-coated tool, and the service life of usual coated cutting tool is than non-coated tool height
2-5 times.
At present, oneself successfully prepares a variety of coatings in carbide tool surface, from binary coating to complicated multilayer, polynary
Coating.Wherein, it is most widely used for transition metal nitride coating, such as TiN and TiAlN.With the development of cutting element
With the requirement of machined material, harsher requirement is proposed to the performance of cutting tool.Cutting tool will have high-wearing feature,
High tenacity will also have the characteristics that high temperature resistant, impact resistance.
Therefore, in view of the shortcomings of the prior art, provide it is a kind of suitable for carbide tool surface performance enhancement (Ti, Al,
Zr) N multicomponents composite coating, have the gradient ultra-fine cemented carbide cutter and preparation method thereof of the composite coating existing to overcome
Technical deficiency is very necessary.
Invention content
One of the objects of the present invention is to provide a kind of gradient with (Ti, Al, Zr) N multicomponent composite coatings is ultra-fine hard
Matter alloy cutter and preparation method thereof, (Ti, Al, Zr) N multicomponents composite coating and tool matrix associativity are good, and cutter has
Abrasion-proof and temperature-resistant is good, and intensity is high, shock resistance is excellent.
A kind of (Ti, Al, Zr) N multicomponents are provided another object of the present invention is to avoid the deficiencies in the prior art part
Composite coating and preparation method thereof, (Ti, Al, Zr) N multicomponents composite coating and tool matrix associativity are good, have the coating
Cutter abrasion-proof and temperature-resistant it is good, intensity is high, shock resistance is excellent.
The above-mentioned purpose of the present invention is realized by following technological means.
A kind of gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings is provided, by cutter base
Body and (Ti, Al, Zr) the N multicomponents composite coating being set on tool matrix are formed；
The tool matrix includes normal structure layer, rich cobalt transition zone and poor cobalt richness cubic layer, the normal structure layer,
Rich cobalt transition zone and poor cobalt richness cubic layer are arranged in order according to sequence from inside to outside；
(Ti, Al, Zr) the N multicomponents composite coating includes being deposited on poor cobalt richness cubic layer surface as transition
The TiAlN layers of layer be deposited on transition zone as N layers of (Ti, Al, the Zr) of functional layer.
The content of cobalt is 5-15wt.% in the upper tool matrix；
The normal structure layer is ultra-fine cemented carbide, and WC grain size is 1-10000nm；
The thickness of the normal structure layer is more than 2mm, and the thickness of the richness cobalt transition zone is 20-100 microns；The poor cobalt
The thickness of rich cubic layer is 20-50 microns；
The thickness of the functional layer is 10-30 microns, and the transition region thickness is 0.1-2 microns.
The content of cobalt is 8-12wt.% in above-mentioned tool matrix；The WC grain size of the normal structure layer is 1nm-
400nm, above-mentioned (Ti, Al, Zr) N multicomponent composite coatings are prepared by multi-arc ion plating process.
The above-mentioned gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings, (Ti, Al, Zr) N
The specific preparation process of multicomponent composite coating is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 400-500 DEG C, vacuum degree be 1.50 × 10-2 -
2.0×10-2The Ar gas of high-purity is passed through during Pa, it is 1.5-2.5 Pa that pressure is kept when Ar throughputs are 250-300SCCM, profit
The tool matrix 25-40min being installed on turntable is cleaned with Ar ion aura；
Turntable is kept to be rotated with the rotating speed of 2-5rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is
45-550%, pulsed bias -1000V, the electric current that Ti targets and Al targets are passed through to 80-100A carry out burning target, then by two AlTi
Alloys target is passed through 70-90A electric currents burning target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
In 250 to -150 V of pulsed bias, duty ratio 90%, operating pressure 0.5-0.8 Pa, N2 flows 180-250
Under conditions of SCCM, 60-80A electric currents are passed through in Ti targets, high-energy metals Ti ion bombardment cutters are utilized for 380-420 DEG C in temperature
Matrix 3-8min is roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, in 180 to 130 V of pulsed bias, duty ratio 90%, work pressure
Strong is under conditions of 0.5-0.8Pa, N2 flow are 220-280 SCCM, and Ti targets are passed through 60-90A electric currents, deposit 15-30min systems
It is standby to obtain the TiAlN layers as transition zone；
（3）Deposit functional layers
Pulsed bias -50V~-200V, duty ratio 90%, pressure 1.5Pa~3.0Pa adjusting under, Zr targets are led to
70-90A electric currents, AlTi alloys targets lead to 60A~90A electric currents, at 400 DEG C of temperature sedimentation time 35-50 min obtain (Ti,
Al, Si, Zr) N layers.
Preferably, above-mentioned multi-arc ion plating equipment with Magnetic filter driving power drive, use purity for 99.99% pure Zr
Target, pure Ti targets and two AlTi alloys targets, the ratio of Al atoms and Ti atoms is 67 in AlTi alloys targets:33；
The specific preparation process of (Ti, Al, Zr) N multicomponent composite coatings is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 450 DEG C, vacuum degree be 1.52 × 10-2Lead to during Pa
Enter the Ar gas of high-purity, it is 2 Pa that pressure is kept when Ar throughputs are 260SCCM, and rotation is installed on using the cleaning of Ar ions aura
Tool matrix 30min on turntable；
Turntable is kept to be rotated with the rotating speed of 3rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is 50%
, pulsed bias -1000V, the electric current that Ti targets and Al targets are passed through to 90A carries out burning target, two AlTi alloys targets then is passed through 80A
Electric current burns target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
Under conditions of 200 V of pulsed bias, duty ratio 90%, 0.6 Pa, N2 flow of operating pressure, 200 SCCM,
Ti targets are passed through 70A electric currents, utilize high-energy metals Ti ion bombardment tool matrix 5min for 400 DEG C in temperature, are roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, it is in 150 V of pulsed bias, duty ratio 90%, operating pressure
Under conditions of 0.6 Pa, N2 flow is 250 SCCM, Ti targets are passed through 80A electric currents, and deposition 20min is prepared as transition zone
TiAlN layers；
（3）Deposit functional layers
Pulsed bias -150V, duty ratio 90%, pressure 2.0Pa adjusting under, 80A electric currents, AlTi are led to Zr targets
Alloys target leads to 80A electric currents, and 45 min of sedimentation time obtains N layers of (Ti, Al, Si, Zr) at 400 DEG C of temperature.
The preparation method of gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings, packet are provided
It includes the preparation of tool matrix and (Ti, Al, Zr) N multicomponent composite coatings is prepared on tool matrix surface；
(Ti, Al, Zr) N multicomponent composite coatings are prepared by multi-arc ion plating process.
The specific preparation process of (Ti, Al, Zr) N multicomponent composite coatings is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 400-500 DEG C, vacuum degree be 1.50 × 10-2 -
2.0×10-2The Ar gas of high-purity is passed through during Pa, it is 1.5-2.5 Pa that pressure is kept when Ar throughputs are 250-300SCCM, profit
The tool matrix 25-40min being installed on turntable is cleaned with Ar ion aura；
Turntable is kept to be rotated with the rotating speed of 2-5rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is
45-550%, pulsed bias -1000V, the electric current that Ti targets and Al targets are passed through to 80-100A carry out burning target, then by two AlTi
Alloys target is passed through 70-90A electric currents burning target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
In 250 to -150 V of pulsed bias, duty ratio 90%, operating pressure 0.5-0.8 Pa, N2 flows 180-250
Under conditions of SCCM, 60-80A electric currents are passed through in Ti targets, high-energy metals Ti ion bombardment cutters are utilized for 380-420 DEG C in temperature
Matrix 3-8min is roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, in 180 to 130 V of pulsed bias, duty ratio 90%, work pressure
Strong is under conditions of 0.5-0.8Pa, N2 flow are 220-280 SCCM, and Ti targets are passed through 60-90A electric currents, deposit 15-30min systems
It is standby to obtain the TiAlN layers as transition zone；
（3）Deposit functional layers
Pulsed bias -50V~-200V, duty ratio 90%, pressure 1.5Pa~3.0Pa adjusting under, Zr targets are led to
70-90A electric currents, AlTi alloys targets lead to 60A~90A electric currents, at 400 DEG C of temperature sedimentation time 35-50 min obtain (Ti,
Al, Si, Zr) N layers.
A kind of (Ti, Al, Zr) N multicomponent composite coatings for gradient ultra-fine cemented carbide cutter are provided, including being used for
Tool matrix surface is deposited on as the TiAlN layers of transition zone and and is deposited on transition zone as (Ti, Al, the Zr) of functional layer
N layers.
The thickness of above-mentioned functional layer is 10-30 microns, and the transition region thickness is 0.1-2 microns.
A kind of preparation method of (Ti, Al, Zr) N multicomponent composite coatings is provided, specific preparation process is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 400-500 DEG C, vacuum degree be 1.50 × 10-2 -
2.0×10-2The Ar gas of high-purity is passed through during Pa, it is 1.5-2.5 Pa that pressure is kept when Ar throughputs are 250-300SCCM, profit
The tool matrix 25-40min being installed on turntable is cleaned with Ar ion aura；
Turntable is kept to be rotated with the rotating speed of 2-5rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is
45-550%, pulsed bias -1000V, the electric current that Ti targets and Al targets are passed through to 80-100A carry out burning target, then by two AlTi
Alloys target is passed through 70-90A electric currents burning target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
In 250 to -150 V of pulsed bias, duty ratio 90%, operating pressure 0.5-0.8 Pa, N2 flows 180-250
Under conditions of SCCM, 60-80A electric currents are passed through in Ti targets, high-energy metals Ti ion bombardment cutters are utilized for 380-420 DEG C in temperature
Matrix 3-8min is roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, in 180 to 130 V of pulsed bias, duty ratio 90%, work pressure
Strong is under conditions of 0.5-0.8Pa, N2 flow are 220-280 SCCM, and Ti targets are passed through 60-90A electric currents, deposit 15-30min systems
It is standby to obtain the TiAlN layers as transition zone；
（3）Deposit functional layers
Pulsed bias -50V~-200V, duty ratio 90%, pressure 1.5Pa~3.0Pa adjusting under, Zr targets are led to
70-90A electric currents, AlTi alloys targets lead to 60A~90A electric currents, at 400 DEG C of temperature sedimentation time 35-50 min obtain (Ti,
Al, Si, Zr) N layers.
The present invention has the gradient ultra-fine cemented carbide cutter for being somebody's turn to do (Ti, Al, Zr) N multicomponent composite coatings, cutter base
Body and (Ti, Al, Zr) N multicomponent composite coating associativities are good, and solid tool has a good abrasion-proof and temperature-resistant performance, intensity is high,
Shock resistance is excellent.(Ti, Al, Zr) N multicomponent composite coatings, the painting of composite coating good with tool matrix associativity
Adhesive force is good between layer, and heat-resisting quantity, corrosion resistance, wearability are good.
Description of the drawings
Using attached drawing, the present invention is further illustrated, but the content in attached drawing does not form any limit to the present invention
System.
Fig. 1 is a kind of gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings of the invention
Schematic diagram.
Fig. 2 is a kind of gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings of the invention
Interlayer structure schematic diagram.
Specific embodiment
The invention will be further described with the following Examples.
Embodiment 1.
One kind has the gradient ultra-fine cemented carbide cutter of (Ti, Al, Zr) N multicomponent composite coatings, as shown in Figure 1, Figure 2 institute
Show, be made of tool matrix and (Ti, Al, Zr) the N multicomponents composite coating being set on tool matrix.
Tool matrix includes normal structure layer, rich cobalt transition zone and poor cobalt richness cubic layer, normal structure layer, rich cobalt transition
Layer and poor cobalt richness cubic layer are arranged in order according to sequence from inside to outside.The content of cobalt is 5-15wt.% in tool matrix, excellent
The content for selecting cobalt is 8-12wt.%.Normal structure layer is ultra-fine cemented carbide, and WC grain size is 1-10000nm, and preferably WC is brilliant
Particle size is 1-500nm.
Rich in cubic phase nitride or carbonitride in poor cobalt richness cubic layer, cubic phase nitride in hard alloy and
Therefore carbonitride has hardness more higher than the WC of close-packed hexagonal phase, the surface layer of poor cobalt richness cubic phase has higher hardness.
It,, can due to its good toughness when the crackle formed in coating is diffused into the region rich in Binder Phase in rich cobalt transition zone
To absorb energy during crackle diffusion, therefore, it is possible to effectively prevent crackle to alloy diffusion inside, and can preferably inhale
Impact energy during Tool in Cutting is received, thus has high toughness characteristic, and then is conducive to improve the use of cutter material
Service life.Core is rigid tissue regions, that is, normal structure layer, and WC grain is evenly distributed and tiny, and average WC grain sizes are less than etc.
In 500nm, the mechanical property for having ultra-fine cemented carbide excellent.
The thickness of normal structure layer is more than 2mm, and the thickness of rich cobalt transition zone is 20-100 microns, poor cobalt richness cubic layer
Thickness is 20-50 microns.
The thickness of functional layer is 10-30 microns.When coating layer thickness is less than 1um, wearability is poor, in machining mistake
It is worn quickly in journey, it is impossible to play the role of being effectively improved Tool in Cutting performance and service life, and when coating layer thickness is blocked up, it applies
The combination force difference of layer and matrix, excessively high compression lead to coating cracking and peeling, shorten cutter life.The thickness of coating
It is controlled by adjusting sedimentation time.
Transition region thickness is 0.1-2 microns, and transition zone promotes its binding force between poor cobalt richness cubic layer, in reduction
Stress.
The present invention has the gradient ultra-fine cemented carbide cutter for being somebody's turn to do (Ti, Al, Zr) N multicomponent composite coatings, cutter base
Body and (Ti, Al, Zr) N multicomponent composite coating associativities are good, and solid tool has a good abrasion-proof and temperature-resistant performance, intensity is high,
Shock resistance is excellent.
Embodiment 2.
A kind of preparation side of the gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings is provided
Method, preparation including tool matrix and prepares (Ti, Al, Zr) N multicomponent composite coatings on tool matrix surface.
The specific preparation process of tool matrix is as follows：
(1) with refractory carbide, binding metal and TiCN and other powder such as TiC, TaC, or other strong nitridations
Carbide, the carbonitride of object formation element are raw material, pass through four ball milling mixing, drying and screening, compression moulding and sintering steps
Suddenly hard alloy substrate presoma is prepared.
(2) fine grinding processing is carried out to hard alloy substrate presoma.
(3) gradient sintering is carried out to fine grinding treated hard alloy substrate presoma, the poor cobalt in surface layer is prepared
With rich cubic phase Graded-structure Cemented Carbides tool matrix.
(4) after carrying out chemical cleaning to tool matrix, then the compound painting of (Ti, Al, Zr) N multicomponents is deposited on its surface
Layer.
(Ti, Al, Zr) N multicomponents composite coating is prepared by arc ion plating mode, and specific preparation process is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 400-500 DEG C, vacuum degree be 1.50 × 10-2 -
2.0×10-2The Ar gas of high-purity is passed through during Pa, it is 1.5-2.5 Pa that pressure is kept when Ar throughputs are 250-300SCCM, profit
The tool matrix 25-40min being installed on turntable is cleaned with Ar ion aura；
Turntable is kept to be rotated with the rotating speed of 2-5rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is
45-550%, pulsed bias -1000V, the electric current that Ti targets and Al targets are passed through to 80-100A carry out burning target, then by two AlTi
Alloys target is passed through 70-90A electric currents burning target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
In 250 to -150 V of pulsed bias, duty ratio 90%, operating pressure 0.5-0.8 Pa, N2 flows 180-250
Under conditions of SCCM, 60-80A electric currents are passed through in Ti targets, high-energy metals Ti ion bombardment cutters are utilized for 380-420 DEG C in temperature
Matrix 3-8min is roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, in 180 to 130 V of pulsed bias, duty ratio 90%, work pressure
Strong is under conditions of 0.5-0.8Pa, N2 flow are 220-280 SCCM, and Ti targets are passed through 60-90A electric currents, deposit 15-30min systems
It is standby to obtain the TiAlN layers as transition zone；
（3）Deposit functional layers
Pulsed bias -50V~-200V, duty ratio 90%, pressure 1.5Pa~3.0Pa adjusting under, Zr targets are led to
70-90A electric currents, AlTi alloys targets lead to 60A~90A electric currents, at 400 DEG C of temperature sedimentation time 35-50 min obtain (Ti,
Al, Si, Zr) N layers.
The present invention has the gradient ultra-fine cemented carbide cutter for being somebody's turn to do (Ti, Al, Zr) N multicomponent composite coatings, cutter base
Body and (Ti, Al, Zr) N multicomponent composite coating associativities are good, and solid tool has a good abrasion-proof and temperature-resistant performance, intensity is high,
Shock resistance is excellent.Embodiment 3.
A kind of preparation side of the gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings is provided
Method, preparation including tool matrix and prepares (Ti, Al, Zr) N multicomponent composite coatings on tool matrix surface.
Tool matrix is sintered by each component of following mass percent：The TaC of the TiC of 5-15%, 2-5%, 10-15%
Alloy bonding phase, surplus WC.Alloy bonding is mutually made of the powder of following mass percent：The Cr of 0.5-5.5%, 0.5-
The Si of the Y of the V of the Al of the B of 5.5% Mo, 0.5-5.5%, 0.5-5.5%, 0.5-5.5%, 0.5-5.5%, 0.5-5.5%, surplus are
Co, and the quality sum of Cr, Mo, B, Al, V, Y and Si are the 7-20% of alloy bonding phase quality in alloy bonding phase.
The preparation method of tool matrix, includes the following steps：
S1, alloy bonding phase is prepared：Weigh eight kinds of powders of Cr, Mo, B, Al, V, Y, Si, Co respectively by mass percentage, it will
Eight kinds of powders are uniformly mixed, and obtain alloy bonding phase.It is preferred that eight kinds of powders are placed in ball mill, with hard alloy mill ball ball milling
72 hours, and just suspend ball milling 10min per ball milling 1h, obtain alloy bonding phase.
S2, blank is prepared：Weigh tetra- kinds of alloy bonding phase, TiC, TaC, WC components, four kinds of groups respectively by mass percentage
It is grouped as material powder；Paraffin is weighed, and paraffin is uniformly mixed with material powder by the 1.5-2.5% of material powder gross mass,
Obtain blank.
S3, pressing blank：By blank compression moulding, green body is obtained.
Can be first with molding press by blank compression moulding, green body at the beginning of obtaining；Just green body is further suppressed with cold isostatic press again, is obtained
Green body.
S4, sintering：Green body is placed in sintering furnace, 1200-1250 DEG C is warming up to the speed of 5-8 DEG C/min, keeps the temperature 18-
22min, and keep 10-3The vacuum degree of below Pa；Then nitrogen is filled with into sintering furnace and is warming up to the speed of 1-3 DEG C/min
It 1420-1450 DEG C, keeps the temperature 55-65min and keeps the pressure of more than 0.2MPa；Then it is cooled to again with the speed of 2-6 DEG C/min
1000-1200 DEG C, 110-130min is kept the temperature, and keep the pressure of more than 0.2MPa；Followed by green body furnace cooling, and keep
Case-hardened gradient hard alloy is made in the pressure of more than 0.2MPa.
Pre-sintering step can be carried out, the pre-sintering step is that green body is placed in sintering furnace, in inertia before step S4
Under gas atmosphere, with 1400 DEG C of sintering 10min；Refine green body shape after green body furnace cooling.
Hard alloy substrate prepared by this method has excellent mechanical property, improves the red hardness of hard alloy.
Crystal grain in carbide matrix body is tiny, is normal structure layer；The surface layer richness cubic phase of hard alloy and poor Binder Phase, that is, poor cobalt
Rich cubic phase, and also have the i.e. rich cobalt transition zone of transition zone of a rich alloy Binder Phase under surface layer, so as to have hard alloy
Excellent hardness, wearability and toughness.
After the completion of prepared by alloy substrate, chemical cleaning is carried out to it, then deposits (Ti, Al, Zr) N multicomponents on its surface
Composite coating.
Multi-arc ion plating equipment with Magnetic filter driving power drive, use purity for 99.99% pure Zr targets, pure Ti targets and
Two AlTi alloys targets, the ratio of Al atoms and Ti atoms is 67 in AlTi alloys targets:33.
The specific preparation process of (Ti, Al, Zr) N multicomponent composite coatings is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 450 DEG C, vacuum degree be 1.52 × 10-2Lead to during Pa
Enter the Ar gas of high-purity, it is 2 Pa that pressure is kept when Ar throughputs are 260SCCM, and rotation is installed on using the cleaning of Ar ions aura
Tool matrix 30min on turntable；
Turntable is kept to be rotated with the rotating speed of 3rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is 50%
, pulsed bias -1000V, the electric current that Ti targets and Al targets are passed through to 90A carries out burning target, two AlTi alloys targets then is passed through 80A
Electric current burns target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
Under conditions of 200 V of pulsed bias, duty ratio 90%, 0.6 Pa, N2 flow of operating pressure, 200 SCCM,
Ti targets are passed through 70A electric currents, utilize high-energy metals Ti ion bombardment tool matrix 5min for 400 DEG C in temperature, are roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, it is in 150 V of pulsed bias, duty ratio 90%, operating pressure
Under conditions of 0.6 Pa, N2 flow is 250 SCCM, Ti targets are passed through 80A electric currents, and deposition 20min is prepared as transition zone
TiAlN layers；
（3）Deposit functional layers
Pulsed bias -150V, duty ratio 90%, pressure 2.0Pa adjusting under, 80A electric currents, AlTi are led to Zr targets
Alloys target leads to 80A electric currents, and 45 min of sedimentation time obtains N layers of (Ti, Al, Si, Zr) at 400 DEG C of temperature.
There is the gradient ultra-fine cemented carbide cutter for being somebody's turn to do (Ti, Al, Zr) N multicomponent composite coatings prepared by the present invention,
Its tool matrix and (Ti, Al, Zr) N multicomponent composite coating associativities are good, and solid tool has good abrasion-proof and temperature-resistant performance,
Intensity is high, shock resistance is excellent.
Embodiment 4.
A kind of (Ti, Al, Zr) N multicomponent composite coatings for gradient ultra-fine cemented carbide cutter, structure is with implementing
(Ti, Al, Zr) N multicomponent composite coatings in example 1-3 in any one are identical, and tool matrix surface work is deposited on including being used for
TiAlN layers for transition zone are deposited on transition zone as N layers of (Ti, Al, the Zr) of functional layer.
(Ti, Al, Zr) N multicomponent composite coatings prepared by the present invention, composite coating good with tool matrix associativity
Coating between adhesive force is good, heat-resisting quantity, corrosion resistance, wearability are good, and intensity is high, shock resistance is excellent.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of range, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should manage
Solution, technical scheme of the present invention can be modified or replaced equivalently, without departing from technical solution of the present invention essence and
Range.
Claims (4)
1. one kind has the gradient ultra-fine cemented carbide cutter of (Ti, Al, Zr) N multicomponent composite coatings, it is characterised in that：
It is made of tool matrix and (Ti, Al, Zr) the N multicomponents composite coating being set on tool matrix；
The tool matrix includes normal structure layer, rich cobalt transition zone and poor cobalt richness cubic layer, the normal structure layer, rich cobalt
Transition zone and poor cobalt richness cubic layer are arranged in order according to sequence from inside to outside；
(Ti, Al, Zr) the N multicomponents composite coating includes being deposited on poor cobalt richness cubic layer surface as transition zone
It TiAlN layers and is deposited on transition zone as N layers of (Ti, Al, the Zr) of functional layer；
The thickness of the normal structure layer is more than 2mm, and the thickness of the richness cobalt transition zone is 20-100 microns；The poor cobalt richness is stood
The thickness of square phase layer is 20-50 microns；
The thickness of the functional layer is 10-30 microns, and the transition region thickness is 0.1-2 microns；(Ti, Al, the Zr) N is multigroup
First composite coating is prepared by multi-arc ion plating process；
The specific preparation process of (Ti, Al, Zr) N multicomponent composite coatings is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 400-500 DEG C, vacuum degree be 1.50 × 10-2 -2.0×
10-2The Ar gas of high-purity is passed through during Pa, it is 1.5-2.5 Pa that pressure is kept when Ar throughputs are 250-300SCCM, utilizes Ar
The cleaning of ion aura is installed on the tool matrix 25-40min on turntable；
Turntable is kept to be rotated with the rotating speed of 2-5rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is 45-
50%th, pulsed bias -1000V, the electric current that Ti targets and Al targets are passed through to 80-100A carry out burning target, then by two AlTi alloys
Target is passed through 70-90A electric currents burning target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
In 250 to -150 V of pulsed bias, duty ratio 90%, operating pressure 0.5-0.8 Pa, N2Flow 180-250 SCCM's
Under the conditions of, 60-80A electric currents are passed through in Ti targets, high-energy metals Ti ion bombardment tool matrix 3- is utilized for 380-420 DEG C in temperature
8min is roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, it is in 180 to 130 V of pulsed bias, duty ratio 90%, operating pressure
0.5-0.8Pa、N2Under conditions of flow is 220-280 SCCM, Ti targets are passed through 60-90A electric currents, and deposition 15-30min is prepared into
To the TiAlN layers as transition zone；
（4）Deposit functional layers
Pulsed bias -50V~-200V, duty ratio 90%, pressure 1.5Pa~3.0Pa adjusting under, 70- is led to Zr targets
90A electric currents, AlTi alloys targets lead to 60A~90A electric currents, at 400 DEG C of temperature sedimentation time 35-50 min obtain (Ti, Al,
Zr) N layers.
2. the gradient ultra-fine cemented carbide cutter with (Ti, Al, Zr) N multicomponent composite coatings according to right wants 1,
It is characterized in that：
Multi-arc ion plating equipment is driven with Magnetic filter driving power, uses purity as 99.99% pure Zr targets, pure Ti targets and two
AlTi alloys targets, the ratio of Al atoms and Ti atoms is 67 in AlTi alloys targets:33；
The specific preparation process of (Ti, Al, Zr) N multicomponent composite coatings is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 450 DEG C, vacuum degree be 1.52 × 10-2Height is passed through during Pa
The Ar gas of purity, it is 2 Pa that pressure is kept when Ar throughputs are 260SCCM, and turntable is installed on using the cleaning of Ar ions aura
On tool matrix 30min；
Turntable is kept to be rotated with the rotating speed of 3rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is 50%, arteries and veins
Bias -1000V is rushed, the electric current that Ti targets and Al targets are passed through to 90A carries out burning target, and two AlTi alloys targets then are passed through 80A electricity
Stream burns target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
In 200 V of pulsed bias, duty ratio 90%, operating pressure 0.6 Pa, N2Under conditions of 200 SCCM of flow, in Ti targets
70A electric currents are passed through, high-energy metals Ti ion bombardment tool matrix 5min is utilized for 400 DEG C in temperature, is roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, in 150 V of pulsed bias, duty ratio 90%, operating pressure 0.6
Pa、N2Under conditions of flow is 250 SCCM, Ti targets are passed through 80A electric currents, and deposition 20min is prepared as transition zone
TiAlN layers；
（3）Deposit functional layers
Pulsed bias -150V, duty ratio 90%, pressure 2.0Pa adjusting under, 80A electric currents, AlTi alloys are led to Zr targets
Target leads to 80A electric currents, and 45 min of sedimentation time obtains N layers of (Ti, Al, Zr) at 400 DEG C of temperature.
3. the ultra-fine hard of gradient with (Ti, Al, Zr) N multicomponent composite coatings as described in claim 1 to 2 any one
The preparation method of alloy cutter, it is characterised in that：
Preparation including tool matrix and (Ti, Al, Zr) N multicomponent composite coatings are prepared on tool matrix surface；(Ti,Al,
Zr) N multicomponents composite coating is prepared by multi-arc ion plating process.
4. there is the gradient ultra-fine cemented carbide cutter of (Ti, Al, Zr) N multicomponent composite coatings as claimed in claim 3
Preparation method, it is characterised in that：
The specific preparation process of (Ti, Al, Zr) N multicomponent composite coatings is as follows：
（1）Tool matrix and target cleaning
Vacuum chamber is heated and is vacuumized, chamber temp reach 400-500 DEG C, vacuum degree be 1.50 × 10-2 -2.0×
10-2The Ar gas of high-purity is passed through during Pa, it is 1.5-2.5 Pa that pressure is kept when Ar throughputs are 250-300SCCM, utilizes Ar
The cleaning of ion aura is installed on the tool matrix 25-40min on turntable；
Turntable is kept to be rotated with the rotating speed of 2-5rpm, is evacuated to 10-3During Pa, on tool matrix plus duty ratio is 45-
50%th, pulsed bias -1000V, the electric current that Ti targets and Al targets are passed through to 80-100A carry out burning target, then by two AlTi alloys
Target is passed through 70-90A electric currents burning target and carries out burning target, completes the cleaning to target；
（2）High energy titanium ion bombards tool matrix
In 250 to -150 V of pulsed bias, duty ratio 90%, operating pressure 0.5-0.8 Pa, N2Flow 180-250 SCCM's
Under the conditions of, 60-80A electric currents are passed through in Ti targets, high-energy metals Ti ion bombardment tool matrix 3- is utilized for 380-420 DEG C in temperature
8min is roughened matrix surface；
（3）AlN layers of depositing Ti
After Ti metal ions bombard tool matrix, it is in 180 to 130 V of pulsed bias, duty ratio 90%, operating pressure
0.5-0.8Pa、N2Under conditions of flow is 220-280 SCCM, Ti targets are passed through 60-90A electric currents, and deposition 15-30min is prepared into
To the TiAlN layers as transition zone；
（3）Deposit functional layers
Pulsed bias -50V~-200V, duty ratio 90%, pressure 1.5Pa~3.0Pa adjusting under, 70- is led to Zr targets
90A electric currents, AlTi alloys targets lead to 60A~90A electric currents, at 400 DEG C of temperature sedimentation time 35-50 min obtain (Ti, Al,
Zr) N layers.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610083506.2A CN105586572B (en) | 2016-02-11 | 2016-02-11 | (Ti, Al, Zr) N multicomponents composite coating, the gradient ultra-fine cemented carbide cutter with the composite coating and preparation method thereof |
| PCT/CN2016/075360 WO2017136971A1 (en) | 2016-02-11 | 2016-03-02 | (ti, al, zr)n multi-component composite coating, graded structure ultrafine hard alloy cutting tool with the composite coating, and method for manufacturing same |
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|---|---|---|---|
| CN201610083506.2A CN105586572B (en) | 2016-02-11 | 2016-02-11 | (Ti, Al, Zr) N multicomponents composite coating, the gradient ultra-fine cemented carbide cutter with the composite coating and preparation method thereof |
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| CN105951047A (en) * | 2016-06-26 | 2016-09-21 | 苏州思创源博电子科技有限公司 | Preparation method for tungsten-nickel alloy with nitrogen-yttrium-zirconium hard coating |
| CN106270513B (en) * | 2016-09-18 | 2018-10-19 | 广东工业大学 | It melts surface layer prepared by 3D method of direct printing and is rich in cube phase cemented carbide and its application in selective laser |
| CN106319449B (en) * | 2016-10-25 | 2018-09-25 | 郑州航空工业管理学院 | Fluid erosion prevention Gradient Film and preparation method thereof for turbo-jet engine compressor blade |
| CN108149194A (en) * | 2018-01-26 | 2018-06-12 | 锐胜精机（深圳）有限公司 | A kind of AlTiN coatings with structure gradient and preparation method thereof |
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| DE112019007736T5 (en) * | 2019-10-15 | 2022-06-02 | Guangdong University Of Technology | Coated cutting tool for machining titanium alloys and super alloys and manufacturing method therefor |
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| CN113088895B (en) * | 2021-04-01 | 2022-07-19 | 九牧厨卫股份有限公司 | Decorative low-temperature hard coating and coating method and application thereof |
| CN114000118B (en) * | 2021-10-25 | 2024-03-22 | 哈尔滨工程大学 | Preparation method of titanium alloy surface hardness gradient distribution layer thickness adjustable nitride layer |
| CN114657510B (en) * | 2022-03-28 | 2022-12-20 | 中国科学院兰州化学物理研究所 | Protective coating for surface of zirconium tube and preparation method thereof |
| CN115305443B (en) * | 2022-08-16 | 2024-04-26 | 郑州大学 | Preparation method and application of zirconium-based amorphous multicomponent oxide coating |
| CN115584470B (en) * | 2022-10-24 | 2024-09-10 | 安徽工业大学 | By Zr/Zr2Method for improving corrosion and wear resistance of titanium alloy surface by using N/ZrN multilayer coating |
| CN116043162B (en) * | 2023-03-09 | 2023-06-06 | 中国地质大学（北京） | Nano composite structural coating on surface of titanium alloy cutting tool and preparation method thereof |
| CN116607108B (en) * | 2023-07-18 | 2023-12-08 | 中国科学院宁波材料技术与工程研究所 | MAX-Ag conductive composite coating and preparation method thereof |
| CN117344107B (en) * | 2023-09-14 | 2024-09-10 | 成都飞机工业（集团）有限责任公司 | Composite lubricating coating applied to severe working conditions and preparation and use methods thereof |
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