CN106835037A - A kind of high rigidity, multicomponent nitride coatings of high elastic modulus and preparation method thereof - Google Patents

Abstract

The present invention is a multi-component nitride coating with high hardness and high elastic modulus. Its chemical formula is AlCrTiZrNbN, and the atomic ratios of Al, Cr, Ti, Zr, Nb and N are respectively 8-12%: 8-12 %: 8~12%: 8~12%: 8~12%: 48~52%, the thickness of the coating is 2~5μm. The present invention also provides a method for preparing the above-mentioned nitride coating. Firstly, the surface of the substrate is subjected to mirror polishing, then ultrasonically cleaned with acetone and alcohol, and after vacuum ion cleaning, the AlCrTiZrNbN layer is deposited by radio frequency reactive sputtering, wherein AlCrTiZrNbN is mostly The component nitride coating is prepared from the AlCrTiZrNb alloy target with equiatomic molar ratio under (Ar+N ₂ ) atmosphere. The coating of the invention has high hardness and high modulus of elasticity, and can be used as a novel protective coating in various service occasions such as cutting tools and molds.

Description

A multi-component nitride coating with high hardness and high elastic modulus and its preparation method

technical field

The invention belongs to the field of material surface engineering and relates to a coating, in particular to a multi-component nitride coating with high hardness and high elastic modulus and a preparation method thereof.

Background technique

With the development of advanced manufacturing industry, the cutting of materials is developing in two directions of high speed and dry cutting. Therefore, higher and higher requirements are put forward for the surface properties of tool materials, and the surface of tool materials is required to have higher hardness and wear resistance. , corrosion resistance and low coefficient of friction. Coating technology is an important way to improve tool performance and life. With the continuous development of advanced cutting technologies such as high-speed cutting and dry cutting, higher requirements are put forward for the performance of tool coatings. Not only must they have mechanical properties such as high hardness, high modulus of elasticity, wear resistance and toughness, It also has high temperature oxidation resistance, corrosion resistance and a low coefficient of friction. Traditional tool coatings, such as TiN, CrN and even TiAlN coatings, have gradually failed to meet the demanding performance requirements.

In 2004, Taiwanese scholar Professor Ye Junwei broke through the traditional concept of alloy design and innovatively proposed a multi-component high-entropy alloy (HEA). High-entropy alloys refer to alloys that contain 5 to 13 components and can form high-entropy solid solutions. Due to the high entropy effect, the solidified high entropy alloy not only does not form a large number of intermetallic compounds, but presents a simple face-centered cubic (FCC) or body-centered cubic (BCC) crystal phase. High-entropy alloys will precipitate nano-phase structures, even amorphous structures, in the as-cast state and in the fully tempered state, showing a high-temperature precipitation strengthening phenomenon. A large number of studies have shown that high-entropy alloys have properties that cannot be compared with traditional alloys.

High-entropy alloy coatings have excellent properties such as high strength, high hardness, high resistance to temper softening, high wear resistance, high oxidation resistance and corrosion resistance, and have shown great potential in the application of tools, tools and molds. The choice of material system provides a good opportunity.

According to literature review, hard composite coatings have been successfully prepared by various methods, and high hardness has also been obtained in many systems. The research on this type of coatings has also achieved many beneficial results. Through the query, the following Chinese patents related to hard composite coatings were retrieved:

The patent application No. 201010176320 relates to a nanocomposite titanium chromium silicon nitride tool coating, which belongs to the field of ceramic coatings. The invention discloses a nanocomposite titanium-chromium-silicon-nitride tool coating and a preparation method thereof. The tool substrate is WC/Co hard alloy, and the coating contains a transition layer of titanium-chromium-silicon nitride coating, which contains titanium, Chromium, silicon, and nitrogen elements, the grain size is 5-15nm, the coating thickness is 1-4μm, the coating microhardness is 26GPa, and the high-temperature stability reaches above 1068°C. The nanocomposite titanium-chromium-silicon nitride-coated tool of the present invention The coated tool prepared by combining ion plating and sputtering plating is suitable for cutting high-hardness steel materials under high-speed conditions.

The patent with application number 200510095785 relates to a hard composite nano-ceramic film coating applied to the inner wall of an internal combustion engine cylinder, which belongs to the field of ceramic coatings. The coating of the hard composite nano-ceramic thin film applied on the inner wall of the cylinder of an internal combustion engine can be realized by a general processing technology for depositing a solid film. The processing technology for depositing a solid film includes vacuum evaporation, magnetron sputtering , ion beam sputtering, ion plating, liquid phase epitaxy, chemical beam epitaxy, molecular beam epitaxy, pulsed laser deposition, electrochemical deposition, chemical vapor deposition and physical vapor deposition; The basic method of the coating of nano-ceramic film is to apply the technology of depositing solid film, and deposit one or more coatings of hard composite nano-ceramic film on the inner wall of the internal combustion engine cylinder; the coating is used to make the internal combustion engine cylinder The surface modification of the inner wall of the material occurs; the overall Vickers hardness HV of the coating is not less than 3350; the overall thickness of the coating is not more than 60 μm; the inner wall of the internal combustion engine cylinder includes the inner wall of the gasoline engine internal combustion engine cylinder and the inner wall of the diesel engine internal combustion engine cylinder.

The invention with application number 201010192876 relates to a high-hardness nanocomposite coating on cemented carbide. Specifically described is a method of producing a bonded surface coating on a cemented carbide cutting tool or other workpiece substrate by forming a polycrystalline diamond coating or a composite coating comprising refractory metal carbide and polycrystalline diamond. The coating is deposited by a sequential chemical vapor deposition process, first using a specific gas mixture of hydrogen and refractory metal halide to deposit a base layer of refractory metal carbide. This step is followed by a second step in which polycrystalline diamond is deposited from a gas mixture comprising hydrocarbons and hydrogen. It is also envisaged to co-deposit refractory metal carbide and diamond in a second step to produce a strengthened diamond coating.

The patent with the application number 201010274793 relates to a method for preparing a nanostructured yttrium-zirconium nitride hard coating on the surface of a cemented carbide substrate. Carbide. Provided is a method for preparing a nanostructure yttrium-zirconium nitride hard coating on the surface of a hard alloy substrate by using a magnetron sputtering method. On the surface of the cemented carbide substrate that has been treated by mechanical polishing, ultrasonic cleaning and ion source cleaning, direct current and radio frequency reactive co-sputtering are used to deposit, the total pressure is controlled at 0.3-0.5Pa, the nitrogen flow rate is 15-20%, and the direct current power of the Zr target 250W, the RF power of the Y target is 50-200W, the substrate temperature is 300°C, and the deposition time is 90min. After the sputtering deposition is completed, a hard coating of yttrium zirconium nitride is obtained, which is a nanocomposite structure and the coating has high hardness. .

The application number is 200810197643, and the invention discloses a preparation method of a Ti-Si-N nanocrystalline-amorphous composite superhard coating. This method utilizes a high-density arc discharge controlled by a magnetic field to evaporate Ti on the Ti arc target, and nitrogen gas is introduced to react with the evaporated Ti to form TiN, while silane is introduced to ionize and decompose silane (SiN↓[4]) into Si ions and H ions, Si ions and nitrogen react to form Si ₃ N ₄ . Under the bias voltage, TiN crystal and Si ₃ N ₄ compete to grow on the workpiece substrate to form a film at the same time, forming a Ti-Si-N nanocrystalline-amorphous composite coating. The Ti-Si-N nanocrystalline composite coating prepared by the present invention has the characteristics of high coating hardness, strong adhesion, fast coating growth rate, high production efficiency, low production cost, and simple structure of coating equipment. Preparation of Ti-Si-N nanocrystalline-amorphous composite superhard coatings with different thicknesses on various workpieces such as cemented carbide, stainless steel, and carbon steel.

However, the above-mentioned existing coatings still have the disadvantages that the hardness and friction coefficient cannot meet the performance requirements of high-speed cutting and dry cutting, and the problems that the coating performance, deposition conditions and deposition efficiency cannot be balanced.

Contents of the invention

Aiming at the above-mentioned technical problems in the prior art, the present invention provides a multi-component nitride coating with high hardness and high elastic modulus and a preparation method thereof, the multi-component nitride coating with high hardness and high elastic modulus The component nitride coating and its preparation method should solve the problem that the hardness and friction coefficient of the coating in the prior art cannot meet the performance requirements of high-speed cutting and dry cutting, and the coating performance, deposition conditions and deposition efficiency cannot be balanced. technical problem.

The invention provides a multi-component nitride coating with high hardness and high elastic modulus. Its chemical formula is AlCrTiZrNbN, and the atomic ratios of Al, Cr, Ti, Zr, Nb and N elements are 8-12%: 8 ~12%: 8~12%: 8~12%: 8~12%: 48~52%, the thickness of the coating is 2~5 μm.

Further, Al, Cr, Ti, Zr, Nb and N elements are calculated as 10%: 10%: 10%: 10%: 10%: 50% by atomic ratio.

Further, the coating has a face-centered cubic crystal structure.

The present invention also provides a method for preparing the above-mentioned multi-component nitride coating with high hardness and high elastic modulus, comprising the following steps:

1) A step of cleaning the substrate, cleaning the polished and mirror-polished substrate with 15-30kHz ultrasonic waves in alcohol and acetone for 10-15 minutes; then performing ion cleaning, during which the substrate is packed Into the sample chamber, evacuate to 3*10 ^-3 Pa ~8*10 ^-3 Pa, then turn on Ar gas, maintain the vacuum at 2-4Pa, use intermediate frequency radio frequency to bombard the substrate with ions for 20~40min, the power is 80-100W;

1) A step of using a multi-target magnetron sputtering apparatus to perform magnetron sputtering reaction deposition on a substrate with an AlCrTiZrNb alloy target with a molar ratio of 1:1:1:1:1; the cleaned substrate is placed in Multi-target magnetron sputtering instrument and stay before AlCrTiZrNb alloy target material, the condition of above-mentioned magnetron sputtering reaction deposition is: argon gas flow: 10-50sccm; N flow: _5-30sccm ; RF power supply: 150- 300W, rotation speed: 10 r/min, time: 7200s; target base distance: 3-7cm; total air pressure range: 0.2-0.8Pa; substrate temperature range: 60-200°C, to obtain multiple sets of high hardness and high elastic modulus Nitride coating.

Further, the substrate is a metal, hard alloy or ceramic substrate.

The invention adopts the way of radio frequency reactive sputtering, and the AlCrTiZrNbN multi-element nitride coating is deposited on the metal, hard alloy or ceramic substrate to form. The thickness of the AlCrTiZrNbN multi-component nitride coating is 2-5 μm. The AlCrTiZrNbN multi-component nitride coating is prepared from an AlCrTiZrNb alloy target with an equiatomic molar ratio under (Ar+N ₂ ) atmosphere. The AlCrTiZrNbN multi-component nitride coating has a face-centered cubic crystal structure. The AlCrTiZrNb alloy target is used in (Ar+N ₂ ) atmosphere to obtain a nanocomposite coating with a composition modulation structure, and the composition of the coating can be controlled by adjusting the ratio of N ₂ and Ar.

Compared with the prior art, the technical progress of the present invention is remarkable. The invention provides an AlCrTiZrNbN multi-component nitride coating with high hardness and high elastic modulus, which overcomes the high hardness and unsatisfactory elastic modulus of the coating in the prior art, as well as the low production efficiency of the coating and the easy damage to the environment. Technical problems causing pollution. The coating of the invention can be used in high hardness, high wear resistance and other occasions, and can be widely used in protective coatings of cutting tools and molds. The preparation process of the coating also has the characteristics of simple process, fast deposition speed, low cost, no pollution to the environment and the like.

detailed description

The present invention will be described in further detail below through specific examples, but the present invention is not limited.

Preparation, characterization and measuring instruments used in the present invention:

JGP-450 Magnetron Sputtering System, Shenyang Scientific Instrument Development Center Co., Ltd., Chinese Academy of Sciences

D8 Advance X-ray diffractometer, Bruker, Germany

NANO Indenter G200 nanoindenter, Agilent Technologies, USA

Tecnai G ² 20 high-resolution transmission electron microscope, American FEI company

Quanta FEG450 scanning electron microscope (with Oxford energy spectrometer), American FEI company

Example 1

A method for preparing a multi-component nitride coating with high hardness and high elastic modulus, comprising the steps of:

1) A step of cleaning the substrate, cleaning the polished and mirror-polished substrate with 15-30kHz ultrasonic waves in alcohol and acetone for 10-15 minutes; then performing ion cleaning, during which the substrate is packed Into the sample chamber, after vacuuming to 5*10 ^-3 Pa, turn on Ar gas, maintain the vacuum at 2-4Pa, use 13.56Hz (intermediate frequency) radio frequency to bombard the substrate with ions for 20-40min, and the power is 80-100W ; The matrix is Cu.

2) Using a multi-target magnetron sputtering apparatus, the step of magnetron sputtering reaction deposition is carried out on the substrate by an AlCrTiZrNb alloy target with an equal atomic molar ratio; the cleaned substrate is placed in a multi-target magnetron sputtering apparatus and left Before the AlCrTiZrNb alloy target, the above magnetron sputtering reactive deposition conditions are: Ar gas flow 10sccm, N ₂ flow 20sccm, RF reactive sputtering power 300W, time 7200s, substrate temperature 120°C, deposition pressure 0.4Pa , the thickness of the AlCrTiZrNbN multi-component nitride coating is about 2.8 μm.

Measured by the energy dispersive spectrometer (EDS) attached to the scanning electron microscope, the Al, Cr, Ti, Zr, Nb and N elements in the multi-component nitride coating are calculated as 10.15% by atomic ratio: 8.97%: 11.04%: 9.76%: 10.25%: 49.83%. The obtained coating has a hardness of 28.7GPa and an elastic modulus of 319GPa.

Example 2

A method for preparing a multi-component nitride coating with high hardness and high elastic modulus, comprising the steps of:

1) A step of cleaning the substrate, cleaning the polished and mirror-polished substrate with 15-30kHz ultrasonic waves in alcohol and acetone for 10-15 minutes; then performing ion cleaning, during which the substrate is packed Introduce the sample chamber, evacuate to 5*10 ^-3 Pa, turn on Ar gas, maintain the vacuum at 2-4Pa, use 13.56Hz radio frequency to bombard the substrate with ions for 20-40min, and the power is 80-100W; The matrix is Al.

2) Using a multi-target magnetron sputtering apparatus, the step of magnetron sputtering reaction deposition is carried out on the substrate by an AlCrTiZrNb alloy target with an equal atomic molar ratio; the cleaned substrate is placed in a multi-target magnetron sputtering apparatus and left Before the AlCrTiZrNb alloy target, the above magnetron sputtering reactive deposition conditions are: Ar gas flow 15 sccm, N ₂ flow 20 sccm, radio frequency reactive sputtering power 300W, time 7200s, substrate temperature 80 ℃, deposition pressure 0.8Pa , the thickness of AlCrTiZrNbN multi-component nitride coating is about 3.1 μm.

Measured by the energy dispersive spectrometer (EDS) attached to the scanning electron microscope, the Al, Cr, Ti, Zr, Nb and N elements in the multi-component nitride coating are calculated as 9.40% by atomic ratio: 9.52%: 9.72%: 11.04%: 8.98%: 51.34%. The obtained coating has a hardness of 30.6GPa and an elastic modulus of 336GPa.

Example 3

A method for preparing a multi-component nitride coating with high hardness and high elastic modulus, comprising the steps of:

1) A step of cleaning the substrate, cleaning the polished and mirror-polished substrate with 15-30kHz ultrasonic waves in alcohol and acetone for 10-15 minutes; then performing ion cleaning, during which the substrate is packed Introduce the sample chamber, evacuate to 5*10 ^-3 Pa, turn on Ar gas, maintain the vacuum at 2-4Pa, use 13.56Hz radio frequency to bombard the substrate with ions for 20-40min, and the power is 80-100W; The substrate is a ceramic substrate.

2) Using a multi-target magnetron sputtering apparatus, the step of magnetron sputtering reaction deposition is carried out on the substrate by an AlCrTiZrNb alloy target with an equiatomic molar ratio; the cleaned substrate is placed in a multi-target magnetron sputtering apparatus and stops Before the AlCrTiZrNb alloy target, the above magnetron sputtering reactive deposition conditions are: Ar gas flow 15 sccm, N ₂ flow 15 sccm, radio frequency reactive sputtering power 300W, time 7200s, substrate temperature 160 ℃, deposition pressure 0.4Pa , the thickness of the AlCrTiZrNbN multi-component nitride coating is about 3.8 μm.

Measured by the energy dispersive spectrometer (EDS) attached to the scanning electron microscope, the Al, Cr, Ti, Zr, Nb and N elements in the multi-component nitride coating are calculated as 9.76% by atomic ratio: 10.52%: 9.05%: 10.21%: 11.79%: 48.67%. The obtained coating has a hardness of 32.3GPa and an elastic modulus of 358GPa.

Example 4

A method for preparing a multi-component nitride coating with high hardness and high elastic modulus, comprising the steps of:

1) A step of cleaning the substrate, cleaning the polished and mirror-polished substrate with 15-30kHz ultrasonic waves in alcohol and acetone for 10-15 minutes; then performing ion cleaning, during which the substrate is packed Introduce the sample chamber, evacuate to 5*10 ^-3 Pa, turn on Ar gas, maintain the vacuum at 2-4Pa, use 13.56Hz radio frequency to bombard the substrate with ions for 20-40min, and the power is 80-100W; The substrate is cemented carbide.

2) Using a multi-target magnetron sputtering apparatus, the step of magnetron sputtering reaction deposition is carried out on the substrate by an AlCrTiZrNb alloy target with an equal atomic molar ratio; the cleaned substrate is placed in a multi-target magnetron sputtering apparatus and left Before the AlCrTiZrNb alloy target, the above magnetron sputtering reactive deposition conditions are: Ar gas flow 15 sccm, N ₂ flow 12 sccm, radio frequency reactive sputtering power 300W, time 7200s, substrate temperature 200 ℃, deposition pressure 0.2Pa , the thickness of the AlCrTiZrNbN multi-component nitride coating is about 4.4 μm.

Measured by the energy dispersive spectrometer (EDS) attached to the scanning electron microscope, the Al, Cr, Ti, Zr, Nb and N elements in the multi-component nitride coating are calculated as 10.55% by atomic ratio: 10.20%: 8.96%: 10.34%: 9.08%: 50.87%. The obtained coating has a hardness of 35.9GPa and an elastic modulus of 384GPa.

Example 5

A method for preparing a multi-component nitride coating with high hardness and high elastic modulus, comprising the steps of:

1) A step of cleaning the substrate, cleaning the polished and mirror-polished substrate with 15-30kHz ultrasonic waves in alcohol and acetone for 10-15 minutes; then performing ion cleaning, during which the substrate is packed Introduce the sample chamber, evacuate to 5*10 ^-3 Pa, turn on Ar gas, maintain the vacuum at 2-4Pa, use 13.56Hz radio frequency to bombard the substrate with ions for 20-40min, and the power is 80-100W; The substrate is a ceramic substrate.

2) Using a multi-target magnetron sputtering apparatus, the step of magnetron sputtering reaction deposition is carried out on the substrate by an AlCrTiZrNb alloy target with an equal atomic molar ratio; the cleaned substrate is placed in a multi-target magnetron sputtering apparatus and left Before the AlCrTiZrNb alloy target, the above magnetron sputtering reactive deposition conditions are: Ar gas flow rate 18sccm, _N2 flow rate 12sccm, RF reactive sputtering power 300W, time 7200s, substrate temperature 180°C, deposition pressure 0.6Pa , the thickness of the AlCrTiZrNbN multi-component nitride coating is about 3.2 μm.

Measured by the energy dispersive spectrometer (EDS) attached to the scanning electron microscope, the Al, Cr, Ti, Zr, Nb and N elements in the multi-component nitride coating are calculated as 10.44% by atomic ratio: 9.77%: 10.18%: 9.42%: 11.30%: 48.89%. The obtained coating has a hardness of 34.6GPa and an elastic modulus of 370GPa.

Claims (5)

1. A multi-component nitride coating with high hardness and high elastic modulus, characterized in that: its chemical formula is AlCrTiZrNbN, and the atomic ratios of Al, Cr, Ti, Zr, Nb and N elements are 8 to 12% respectively : 8~12%: 8~12%: 8~12%: 8~12%: 48~52%, the thickness of the coating is 2~5 μm. 2. a kind of high hardness, high elastic modulus multi-component nitride coating according to claim 1, is characterized in that: wherein, Al, Cr, Ti, Zr, Nb and N element are calculated as 10%: 10%: 10%: 10%: 10%: 50%. 3. A multi-component nitride coating with high hardness and high elastic modulus according to claim 1, characterized in that said coating has a face-centered cubic crystal structure. 4. the preparation method of a kind of high hardness, high elastic modulus multi-component nitride coating described in claim 1, is characterized in that comprising the steps: 1) A step of cleaning the substrate, cleaning the polished and mirror-polished substrate with 15-30kHz ultrasonic waves in alcohol and acetone for 10-15 minutes; then performing ion cleaning. During the ion cleaning process, the substrate is packed Into the sample chamber, evacuate to 3*10 ^-3 Pa ~8*10 ^-3 Pa, then turn on Ar gas, maintain the vacuum at 2-4Pa, use intermediate frequency radio frequency to bombard the substrate with ions for 20~40min, the power is 80-100W; 2) A step of using a multi-target magnetron sputtering apparatus to perform magnetron sputtering reaction deposition on the substrate with an AlCrTiZrNb alloy target with a molar ratio of 1:1:1:1:1; the cleaned substrate is placed in Multi-target magnetron sputtering instrument and stay before AlCrTiZrNb alloy target material, the condition of above-mentioned magnetron sputtering reaction deposition is: argon gas flow: 10-50sccm; N flow: _5-30sccm ; RF power supply: 150- 300W, rotation speed: 10 r/min, time: 7200s; target base distance: 3-7cm; total air pressure range: 0.2-0.8Pa; substrate temperature range: 60-200°C, to obtain multiple sets of high hardness and high elastic modulus Nitride coating. 5 . The method for preparing a high-hardness, high-elastic-modulus multi-component nitride coating according to claim 4 , wherein the substrate is a metal, hard alloy or ceramic substrate. 5 .