CN110004415B - High-toughness and high-hardness thick Ti/TiAlN multilayer coating and preparation method thereof - Google Patents
High-toughness and high-hardness thick Ti/TiAlN multilayer coating and preparation method thereof Download PDFInfo
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- 229910010037 TiAlN Inorganic materials 0.000 title claims abstract description 133
- 238000000576 coating method Methods 0.000 title claims abstract description 123
- 239000011248 coating agent Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 57
- 238000000151 deposition Methods 0.000 claims abstract description 46
- 230000007704 transition Effects 0.000 claims abstract description 36
- 230000008021 deposition Effects 0.000 claims abstract description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910010038 TiAl Inorganic materials 0.000 claims abstract description 13
- 238000007733 ion plating Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005137 deposition process Methods 0.000 claims description 6
- 238000010849 ion bombardment Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000011253 protective coating Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 54
- 238000007373 indentation Methods 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 244000137852 Petrea volubilis Species 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910016002 MoS2a Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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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
- C23C14/0641—Nitrides
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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
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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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
- C23C14/325—Electric arc evaporation
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Abstract
本发明涉及硬质防护涂层领域，具体为一种高韧性和高硬度的厚Ti/TiAlN多层涂层及其制备方法。采用通用的弧光离子镀设备进行沉积，选用Ti靶和TiAl靶作为阴极靶材，该Ti/TiAlN多层涂层沉积于硬质合金基体表面；所述Ti/TiAlN多层涂层为层状结构，包括TiN过渡层、多个TiAlN子层和Ti子层，沉积于基体的第一层为TiN过渡层，第二层为TiAlN子层，之后为Ti子层，TiAlN子层和Ti子层相互交替叠加沉积，最外层为TiAlN子层。本发明Ti/TiAlN多层涂层具备高厚度、良好的膜基结合强度、高硬度、高韧性等特点，并具备良好的抗氧化性能。The invention relates to the field of hard protective coatings, in particular to a thick Ti/TiAlN multilayer coating with high toughness and high hardness and a preparation method thereof. The general arc ion plating equipment is used for deposition, and Ti target and TiAl target are selected as cathode targets. The Ti/TiAlN multilayer coating is deposited on the surface of the cemented carbide substrate; the Ti/TiAlN multilayer coating is a layered structure , including a TiN transition layer, multiple TiAlN sublayers and Ti sublayers, the first layer deposited on the substrate is a TiN transition layer, the second layer is a TiAlN sublayer, followed by a Ti sublayer, and the TiAlN sublayer and the Ti sublayer are mutually Alternately stacked deposition, the outermost layer is TiAlN sublayer. The Ti/TiAlN multi-layer coating of the present invention has the characteristics of high thickness, good film-base bonding strength, high hardness, high toughness, etc., and has good oxidation resistance.
Description
The technical field is as follows:
the invention relates to the field of hard protective coatings, in particular to a thick Ti/TiAlN multilayer coating with high toughness and high hardness and a preparation method thereof.
Background art:
the hard alloy cutting tool is the dominant force of modern high-efficiency tools which are developed in China, and the demand is increased by more than 30% every year. With the development of modern manufacturing industry, cutting machine tools and cutting processing technology are greatly improved, and higher requirements are put on cutting tools. Increasingly severe service conditions require cutting tools to have high hardness, high wear resistance, high toughness, sufficient strength, good oxidation resistance, and the like. The hard coating is applied on the hard alloy cutter, so that the comprehensive properties of hardness, toughness, oxidation resistance and the like of the surface of the cutter can be improved.
Researchers found that increasing the thickness of the coating layer can significantly improve the cutting performance and the processing efficiency of the cutting tool and prolong the service life of the cutting tool (see the literature: surf. coat. Technol.188-189(2004) 636-643). However, for hard ceramic coatings, the internal stress of the coating increases with increasing coating thickness, and the high internal stress and intrinsic brittleness of the coating cause the bonding properties of the coating to the substrate to decrease with increasing thickness. The stripping tendency of the single-layer nitride coating is obviously increased when the thickness exceeds 6-7 mu m, the thickness of the hard coating is severely limited, and the industrial application of the hard coating is greatly limited. The metal transition layer is introduced into the nitride hard coating to form the metal/nitride multilayer composite coating, and the metal layer is used as a buffer layer, so that residual stress in the coating can be relaxed, the internal stress is greatly reduced, and the thick metal/nitride coating (more than 10 mu m) with excellent mechanical properties such as bonding strength, toughness, hardness and the like is obtained.
Chinese patent application (publication number is CN102676982A) provides an Al-TiN composite coating, and the prepared composite coating has excellent internal structure and good bonding strength with a matrix, improves the cracking resistance and the wear resistance of the coating, prolongs the service life, and simultaneously improves the high-temperature oxidation resistance of the coating.
The Chinese patent application (with the publication number of CN107012437A) provides a high-performance Ti/TiN/(AlTiCuSi) N coating, and the coating prepared by alternate deposition has high surface quality, good bonding force with a substrate, compact and uniform coating and good mechanical property.
Chinese patent application (publication number CN102161106A) proposes a Ti-TiN coating&Ti-MoS2a/Ti double-cutter-face coating cutter, which integrates a Ti-TiN high-hardness coating cutter and a Ti-MoS2The Ti lubricating coating cutter has the advantages of higher hardness and lower friction coefficient, so that the performance of the coating cutter is obviously improved.
The invention content is as follows:
aiming at the problems in the current application practice, the invention aims to provide a Ti/TiAlN multilayer coating with high toughness and high hardness and a preparation method thereof. In addition, the invention provides and prepares the Ti/TiAlN multilayer coating with different Ti sublayer thicknesses, and the hardness and toughness of the multilayer coating are regulated and controlled by using the thickness of the Ti sublayer on the premise of not changing the content of the constituent elements of the coating.
The technical scheme of the invention is as follows:
a high-toughness and high-hardness thick Ti/TiAlN multilayer coating is deposited by adopting general arc ion plating equipment, a Ti target and a TiAl target are selected as cathode targets, and the Ti/TiAlN multilayer coating is deposited on the surface of a hard alloy substrate; the Ti/TiAlN multilayer coating is of a layered structure and comprises a TiN transition layer, a plurality of TiAlN sublayers and a Ti sublayer, wherein the first layer deposited on the substrate is the TiN transition layer, the second layer is the TiAlN sublayer and then the Ti sublayer, the TiAlN sublayers and the Ti sublayer are alternately stacked and deposited with each other, and the outermost layer is the TiAlN sublayer.
According to the thick Ti/TiAlN multilayer coating with high toughness and high hardness, the thickness of a TiN transition layer is 0.1 mu m, the thickness of each TiAlN sublayer is 1.5-1.7 mu m, the thickness of each Ti sublayer is 0.1-0.8 mu m, and the total number of layers of the Ti/TiAlN multilayer coating is an even number in 14-24 layers.
The high-toughness and high-hardness thick Ti/TiAlN multilayer coating is preferably adjustable in the total thickness of 14.4-17.1 mu m.
The preparation method of the thick Ti/TiAlN multilayer coating with high toughness and high hardness comprises the following specific steps:
(1) pre-treating a substrate: putting the hard alloy matrix into a mixed solvent of absolute ethyl alcohol and acetone for ultrasonic cleaning for 5-15 min to remove surface oil stains and oxidation film stains;
(2) cleaning a matrix by ion bombardment: loading the pretreated substrate on a sample rack, placing the sample rack in an ion plating vacuum chamber, closing a chamber door, and vacuumizing to a vacuum degree of 8.0 × 10-3Introducing argon after the pressure is lower than Pa, maintaining the vacuum degree at 0.3-0.5 Pa, applying negative bias voltage value of 800-1200V to the substrate, and performing ion bombardment cleaning on the substrate for 5-15 min at a duty ratio of 50-70%;
(3) and (3) depositing a TiN transition layer: cutting off argon, introducing nitrogen, maintaining the vacuum degree and the gas pressure at 1.0-2.0 Pa, controlling the matrix pulse negative bias value at 500-700V, opening Ti target current, and carrying out deposition for 1-10 min;
(4) alternately depositing TiAlN sublayers and Ti sublayers: firstly, depositing a TiAlN sublayer, closing the current of a Ti target, maintaining the nitrogen gas pressure at 1.5-2.0 Pa, keeping the negative bias value of a substrate at 500-600V, and depositing for 18-20 min; then depositing a Ti sublayer, closing TiAl target current, cutting off nitrogen, introducing argon, keeping the working pressure at 0.3-0.6 Pa, changing the negative bias value of the substrate to 100-200V, and controlling the deposition time to be 2-9 min; alternately depositing TiAlN sublayers and Ti sublayers in sequence;
(5) deposition of TiAlN on the outermost layer: and (4) after the final Ti sublayer is deposited, depositing a TiAlN outermost layer again, wherein the process parameters are the same as those in the step (4).
According to the preparation method of the thick Ti/TiAlN multilayer coating with high toughness and high hardness, in the step (1), before pretreatment of a substrate, the substrate is subjected to SiC sand paper grinding and polishing treatment.
According to the preparation method of the thick Ti/TiAlN multilayer coating with high toughness and high hardness, in the steps (2) to (5), the volume purity of argon and nitrogen is 99.99%.
In the preparation method of the thick Ti/TiAlN multilayer coating with high toughness and high hardness, in the steps (3) to (5), the purity of a Ti target is 99.99 wt%, the atomic ratio of the TiAl target is Ti to Al 1:1, the sizes of the Ti target and the TiAl target are 80-120 mm in diameter and 50-70 mm in height, and the distance between target bases is 180-220 mm; in the TiN transition layer, the atomic ratio Ti to N is 1: 1; in the TiAlN sublayer, the atomic ratio of Ti to Al to N is 1 to 2.
According to the preparation method of the thick Ti/TiAlN multilayer coating with high toughness and high hardness, in the deposition process of the steps (3) to (5), the target current is controlled to be 60-80A, and the duty ratio is stabilized to be 15-25%.
According to the preparation method of the thick Ti/TiAlN multilayer coating with high toughness and high hardness, in the deposition process of the steps (3) to (5), the sample holder rotates automatically, and the rotating speed is controlled to be 4-6 rpm.
According to the preparation method of the thick Ti/TiAlN multilayer coating with high toughness and high hardness, the substrate is not heated in the whole process.
The design idea of the invention is as follows:
the invention prepares the thick Ti/TiAlN multilayer coating with different sublayer proportions, the bonding condition of the coating and a substrate is good, the thickness proportion of the sublayers determines the hardness and toughness of the coating, the multilayer coating with different hardness and toughness values can be obtained by regulating and controlling the thickness proportion of the sublayers, and the coating system is suitable for application environments with different working conditions.
The invention has the advantages and beneficial effects that:
1. according to the invention, by controlling the thickness of the metal layer, the internal stress of the coating can be effectively reduced, cracking and peeling are avoided, the multilayer coating with the thickness of more than 10 mu m and excellent bonding strength is obtained, the protection time of the coating can be prolonged, and the service life of the cutter is prolonged.
2. The Ti/TiAlN multilayer coating with the advantages of inhibiting the generation and the expansion of cracks, high hardness and high toughness can be quickly obtained by the ion plating deposition technology, and the technical indexes are as follows: the hardness HV is 1758-2915, and the crack length generated by the indentation of the cross section of the coating is observed to evaluate that the longer the crack is, the poorer the toughness is, and the capability of the Ti/TiAlN multilayer coating system for resisting crack propagation is stronger. As the TiAlN layer has good oxidation resistance, the Ti/TiAlN multilayer coating system also has good oxidation resistance.
3. The total thickness of the sub-layer and the coating is easy to control, the preparation method is simple, the cost is low, and the design of the thick hard coating can be easily realized.
Description of the drawings:
FIG. 1 is a scanning electron micrograph of the surface (a) and the cross section (b) of the Ti/TiAlN multilayer coating obtained in example 1;
FIG. 2 is a photograph of the cross-sectional indentation crack morphology of the Ti/TiAlN multilayer coating obtained in example 1;
FIG. 3 is a photograph of the cross-sectional profile and the cross-sectional indentation crack profile of the Ti/TiAlN multilayer coating obtained in example 4;
FIG. 4 is a photograph of the TiAlN single-layer coating cross-sectional morphology (a) and the cross-sectional indentation crack morphology (b) obtained by the comparative example.
The specific implementation mode is as follows:
in the specific implementation process, the preparation method of the thick Ti/TiAlN multilayer coating with high toughness and high hardness comprises the steps of pretreating a substrate, cleaning the substrate by ion bombardment, depositing a TiN transition layer, alternately depositing a TiAlN sublayer and a Ti sublayer, and depositing TiAlN on the outermost layer. The Ti/TiAlN multilayer coating is deposited by adopting general arc ion plating equipment, a Ti target and a TiAl target are selected as cathode targets, and the Ti/TiAlN multilayer coating is deposited on the surface of a hard alloy substrate; the Ti/TiAlN multilayer coating is of a layered structure and comprises a TiN transition layer, a plurality of TiAlN sublayers and a Ti sublayer, wherein the first layer deposited on the substrate is the TiN transition layer, the second layer is the TiAlN sublayer and then the Ti sublayer, the TiAlN sublayers and the Ti sublayer are alternately stacked and deposited with each other, and the outermost layer is the TiAlN sublayer.
The performance test of the thick Ti/TiAlN multilayer coating with high toughness and high hardness comprises the following steps:
1. and (3) hardness testing: a Vickers microhardness tester (model: Buehler Micromet 5114) is adopted, the external load is 25gf, and the pressure maintaining time is 10 s;
grinding and polishing the cross section of the coating, cleaning the cross section of the coating in absolute ethyl alcohol, putting a sample on a glass sheet (with the selected test surface facing upwards), and putting the sample on an objective table; firstly, selecting a proper section hardness testing position by adopting a 500-time objective lens, then loading 25gf, keeping the pressure for 10s, calibrating the length of two diagonal lines of an indentation to obtain a corresponding hardness value, testing each sample for 8 times, and taking an average value.
2. And (3) toughness evaluation: analyzing the toughness of the coating by adopting an impressed load indentation method of the coating section, applying a load by using a Vickers microhardness tester for the hardness test, wherein the impressed load is 100gf, and the pressure maintaining time is 10 s; the morphology of the cracks around the indentations was then observed using a scanning electron microscope (SEM, model: Philips FEI-aspect F) to evaluate the toughness of the coatings.
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
In this example, after a hard alloy (WC-6 wt.% Co, mass fraction) was ground and polished with SiC sand paper, acetone and water were addedEthanol is added according to the volume ratio of 1:1, ultrasonic cleaning for 15min to remove dirt such as oil stain and oxide film on the surface, loading the pretreated substrate on a sample rack, putting the sample rack into an ion plating vacuum chamber, closing the chamber door, and vacuumizing to a vacuum degree of 5.0 × 10-3And introducing argon after Pa, maintaining the vacuum degree at 0.4Pa, applying a negative bias voltage value of 1000V to the substrate, and performing ion bombardment cleaning on the substrate for 10min at a duty ratio of 60%.
And after cleaning, cutting off argon, introducing nitrogen, maintaining the vacuum degree and the gas pressure at 1.5Pa, controlling the pulse negative bias value of the substrate at 600V, opening the Ti target current, and depositing for 3min to form the TiN transition layer. Alternating deposition of TiAlN sublayers and Ti sublayers is then performed: firstly, depositing a TiAlN sublayer, closing the current of a Ti target, maintaining the gas pressure of nitrogen at 1.5Pa, setting the negative bias value of a substrate at 550V, and setting the deposition time at 18.5 min; then depositing a Ti sublayer, closing TiAl target current, cutting off nitrogen, introducing argon, keeping the working pressure at 0.3Pa, changing the negative bias value of the substrate to 100V, controlling the deposition time to be 2min, and sequentially and alternately depositing the TiAlN sublayer and the Ti sublayer; and after the final Ti sublayer is deposited, depositing a TiAlN outermost layer, wherein the process parameters are as described above. In the whole deposition process, the sample holder rotates automatically, and the rotating speed is controlled at 5 rpm; the target current is 70A, the duty ratio is 20%, and the substrate is not heated. The purity of the Ti target is 99.99 wt%, the atomic ratio of the TiAl target is 1:1, the sizes of the Ti target and the TiAl target are both 100mm in diameter and 60mm in height, and the distance between the target bases is 200 mm.
The thickness of the TiN transition layer is 0.1 mu m, the thickness of each TiAlN sublayer is 1.7 mu m, the thickness of each Ti sublayer is 0.1 mu m, and the total layer number is 16. In the TiN transition layer, the atomic ratio Ti: N is 1:1 (namely Ti)1N1) (ii) a In the TiAlN sublayer, the atomic ratio of Ti to Al to N is 1:1:2 (i.e., Ti0.5Al0.5N1)。
As shown in fig. 1(a) - (b), surface topography observation of the multilayer coating shows that molten drops with different sizes exist on the surface of the coating, cross section observation shows that the TiAlN sublayer and the Ti sublayer are uniformly distributed and densely organized, the Ti/TiAlN multilayer coating is well combined with a substrate through a transition layer, white is the Ti sublayer, and dark gray is the TiAlN sublayer. The hardness value of the Ti/TiAlN multilayer coating obtained in the embodiment is detected to be HV 2915, the toughness detection is shown in figure 2, and discontinuous cracks with certain lengths appear at the edges of the indentations, which indicates that the cracks are prevented from expanding and the toughness of the coating is improved.
Example 2
The difference from the embodiment 1 is that:
when the TiAlN sublayer is deposited, the nitrogen gas pressure is 1.6Pa, the negative bias value of the substrate is 520V, and the deposition time is 18 min; when Ti sublayers are deposited, argon working pressure is 0.35Pa, the negative bias value of a substrate is 120V, and the deposition time is controlled to be 2.5 min; the thickness of the TiN transition layer is 0.1 mu m, the thickness of each TiAlN sublayer is 1.7 mu m, the thickness of each Ti sublayer is 0.2 mu m, and the total layer number is 16. In the TiN transition layer, the atomic ratio Ti to N is 1: 1; in the TiAlN sublayer, the atomic ratio of Ti to Al to N is 1 to 2.
The TiAlN sublayer and the Ti sublayer of the Ti/TiAlN multilayer coating obtained by the embodiment are uniformly distributed and have compact tissues, and the Ti/TiAlN multilayer coating is well combined with a substrate through a transition layer. The hardness value of the Ti/TiAlN multilayer coating obtained in the embodiment is detected to be HV 2852, and toughness detection finds that the length of discontinuous cracks appearing at the edge of an indentation is shortened, the expansion of the cracks is prevented, and the toughness of the coating is improved.
Example 3
The difference from the embodiment 1 is that:
when the TiAlN sublayer is deposited, the nitrogen gas pressure is 1.7Pa, the negative bias value of the substrate is 500V, and the deposition time is 18 min; when Ti sublayers are deposited, argon working gas pressure is 0.4Pa, the negative bias value of the substrate is 150V, and the deposition time is controlled to be 3.5 min; the thickness of the TiN transition layer is 0.1 mu m, the thickness of each TiAlN sublayer is 1.7 mu m, the thickness of each Ti sublayer is 0.3 mu m, and the total layer number is 16. In the TiN transition layer, the atomic ratio Ti to N is 1: 1; in the TiAlN sublayer, the atomic ratio of Ti to Al to N is 1 to 2.
The TiAlN sublayer and the Ti sublayer of the Ti/TiAlN multilayer coating obtained by the embodiment are uniformly distributed and have compact tissues, and the Ti/TiAlN multilayer coating is well combined with a substrate through a transition layer. The hardness value of the Ti/TiAlN multilayer coating obtained in the embodiment is detected to be HV 2611, and toughness detection finds that the length of discontinuous cracks appearing at the edge of an indentation is further shortened, the expansion of the cracks is prevented, and the toughness of the coating is further improved.
Example 4
The difference from the embodiment 1 is that:
when the TiAlN sublayer is deposited, the nitrogen gas pressure is 1.8Pa, the negative bias value of the substrate is 550V, and the deposition time is 18.5 min; when Ti sublayers are deposited, argon working pressure is 0.45Pa, the negative bias value of the substrate is 180V, and the deposition time is controlled to be 4.5 min; the thickness of the TiN transition layer is 0.1 mu m, the thickness of each TiAlN sublayer is 1.7 mu m, the thickness of each Ti sublayer is 0.4 mu m, and the total layer number is 16. In the TiN transition layer, the atomic ratio Ti to N is 1: 1; in the TiAlN sublayer, the atomic ratio of Ti to Al to N is 1 to 2.
The TiAlN sublayer and the Ti sublayer of the Ti/TiAlN multilayer coating obtained by the embodiment are uniformly distributed and have compact tissues, and the Ti/TiAlN multilayer coating is well combined with a substrate through the transition layer. The hardness value of the Ti/TiAlN multilayer coating obtained in the embodiment is detected to be HV 2611, toughness detection is shown in figure 3, no obvious crack is found at the edge of an indentation, and the toughness of the coating is further improved.
Example 5
The difference from the embodiment 1 is that:
when the TiAlN sublayer is deposited, the nitrogen gas pressure is 1.9Pa, the negative bias value of the substrate is 550V, and the deposition time is 19 min; when Ti sublayers are deposited, argon working gas pressure is 0.5Pa, the negative bias value of the substrate is 190V, and the deposition time is controlled to be 7 min; the thickness of the TiN transition layer is 0.1 mu m, the thickness of each TiAlN sublayer is 1.6 mu m, the thickness of each Ti sublayer is 0.6 mu m, and the total layer number is 16. In the TiN transition layer, the atomic ratio Ti to N is 1: 1; in the TiAlN sublayer, the atomic ratio of Ti to Al to N is 1 to 2.
The TiAlN sublayer and the Ti sublayer of the Ti/TiAlN multilayer coating obtained by the embodiment are uniformly distributed and have compact tissues, and the Ti/TiAlN multilayer coating is well combined with a substrate through the transition layer. The hardness value of the Ti/TiAlN multilayer coating obtained in the embodiment is detected to be HV 2193, and toughness detection shows that no crack is found at the edge of an indentation, so that the toughness of the coating is further improved.
Example 6
The difference from the embodiment 1 is that:
when the TiAlN sublayer is deposited, the nitrogen gas pressure is 2.0Pa, the negative bias value of the substrate is 600V, and the deposition time is 20 min; when Ti sublayers are deposited, argon working gas pressure is 0.6Pa, the negative bias value of the substrate is 200V, and the deposition time is controlled to be 9 min; the thickness of the TiN transition layer is 0.1 mu m, the thickness of each TiAlN sublayer is 1.5 mu m, the thickness of each Ti sublayer is 0.8 mu m, and the total number of layers is 14. In the TiN transition layer, the atomic ratio Ti to N is 1: 1; in the TiAlN sublayer, the atomic ratio of Ti to Al to N is 1 to 2.
The TiAlN sublayer and the Ti sublayer of the Ti/TiAlN multilayer coating obtained by the embodiment are uniformly distributed and have compact tissues, and the Ti/TiAlN multilayer coating is well combined with a substrate through the transition layer. The hardness value of the Ti/TiAlN multilayer coating obtained in the embodiment is detected to be HV 1758, toughness detection shows that no crack is found at the edge of an indentation, and the toughness of the coating is further improved.
Comparative example
In this comparative example, a thick TiAlN monolayer coating was prepared and the TiN transition layer deposition process was the same as in the previous example. When the TiAlN single-layer coating is deposited, the nitrogen gas pressure is 2.0Pa, the negative bias value of the substrate is 600V, the deposition time is 135min, and other deposition parameters are the same as the above.
As shown in FIG. 4a, the TiAlN single-layer coating obtained by the comparative example has the cross-sectional morphology, fine cracks appear in the coating, and the total thickness is 16.9 μm. And (3) carrying out hardness and toughness tests on the single-layer coating, wherein the detection parameters are the same as those of the embodiment, the TiAlN hardness value is HV 3035, the toughness test is shown in figure 4b, long cracks of 15 mu m appear at the tip of a section indentation, and the long cracks are greatly longer than the Ti/TiAlN multi-layer coating, which shows that the toughness of the Ti/TiAlN multi-layer coating is obviously higher than that of the TiAlN single-layer coating.
The results of the examples and the comparative examples show that the Ti/TiAlN multilayer coating has the characteristics of high thickness, good film-substrate bonding strength, high hardness, high toughness and the like, and has good oxidation resistance. The thick Ti/TiAlN multilayer coating prepared by the process can be applied to a hard alloy cutting tool, and effectively plays the roles of improving the hardness and toughness of the tool and prolonging the service life.
Claims (7)
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| CN114807846B (en) * | 2022-04-02 | 2023-11-24 | 中国科学院宁波材料技术与工程研究所 | A gradient multi-layer protective coating resistant to solid particle erosion and its preparation method |
| CN116334536B (en) * | 2023-03-29 | 2024-07-26 | 东北大学 | A high-toughness transition metal nitride TiAl(Ni)NX hard coating and preparation method thereof |
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