KR100818165B1 - Method for Producing Multilayered-film having Lubricant and Anti-abrasive Property - Google Patents

Abstract

Method for producing a multilayer composite coating having excellent lubricity and wear resistance of the present invention comprises the steps of: a) forming a hard ceramic coating on the base material by physical vapor deposition (PVD) or chemical vapor deposition (CVD); b) the droplet hole or the pin hole is exposed through micro-blasting or mirror surface treatment on the surface of the hard ceramic film, or the process variable control during the blasting, polishing or hard ceramic film forming step A surface control step for forming an intaglio (oil hole) which may contain a solid lubricant such as (Pit), irregularities, valleys, and the like; c) forming a multilayer lubricating film by forming a solid lubricating film on the mirror-treated hard ceramic film layer; And d) solidifying the multilayer composite film at 100-450 ° C .; Characterized in that it comprises a.

As described above, the multilayered composite film formed by the present invention has a lubricating property of low friction coefficient, which is an advantage of an excellent wear resistance and a solid lubricating film, which is an advantage of the hard ceramic film, and a defect formed in the hard ceramic film acts as an oil hole to continuously lubricate The components can be supplied to maintain wear resistance and lubricity for a long time even under high load conditions. Through this, it is possible to significantly extend the life of the product, there is an advantage that can greatly improve the slip resistance, wear resistance, tack resistance and mold release properties of the product.

In addition, the production process is simple and can reduce the production cost can increase the production efficiency, there is an advantage to obtain a stable quality.

Low friction, composite coating, hard ceramic coating, ion plating, spattering, lubricating coating, sintering

Description

Method for Producing Multilayered-film having Lubricant and Anti-abrasive Property

1 is a configuration diagram for one actual step of the multi-layer composite film production process according to the present invention.

2 is a cross-sectional view of a multilayer composite film produced according to the present invention.

Figure 3 is a graph of the friction wear test results of the multilayered composite film prepared according to the present invention.

** Description of the symbols for the main parts of the drawings **

100: multilayer composite coating 10: base material

20: hard ceramic coating 30: solid lubricating coating

50: oil hole (engraved) 51: droplet hole

52: pinhole

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a multilayer composite film having excellent lubricity and abrasion resistance. More particularly, the present invention relates to abrasive wear, seizing, and cold welds generated during or in contact with metal and nonmetal materials. The present invention relates to a method for producing a multilayer composite film having excellent lubricity and wear resistance for improving problems such as delamination, spalling, and pull-out.

Generally, as a method for improving the wear resistance of various mechanical parts and tools, coating of hard ceramic coatings by thermal spraying, oxidation treatment, nitriding treatment, physical or chemical vapor deposition, and the like are known.

In the case of using the physical vapor deposition method, there are mainly methods such as ion plating or sputtering of an arc or an electron beam method.

Ion plating is exhausted with high vacuum of 10 ^-5 Torr or higher, and then gas such as Ar, N ₂ , C ₂ H ₂ gas is injected, potential is applied to the base metal to form plasma, and the material is formed using an arc or electron beam. Is a method of depositing a coating material on a substrate by evaporation.

Sputtering refers to the evaporation of metal by sputtering and coating on the substrate. To increase the deposition rate, magnets are attached to the target backside to form a magnetic field perpendicular to the electric field, constraining the movement of electrons around the target and extending the path of travel. This is to increase the sputtering efficiency.

The magnetron sputtering method, which is a method of arranging a magnet on the back of the target, exhausts the high vacuum of 10 ^-5 Torr as in the ion plating, injects Ar gas, applies an electric potential to the target, forms a plasma, and then reacts to the collision of Ar gas. The deposition material is generated from the base metal and the deposition material reacts with a reaction gas such as N _{2 or} C ₂ H ₂ to deposit a hard ceramic coating layer on the substrate.

The above-described physical vapor deposition method is widely used to coat ceramic hard thin films on various machinery parts, press molds, injection molds, punches, etc. in order to improve processing characteristics and lifespan, and in particular, parts requiring wear resistance are essential processes. to be.

Problems that occur during the operation of the machine is not only wear, but also sintering, cold welding, etc., because they adversely affect the performance or life of the machine has been conventionally used liquid lubricants such as oil to improve the lubricity of the product. As environmental regulations become more stringent in recent years, the use of liquid lubricants has been increasingly regulated, and solid lubricant coatings suitable for the environment have been spotlighted instead of liquid lubricants.

As an example of a conventional multilayer composite coating method, Korean Laid-Open Patent Publication No. 10-2003-0094870 has been disclosed. The method comprises evacuating the vacuum chamber to below atmospheric pressure; Cleaning the substrate by applying power to an arc evaporation source while applying a negative voltage to the substrate; Dropping the voltage of the substrate to form a metal interface layer on the base material; Introducing a reaction gas into the vacuum chamber to form a hard coating layer; Blocking the introduction of a power source and a reaction gas applied to the arc evaporation source and sputtering the Ti target to form a metal buffer layer; Sputtering the MoS ₂ target to form a MoS ₂ -Ti coating layer; And forming a MoS ₂ coating layer by cutting off the power to the Ti target to simultaneously implement abrasion resistant coating and lubricating coating in the same system, thereby developing a method of simultaneously coating the wear resistant coating and the low friction coating layer. have.

The multilayer composite film prepared as described above has a complicated process because the hard ceramic film and the solid lubricating film are deposited by the physical vapor deposition method, which is not only difficult to obtain stable quality due to the strict conditions, but also because all the processes are performed in a vacuum. This had a lot of drawbacks.

In addition, since the solid lubricating film is directly deposited without a separate treatment process for a large number of surface defects formed when the hard ceramic film is deposited, it is difficult to fully utilize the lubricating characteristics inherent in the solid lubricant, and it is embedded in the hard ceramic film during operation. Droplet particles are separated and act as new wear particles to promote wear and to reduce the adhesion between the two materials.

Accordingly, the present invention has been made to solve the above problems, the object of the present invention can easily form a film with excellent wear resistance, low friction, lubricity and can maintain excellent wear resistance for a long time even under high load conditions, It is to provide a method for producing a multilayer composite coating that can improve the wear resistance, adhesion resistance and releasability.

In addition, the present invention is to provide a method for producing a multilayer composite film having excellent lubricity and wear resistance that can be obtained a simple and stable quality of the manufacturing process and increase the efficiency by reducing the production cost.

Method for producing a multilayer composite coating having excellent lubricity and wear resistance of the present invention comprises the steps of: a) forming a hard ceramic coating on the base material by physical vapor deposition (PVD) or chemical vapor deposition (CVD); b) the droplet hole or the pin hole is exposed through micro-blasting or mirror surface treatment on the surface of the hard ceramic film, or the process variable control during the blasting, polishing or hard ceramic film forming step A surface control step for forming an intaglio (oil hole) which may contain a solid lubricant such as (Pit), irregularities, valleys, and the like; c) forming a multilayer lubricating film by forming a solid lubricating film on the mirror-treated hard ceramic film layer; And d) solidifying the multilayer composite film at 100-450 ° C .; Characterized in that it comprises a.

Further, in step a), the hard ceramic film is formed of nitrides such as CrN, Cr ₂ N, TiN, AlTiN, TiAlN, CrTiN, TiSiN, AlCrN, carbides such as TiC, CrC, TiNN, TiAlCN, It is characterized in that it is formed of one or a composite layer selected from carbonitrides such as CrCN, or oxides such as Al ₂ O ₃ , SiO ₂ , TiO _2, and the like.

In the step a), the physical vapor deposition method is an ion plating method using an arc, resistance heating, electron beam, etc., sputtering method, etc., and the chemical vapor deposition method is characterized by using chemical vapor deposition (CVD) using plasma or heat. .

In addition, the process variable control of step b) is characterized in that artificially adjusting the arc current, vacuum degree, bias voltage, current in the hard ceramic film forming step.

In addition, the step c) is characterized in that formed by spraying or dipping (solid) the solid lubricant.

In addition, the solid lubricant is characterized in that it is formed of one or a mixture thereof selected from MoS ₂ , WS ₂ , PTFE.

In addition, it is characterized in that it further comprises a degreasing and drying step before step a).

In addition, the step of b) and c) characterized in that it further comprises a degreasing and drying step in the middle.

Hereinafter, with reference to the accompanying drawings with reference to the drawings as follows.

1 is a configuration diagram for one actual step of the multi-layer composite film production process according to the present invention, Figure 2 is a cross-sectional view of a multilayer composite film produced according to the present invention, Figure 3 is a multilayer composite prepared by the present invention This is a graph of the friction wear test results of the film.

As shown in FIG. 1, the method for manufacturing a multilayer composite film according to the present invention includes a polishing and polishing step (S101), a hard ceramic film forming step (S104), a mirror surface and surface control treatment step (S105), and a solid lubricating film treatment step ( S108), it is composed of a drying step (S109) or a solidification step (S110).

The polishing and polishing step (S101) is a step for increasing the surface roughness of the prepared base material 10 and giving a mirror surface to uniform the surface roughness by blasting, buffing or polishing using an abrasive. Processing step.

The hard ceramic film forming step (S104) is a base material 10 using a physical vapor deposition method (PVD), such as arc plating, resistance heating, electron beam, sputtering method, or chemical vapor deposition (CVD) using plasma or heat. The hard ceramic film 20 containing nitride, carbide, carbonitride, and oxide as a main component is deposited on the surface thereof. The hard ceramic film 20 may include nitrides such as CrN, Cr ₂ N, TiN, AlTiN, TiAlN, CrTiN, carbides such as TiC and CrC, carbonitrides such as TiCN, TiAlCN, CrCN, etc. It is characterized by being formed of one or a composite layer thereof selected from oxides such as Al ₂ O ₃ , SiO ₂ , TiO _2, and the like.

The hard ceramic film mirror surface and surface control treatment step (S105) is a step of forming an oil hole (engraved) in which the solid lubricant can stay for a long time. In the present invention, various defects of the film formed during the multilayer composite coating process are actively used as oil holes. It is characterized by using.

Representative defects of the deposition step are droplets (particles attached or stuck to the surface) and pin holes. The droplets and pinholes 52 are formed on the surface of the hard ceramic film 20 during the deposition process, and artificially adjust the arc current, vacuum degree, bias voltage, current, and the like to change the surface state such as size, distribution, and quantity. I can regulate it. Compared to other deposition methods, a plurality of droplets may be formed in the hard ceramic film 20 using the arc ion plating method, and a plurality of pinholes 52 may be formed in the hard ceramic film 20 using the sputtering method. have. However, conventionally, the droplets or pinholes 52 are generally recognized as defects, and efforts have been made to eliminate them.

In addition, even before the hard ceramic film 20 is formed in the physical vapor deposition method or the chemical vapor deposition method, even if the base material 10 is theoretically planar, a fine growth pattern or a cabbage pattern is formed on the surface of the hard ceramic film 20 during deposition. It will have a feature of growth of flower or growth feature of cabbage. This pattern is also regarded as a defect on the surface of the coating, and efforts have been made to eliminate this phenomenon during the deposition process, such as the droplets and pinholes 52. In the present invention, the defect is used as an oil hole 50 to fill a solid lubricant to play a role of maintaining the solid lubricant for a long time while the wear occurs.

In addition, when the physical vapor deposition method is used in the step (S104) of forming the hard ceramic film 20, the state of the surface can be controlled according to the conditions of the ion impact in the ion shock step, which is the previous step in which the hard ceramic film 20 is deposited. Depending on the conditions, fine pits, irregularities, and valleys may be generated. When the hard ceramic film is deposited after forming defects such as pits, unevenness and valleys, the hard ceramic film 20 is deposited along the defects formed on the surface. Defects on the surface of the hard ceramic film 20 also play a role of keeping the solid lubricant for a long time.

The above method suggests a method of artificially creating a defect during the formation of the hard ceramic film 20, and the following various methods are used to determine the surface state of the hard ceramic film 20 after the hard ceramic film 20 is formed. It shows how to adjust. In general, a large number of embossed droplets protruding on the surface deposited by arc ion plating have to be subjected to a process of allowing the droplets to be detached to generate a recessed indentation that can be utilized as an oil hole. That is, the hard ceramic film surface mirror surface and surface control processing step (S105) is a step of exposing a plurality of droplet holes 51 (Droplet holes) by removing the droplet (Droplet) attached to the film. If the hard ceramic film 20 in which the droplet particles are not removed is in contact with the other surface, the droplet particles are released during the contact movement of the two surfaces and act as a new wear factor, thus adversely affecting the performance of the product. Get mad. Hard ceramic coating surface mirror surface and surface control processing step (S105) has a variety of methods such as dry and wet blasting (buffing), buffing (polishing), polishing (Grinding) using an abrasive.

In the hard ceramic film 20 formed during the deposition method, sputtering in which droplets are generally generated on the surface of the hard ceramic film 20, or electron beam deposition in which the pinholes 52 are relatively small, are artificially applied to the surface to artificially harden the hard ceramic film ( 20) Defects may form on the surface. Defects can be formed on the surface by using grinding tools or by wet and dry blasting processes that collide hard particles such as alumina and silica.

Solid lubricating film forming step (S108) is spray (spray) or dipping a solid lubricant dissolved in an organic solvent to fill the defects including the droplet hole 51 or pinhole 52 exposed to the hard ceramic film 20 ( Dipping) to form a solid lubricating film 30. At this time, the solid lubricating film 30 is not particularly limited to use one or a mixture selected from conventional solid lubricants used in this field, MoS ₂ , WS ₂ , PTFE and the like in terms of durability. In the solid lubrication film forming step (S108), moisture and foreign matter should not be mixed and the solid lubrication film 30 should be evenly formed on the surface of the hard ceramic film 20. When the solid lubricating film 30 is formed, defects of the hard ceramic film 20 act as oil holes 50, and the hard ceramic film 20 and the solid lubricating film 30 are formed by an anchoring effect. Adhesion can be improved. In addition, it is possible to form a solid lubricating film 30 without using a strict deposition method, it is possible not only to improve the wear resistance and quality of the product, but also to reduce the production cost and to enable stable product production.

The base material 10 on which the solid lubrication film 30 is formed is manufactured through a drying step (S109) and a solidification step (S110) of a highly functional multilayer composite film 100 having excellent lubricity and wear resistance.

At this time, the drying step (S109) is a step of naturally drying the applied solid lubricating film 30 and the solidification step (S110) is processed from several minutes to several hours as necessary at 100 ~ 450 ℃.

In addition, the present invention provides a degreasing step for cleaning the surface between the polishing and polishing step (S101) and the hard ceramic film forming step (S104) and between the mirror surface treatment step (S105) and the solid lubricating film forming step (S108) as necessary. A drying step may be further included.

The degreasing step (S102) included after the polishing and polishing step (S101) is a step of removing foreign substances (such as oil or rust) present on the surface of the base material 10 by using an organic solvent or an alkali. Foreign matter remaining in the may be affected in the adhesion and performance of the final product is preferably removed in the degreasing step (S102). The drying step (S103) is a step of hot air or natural drying below 60 ℃.

The degreasing step (S106) included after the mirror surface treatment step (S105) is performed by the same method as the degreasing step (S102) included after the polishing and polishing step (S101), and the drying step (S107) is 60 ° C. The following is a step of hot air or natural drying.

Figure 3 is a graph of the friction, wear test results of the multilayered composite film 100 prepared by the present invention. At this time, the test condition is 950g load and 100rpm speed. As shown, the hard ceramic film CrN produced by the present invention and the lubricating film MoS ₂ is It can be seen that the base material on which the formed multilayer composite film 100 is formed has a significantly lower coefficient of friction than the base material on which the hard ceramic film CrN is formed alone. In addition, it can be seen that the CrN + MoS ₂ multilayer composite film 100 prepared according to the present invention shows excellent lubricity for a long time even under high load conditions.

Example 1

Burring punches made of cold die steel (SKD11) with hardness of HRC58 were polished sequentially using 120, 220, 320, 400, and 600 wheel paper using pneumatic polishing tools, and then in olive oil. Polishing with a wool wheel was carried out using an abrasive containing a small amount of artificial diamond having a particle size of 1 ~ 4μm. Then, the Burring Punch was ultrasonically immersed in MC (methylene chloride) solvent, ultrasonically immersed in 111-TCE (trichloroethane) solvent, and rinsed again, followed by the rinsing process, and the trichloroethane solvent. The surface of the burring punch was placed adjacent to and the trichloroethane solvent was evaporated to allow the evaporated trichloroethane solvent to condense and wash on the burring punch surface, followed by natural drying.

A CrN hard ceramic film was formed by an arc ion plating method in an arc ion plating chamber having a high purity Cr target inside the surface. The arc ion plating method is preheated to 450 ℃ for 3 hours, voltage -500V → -800V, vacuum degree 2.5 × 10 ^-2 Torr, primary plasma cleaning with Ar at 450 ℃ temperature, voltage -450V → 650V, target Plasma secondary cleaning with Ar at an arc current of 65 A, vacuum degree of 8 × 10 ^-4 Torr, and 450 ° C., voltage -600V → 700V, target arc current of 85A, vacuum degree of 8 × 10 ^-4 → 1 × 10 ^-3 Torr, After injecting N ₂ at the temperature of 450 ℃ and activating Cr ions generated at the target by impacting the surface of the product, the voltage is -105V, target arc current 95A, vacuum degree 9 × 10 ^-3 Torr, and the temperature is 450 ℃ ₂ Coating with gas and N ₂ at 150 Cool with gas.

The hard coating surface coated with CrN was polished using a wool wheel, and an abrasive containing a small amount of artificial diamond having a particle size of 1 to 4 μm in olive oil was used to increase polishing efficiency. Then, the burring punch was ultrasonically immersed in a methylene chloride solvent, ultrasonically degreased by immersing in a trichloroethane solvent, rinsed, degreased the surface using steam, and then naturally dried.

Using a pneumatic spray gun MoS ₂ (SANDSTROM社product, # 103) is sprayed to dry and solidify for 30 minutes at 180 ℃ in BATCH expression oven of about 15μm MoS ₂ A burring punch having a coating was produced.

In order to evaluate the work performance of the burring punch, a burring process was performed using a 3.2t stainless plate as a molding material, and a burring punch having a single CrN film was simultaneously worked for comparative evaluation. The results are shown in Table 1 below by comparing the number of times of burring punches.

Example 2

In the same manner as in Example 1, except that a forming die of non-heat treated steel (S45C), which is used for drawing processing and has a hardness of HRC 10 or less, is used instead of a burring punch. A multilayer composite film was formed. In addition, in order to evaluate the work performance of the molding die, drawing processing was performed using a 0.8t embossed aluminum sheet as a to-be-molded material. The molding die was also worked at the same time. The number of operations of the molding die is compared and the results are shown in Table 1 below.

Table 1 compares the working efficiency of Example 1 and Example 2.

TABLE 1

Operation count Conventional CrN Monolayer CrN + MoS ₂ Multilayer Composite Film Example 1 1,250 40,000 Example 2 No work due to tearing 25,000

As shown in Table 1, as a result of the burring process using a 3.2t stainless plate as a to-be-molded material, the burring punch having a conventional CrN monolayer was performed after 1,250 operations and was no longer subjected to severe sintering and scratching. The operation was impossible and the CrN + MoS ₂ multilayer composite film according to the present invention was in good condition even after 40,000 operations.

In addition, as a result of drawing processing using 0.8t embossed aluminum sheet as a molding material, the existing die having a CrN single layer coating was not able to work due to tearing, and the CrN + MoS ₂ multilayer composite film according to the present invention was 25,000. The condition was good even after the dog work.

As described above, when the multilayered composite film is formed according to the present invention, the durability of the molding die and the forging mold and the quality of the molding material can be greatly improved. In particular, more remarkable effects can be expected in the molding processing of various wear-resistant industrial parts, such as automobiles, adhesive materials (aluminum alloys, copper, copper alloys, stainless steel, plated steel sheets, etc.) and thick plates.

The present invention is not limited to the above-described embodiments, and the scope of application is not limited, and various modifications can be made without departing from the gist of the present invention as claimed in the claims.

As described above, the multilayered composite film formed by the present invention has a lubricating property of low friction coefficient, which is an advantage of an excellent wear resistance and a solid lubricating film, which is an advantage of the hard ceramic film, and a defect formed in the hard ceramic film acts as an oil hole to continuously lubricate The components can be supplied to maintain wear resistance and lubricity for a long time even under high load conditions. Through this, it is possible to significantly extend the life of the product, there is an advantage that can greatly improve the slip resistance, wear resistance, tack resistance and mold release properties of the product.

In addition, the production process is simple and can reduce the production cost can increase the production efficiency, there is an advantage to obtain a stable quality.

Claims (8)

a) controlling the arc current, the degree of vacuum, the bias voltage, or the current in physical vapor deposition (PVD) or chemical vapor deposition (CVD) to form a hard ceramic film having defects on the surface and in the substrate; b) a surface control step of forming a negative hole (oil hole) by exposing a droplet hole or a pin hole by micro-blasting, mirroring or polishing the hard ceramic film surface; c) forming a multi-layer composite film by forming a solid lubricating film by spraying or dipping a solid lubricant on the surface-controlled hard ceramic film; And d) solidifying the multilayer composite film to 100-450 ° C .; Method for producing a multilayer composite film excellent in lubricity and wear resistance comprising a. The method of claim 1, In step a), the hard ceramic film is formed of nitrides such as CrN, Cr ₂ N, TiN, AlTiN, TiAlN, CrTiN, TiSiN, AlCrN, carbides such as TiC, CrC, TiCN, TiAlCN, CrCN, etc. A method for producing a multilayer composite film having excellent lubricity and abrasion resistance, characterized in that it is formed of one or a composite layer of the same carbonitride or an oxide such as Al ₂ O ₃ , SiO ₂ , TiO _2, or the like. The method of claim 1, In step a), the physical vapor deposition method (PVD) uses an ion plating method, a sputtering method, etc. using an arc, resistance heating, an electron beam, etc., and the chemical vapor deposition method (CVD) uses a chemical vapor deposition method using plasma or heat. Manufacturing method. delete delete The method of claim 1, The solid lubricant is formed of one or a mixture thereof selected from MoS2, WS2, PTFE, the method of producing a multilayer composite film having excellent lubricity and wear resistance. A multilayer composite film produced by the method of any one of claims 1 to 3 or 6 . A metal part, which is a metal mold or a wear-resistant part having the multilayered composite film of claim 7.

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