CN112609156B - Wide-temperature-range self-lubricating film material with thermal cycle service capability and preparation method thereof - Google Patents
Wide-temperature-range self-lubricating film material with thermal cycle service capability and preparation method thereof Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
The invention discloses a wide-temperature-range self-lubricating film material with thermal cycle service capability and a preparation method thereof, belonging to the field of solid lubricating materials, wherein the wide-temperature-range self-lubricating film material comprises two modulation layer materials: the self-lubricating film is formed by alternately superposing two modulation layer materials, wherein the thickness of the self-lubricating film is 1-5 mu m. Or a tri-modulation layer material including an intermediate layer. The beneficial effects of the invention are as follows: the film has excellent thermal cycle service life on the premise of not influencing the overall wide temperature range self-lubricating performance by the structural design of the film and the cooperation of all the modulation layers, so that the film has more industrial application value.
Description
Technical Field
The invention belongs to the field of solid lubricating materials, and particularly relates to a wide-temperature-range self-lubricating nano multilayer film material with thermal cycle service capability and a preparation method thereof.
Background
Power machines and equipment have greatly affected the production and life of human beings since birth, and with the development of modern industry, more severe performance requirements are also put forward on the power machines and equipment, so that core components such as piston rings, bearings, high-speed gears and the like need to be served for a long time under the temperature fluctuation environment from room temperature to high temperature, and the performance requirements of traditional lubricating grease are difficult to meet. Based on solid lubrication science, the design and preparation of a wide-temperature-range self-lubricating hard film material with thermal cycle service capability by using a coating technology are effective ways for solving the problems, and have become one of the leading directions in the field of friction at present.
In order to obtain a film material with excellent wide-temperature-range friction and wear performance, the A.A. Voevodin professor of the American air force laboratory provides a self-adaptive concept to guide the design of the film, and the core idea is that the film spontaneously adjusts the composition and structure of the friction surface according to the change of the service environment so as to achieve the aims of antifriction and wear resistance. According to the adaptive concept, foreign material scientists have prepared, for example, YSZ/Au/MoS by adding a number of different temperature domain lubricating components to Yttria stabilized zirconia (YSZ, yttria-stabilized zirconia) hard films 2 Adaptive oxide-based thin film materials such as DLC, YSZ/Ag/Mo, and the like, and reports on wide-temperature-range adaptive properties thereof. In addition, domestic and foreign scholars successfully design and prepare TiN/Ag, VN/Cu and Mo by adding hard Metal Nitride (MeN) ceramic into the soft Metal coating to improve the mechanical property and bearing capacity of the coating 2 N/Cu and the like. However, the self-lubricating component can generate excessive oxidation consumption in a wide-temperature-range service environment, and the film does not have the thermal cycle service capability in a temperature fluctuation environment from room temperature to high temperature, so that the industrial application value of the film is low. How to utilize the mature film preparation technology to prepare the wide-temperature-range self-lubricating hard film material with the thermal cycle service capability through component and structure design so as to avoid excessive consumption of lubricating components is a key for enabling the wide-temperature-range self-lubricating hard film material to have industrial application value.
Disclosure of Invention
Aiming at the problems, the invention creatively provides a wide-temperature-range self-lubricating nano multilayer film material with thermal cycle service capability and a preparation technology thereof, and aims to prevent excessive oxidation consumption of lubricating components in a film, improve the wide-temperature-range self-lubricating tribological property of the film and enable the film to have the cyclic service capability.
The material mainly comprises two modulation layer materials: one is a Wide temperature range Self-lubricating layer (WSL, wide temperature Self-lubrication Layer), composed ofAmorphous nitrides (e.g., boron nitride, silicon nitride) or oxides (e.g., non-metal oxides: silicon oxide, boron oxide, etc., metal oxides: aluminum oxide, zinc oxide, chromium oxide, etc.), or oxynitrides (e.g., aluminum oxynitride, silicon oxynitride, zinc oxynitride, chromium oxynitride, etc.) shells and lubricating phase cores with wide temperature range self-lubricating properties (e.g., room temperature self-lubricating carbon-based (graphite, graphene, diamond-like, etc.) and sulfide-based (molybdenum sulfide, tungsten sulfide, etc.), medium temperature self-lubricating soft metals (gold, platinum, copper, iron, nickel, etc.), high temperature self-lubricating bimetallic oxides (e.g., ag 2 Mo 2 O 7 、Ag 2 MoO 4 、 AgNbO 3 、AgTaO 3 、Ag 3 VO 4 And Ag 2 Ti 4 O 9 Isochemical formula is MeTM x O y Or bimetallic oxides such as MoO 3 、 V 2 O 5 、VO 3 Isochemical formula TMe n O 2n-1 、TMe n O 3n-1 Or TMe n O 3n-2 Is equal to Magneli), has a nano-capsule structure, and can effectively protect the inner core material in a three-dimensional space by the shell on the premise that the inner core material ensures the wide temperature range self-lubricating performance of the whole multi-layer film, so as to avoid excessive oxidation or migration release; the other layer is a High-temperature oxidation-resistant barrier layer (HORBL, high-temperature Oxidation Resistance and Barrier Layer) composed of nitrides (generally crystalline aluminum nitride, titanium nitride, niobium nitride, tantalum nitride, tungsten nitride, molybdenum nitride, and amorphous boron nitride, silicon nitride) or oxides (such as aluminum oxide, silicon oxide) or oxynitrides (such as aluminum oxynitride, silicon oxynitride) with excellent thermal stability and thermal stability, and capable of further protecting the core material in WSL in the vertical substrate direction. The nano-structure multilayer film prepared by using a physical vapor deposition or chemical vapor deposition technology and alternately depositing two modulating layers of WSL and HORBL is a material related to the invention. An interlayer (ML) is formed by a shell material and a HORBL material in the WSL, so that interlayer stripping caused by the difference of thermal expansion coefficients and microstructures between the WSL and the HORBL in the service process is avoidedNanostructured multilayer films prepared by alternating deposition of three modulating layers, WSL, ML and HORBL, are another class of materials to which the present invention relates.
The beneficial effects of the invention are as follows:
1. the film has excellent thermal cycle service life on the premise of not influencing the overall wide temperature range self-lubricating performance by the structural design of the film and the cooperation of all the modulation layers, so that the film has more industrial application value.
2. Excessive consumption of self-lubricating components is effectively avoided in a three-dimensional space, so that the film has thermal cycle service capability;
3. the multilayer film with the nano structure is designed and prepared in a mode of WSL and HORBL alternate deposition, and the core material in the WSL is further protected in the direction vertical to the substrate on the premise of ensuring the overall bearing capacity and high-temperature heat stability of the film by reasonably selecting HORBL elements and phase constitution;
4. by introducing ML, interlayer stripping caused by the difference of thermal expansion coefficients and microstructures between WSL and HORBL in the service process is avoided, and the service life of the film is further prolonged;
5. the synergistic effect between the shell and the core of the nanocapsule achieves the balance of the consumption and the protection of the lubricating components in the WSL layer, and further has the thermal cycle service capability on the premise of ensuring the self-lubricating tribology performance in a wide temperature range;
6. under the premise that the self-lubricating capability of WSL wide-temperature-range thermal cycle is not weakened, the HORBL ensures the overall bearing capability and high-temperature stability of the film and further protects lubricating components;
7. under the premise of not affecting the performances of each position of the WSL and the HORBL, the synergistic effect of the ML and the WSL and the HORBL avoids interlayer stripping caused by the difference of thermal expansion coefficients and microstructures in the service process, and the service life is prolonged;
8. overcomes the defect of insufficient thermal cycle service capability of the existing wide-temperature-range self-lubricating film, can be prepared by various modes such as magnetron sputtering, multi-arc, ion plating, chemical vapor deposition and the like, and has higher production efficiency and industrial application value.
Drawings
FIG. 1 is a schematic illustration of a WSL/HORBL type multilayer film structure;
FIG. 2 is a schematic illustration of a WSL/HORBL/ML type multilayer film structure;
FIG. 3 is a transmission electron micrograph of BNx-Ag/Al2O3 nanostructured thin film cross-section.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The nanostructured multilayer films to which this patent relates can be specifically classified into two types: WSL/HORBL type and WSL/HORBL/ML type.
1. To enable one of ordinary skill in the art to better understand the technical scheme of the invention, a BN is selected x -Ag/Al 2 O 3 The nanostructure film material is a specific WSL/HORBL film, and the technical scheme of the invention is further described.
Example 1: preparation of BN based on hard matrix surfaces x -Ag/Al 2 O 3 A method of nanostructured thin film material comprising the steps of: the preparation of the film is completed on high vacuum multi-target magnetron sputtering equipment, wherein the magnetron sputtering equipment is called a magnetron sputtering instrument for short, three sputtering targets are arranged on the magnetron sputtering instrument and are respectively arranged on three water-cooled target brackets, and three stainless steel baffles are respectively arranged in front of the three targets and are automatically controlled by a computer; b target, ag target and Al 2 O 3 The targets are respectively arranged on independent radio frequency cathodes, and the diameters of the targets are 75mm;
step one: carrying out mirror surface treatment on the surface of a substrate of the hard alloy, respectively carrying out ultrasonic cleaning on the surface of the substrate for 15min by using absolute ethyl alcohol and acetone, drying the surface of the substrate by using hot air, and then placing the surface of the hard alloy or the ceramic substrate on a rotatable substrate frame in a film making cabin of a magnetron sputtering instrument, wherein the distance from the surface substrate of the hard alloy or the ceramic substrate to a target is fixed at 80cm;
step two: vacuum pumping operation is carried out on a film making cabin of the magnetron sputtering instrument, and the background vacuum degree of the vacuum chamber is better than 6.0 multiplied by 10 -4 Ar with purity of 99.999% is introduced into the vacuum chamber after Pa 2 Striking an arc;
step three: isolating the surface substrate of the hard alloy or ceramic matrix from the ion region by a baffle plate before depositing the film;
step four: after the baffle plate is isolated, the B target, the Ag target and the Al are opened 2 O 3 Targets, each target is subjected to 10min pre-sputtering to remove impurities on the surface of the target;
step five: rotating a baffle plate, and enabling an Al target to work, wherein an Al transition layer with the thickness of 200nm is pre-sputtered on a substrate on the surface of a hard matrix so as to enhance the binding force of a film base; then the baffle plate is removed, the sputtering air pressure is fixed to be 0.2Pa, and BN is deposited x When the Ag layer is formed, fixing the power of the B target and the Ag target to be 50W and 150W, closing the Al target, introducing nitrogen and Ar/N 2 The flow ratio is 10/2, and the deposition time is 400s; in the deposition of Al 2 O 3 And when the layer is formed, fixing an Al target to be 150W, closing a B target and an Ag target, and closing a nitrogen inlet valve, wherein the deposition time is 500s.
At this time, BN x Ag layer thickness 30nm, al 2 O 3 The thickness of the layer is 60nm, the modulation ratio of the two modulation layers is 1:2, and the modulation period is 90nm. The total thickness of the film is 1-5 mu m. The film hardness was 32GPa. After 30 minutes of circumferential friction test, the friction coefficients of room temperature, 300 ℃, 600 ℃ and 800 ℃ are approximately stabilized at 0.5, the friction test is circulated for ten times, and the film is not worn through, so that higher thermal cycle service capability is reflected.
Example 2
Unlike example 1, the following is: in the deposition of BN x The deposition time for the Ag layer was 600s. At this time, BN x Ag layer thickness 40nm, al 2 O 3 The layer thickness is 60nm, and the modulation ratio of the two modulation layers is 2:3, the modulation period is 100nm. The total thickness of the film is 1-5 mu m. The film hardness was 28GPa. Silicon nitride is used as a friction pair, and after 30 minutes of circumferential friction experiment, the friction coefficients at room temperature, 300 ℃, 600 ℃ and 800 ℃ are largeThe friction experiment is circulated for ten times until the stability is 0.4, and the film is not worn through, thus showing higher thermal cycle service capability.
Example 3
Unlike example 1, the following is: in the deposition, BN x The deposition time for the Ag layer was 900s. At this time, BN x Ag layer thickness of 60nm, al 2 O 3 The thickness of the layer is 60nm, the modulation ratio of the two modulation layers is 1:1, and the modulation period is 120nm. The total thickness of the film is 1-5 mu m. The film hardness was 19GPa. After 30 minutes of circumferential friction test, the friction coefficients of room temperature, 300 ℃, 600 ℃ and 800 ℃ are approximately stabilized at 0.3, the friction test is circulated for ten times, and the film is not worn through, so that higher thermal cycle service capability is reflected.
2. To enable one of ordinary skill in the art to better understand the technical scheme of the invention, siO is selected x -MoO 3 -Ag/SiO x -Al x N/Al x N/Al x N-SiO x The nanostructure film material is a specific WSL/HORBL/ML film, and the technical scheme of the invention is further described.
Example 4: preparation of SiO based on hard matrix surface x -MoO 3 -Ag/SiO x -Al x N/Al x N/Al x N-SiO x A method of nanostructured thin film material comprising the steps of: the preparation of the film is completed on a magnetron sputtering instrument, three sputtering targets are arranged on the magnetron sputtering instrument and are respectively arranged on three water-cooled target brackets, and three stainless steel baffles are respectively arranged in front of the three targets and are automatically controlled by a computer; siO (SiO) x Target, moO 3 The Ag composite target and the Al target are respectively arranged on independent radio frequency cathodes, and the diameters of the targets are 75mm;
step one: carrying out mirror surface treatment on the surface of a substrate of the hard alloy, respectively carrying out ultrasonic cleaning on the surface of the substrate for 15min by using absolute ethyl alcohol and acetone, drying the surface of the substrate by using hot air, and then placing the surface of the hard alloy or the ceramic substrate on a rotatable substrate frame in a film making cabin of a magnetron sputtering instrument, wherein the distance from the surface substrate of the hard alloy or the ceramic substrate to a target is fixed at 80cm;
step two: for magnetron sputtering apparatusThe membrane making cabin is vacuumized, and the background vacuum degree of the vacuum chamber is better than 6.0 multiplied by 10 -4 Ar with purity of 99.999% is introduced into the vacuum chamber after Pa 2 Striking an arc;
step three: isolating the surface substrate of the hard alloy or ceramic matrix from the ion region by a baffle plate before depositing the film;
step four: after the baffle plate is isolated, siO is opened x Target, moO 3 Performing pre-sputtering on each of the Ag composite target and the Al target for 10min to remove impurities on the surface of the target;
step five: rotating a baffle plate, and enabling an Al target to work, wherein an Al transition layer with the thickness of 200nm is pre-sputtered on a substrate on the surface of a hard matrix so as to enhance the binding force of a film base; then the baffle plate is removed, the sputtering air pressure is fixed to be 0.3Pa, and SiO is deposited x -MoO 3 When Ag layer, siO is fixed x Target, moO 3 The power of the Ag composite target is 150W and 40W, the Al target is closed, and the deposition time is 300s; on deposition of SiO x -Al x Nitrogen is introduced into the N layer, ar/N 2 The flow ratio of (2) is 10/3, and SiO is fixed x Target power is 150W while MoO is turned off 3 The power of the Al target is controlled to linearly change 80W from 0W along with the deposition time of the Ag composite target, and the deposition time is 60s; in the deposition of Al x In the case of N layers, the target was fixed at 80W while SiO was turned off x Target, moO 3 The deposition time of the Ag composite target is 300s; in the deposition of Al x N-SiO x When the layer is formed, the Al target power is opened to 80W, and MoO is performed simultaneously 3 Ag composite target, control SiO x The target power was linearly varied from 80W to 0W with deposition time, which was 60s.
At this time, siO x -MoO 3 Ag layer thickness 40nm, siO x -Al x N layer thickness is 15nm, al x The thickness of the N layer is 60nm, al x N-SiO x The thickness of the layer is 15nm. The modulation ratio of the four modulation layers is 8:3:12:3, and the modulation period is 130nm. The total thickness of the film is 1-5 mu m. The film hardness was 22GPa. After 30-minute circumferential friction test, the friction coefficients of room temperature, 300 ℃, 600 ℃ and 800 ℃ are approximately stabilized at 0.3, the friction test is circulated for ten times, the film is not worn through, and higher thermal cycle service capacity is reflected。
Example 5
Unlike example 4, the following is: on deposition of SiO x -MoO 3 The deposition time for the Ag layer was 600s. At this time, siO x -MoO 3 The thickness of the Ag layer is 80nm, the thickness of the gradient layer is 5nm, the thickness of the hard layer is 60nm, the modulation ratio of the four modulation layers is 16:3:12:3, and the modulation period is 170nm. The total thickness of the film is 1-5 mu m. The film hardness was 18GPa. After 30 minutes of circumferential friction test, the friction coefficients of room temperature, 300 ℃, 600 ℃ and 800 ℃ are approximately stabilized at 0.3, the friction test is circulated for ten times, and the film is not worn through, so that higher thermal cycle service capability is reflected.
The film preparation mode related to the patent is not limited to magnetron sputtering, and can be obtained by multiple film preparation modes such as multi-arc, ion plating, chemical vapor deposition and the like. In addition, it is worth pointing out that the design concept of amorphous encapsulation nanocrystalline for preventing migration and diffusion of soft metal can also be applied to the fields of microelectronics, semiconductors and the like. The modulation layer material related to the patent can also be independently used as a composite film material.
It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing description merely illustrates the principles of the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. The wide-temperature-range self-lubricating film material with the thermal cycle service capability is characterized by comprising two modulation materials, wherein one layer is a wide-temperature-range self-lubricating layer, the other layer is a high-temperature oxidation-resistant layer, the inner core material in the wide-temperature-range self-lubricating layer is Ag, and the outer shell material is BN x The high-temperature antioxidation barrier layer material is Al 2 O 3 Reaction confocal sputtering of Ag target and B target to form BN x Ag layer deposited with BN x In the case of Ag layers, the deposition times are 400s, 600s or 900s, al 2 O 3 Sputtering to form Al 2 O 3 Layer, BN x Ag layer and Al 2 O 3 The modulation ratio of the layers is 1:2, 2:3 or 1:1, the modulation period is 90nm, 40nm or 120nm, and the BN is formed x -Ag/Al 2 O 3 Nanostructured thin film materials.
2. The wide-temperature-range self-lubricating film material with the thermal cycle service capability is characterized by comprising a wide-temperature-range self-lubricating layer, a high-temperature oxidation-resistant layer and an intermediate layer, wherein the inner core material in the wide-temperature-range self-lubricating layer is Ag, and the outer shell material is SiO x -MoO 3 The high-temperature antioxidation barrier layer material is Al x N, the middle layer is SiO x -Al x N or Al x N-SiO x By SiO x Target, moO 3 Ag composite target and Al target, and depositing to obtain SiO x -MoO 3 Ag layer, siO x -Al x N layer, al x N layer and Al x N-SiO x Layer, deposition of SiO x -MoO 3 Ag layer deposited for 300s or 600s, siO x -MoO 3 Ag layer, siO x -Al x N layer, al x N layer and Al x N-SiO x The modulation ratio of the layers is 8:3:12:3 or 16:3:12:3, the modulation period is 130nm or 170nm, and the SiO is formed by the components x -MoO 3 -Ag/SiO x -Al x N/Al x N/Al x N-SiO x Nanostructured thin film materials.
3. The method for preparing the wide-temperature-range self-lubricating film material with thermal cycle service capability according to claim 2, which is characterized by comprising the following steps:
step one: carrying out mirror surface treatment on the surface of a substrate of the hard alloy, respectively carrying out ultrasonic cleaning by using absolute ethyl alcohol and acetone, drying by using hot air, and then loading the dried substrate on a rotatable substrate frame in a film making cabin of a magnetron sputtering instrument, wherein the distance between the surface substrate of the hard alloy or a ceramic matrix and a target is fixed at 80cm;
step two: vacuum pumping operation is carried out on a film making cabin of the magnetron sputtering instrument, and the background vacuum degree of the vacuum chamber is better than 6.0 multiplied by 10 -4 Pa backward vacuum chamberIntroducing Ar with purity of 99.999 percent to start arc;
step three: isolating the surface substrate of the hard alloy or ceramic matrix from the ion region by a baffle plate before depositing the film;
step four: after the baffle plate is isolated, siO is opened x Target, moO 3 Performing pre-sputtering on each of the Ag composite target and the Al target for 10min to remove impurities on the surface of the target;
step five: rotating a baffle plate, and enabling an Al target to work, wherein an Al transition layer with the thickness of 200nm is pre-sputtered on a substrate on the surface of a hard matrix so as to enhance the binding force of a film base; then the baffle plate is removed, the sputtering air pressure is fixed to be 0.3Pa, and SiO is deposited x -MoO 3 When Ag layer, siO is fixed x Target, moO 3 The power of the Ag composite target is equal to that of the Al target, and the Al target is closed at the same time, so that deposition is carried out; on deposition of SiO x Introducing nitrogen gas into the AlxN layer, ar/N 2 The flow ratio of (2) is 10/3, and SiO is fixed x Target power while turning off MoO 3 The power of the Ag composite target is controlled to linearly increase from 0W along with the deposition time; in the deposition of Al x In the case of N layers, the target is fixed while SiO is turned off x Target, moO 3 The deposition time of the Ag composite target is 300s; in the deposition of Al x N-SiO x In the case of a layer, the Al target is opened while MoO 3 Ag composite target, control SiO x The target power was linearly reduced to 0W with deposition time.
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