KR101190747B1 - Tow layer solid lubrication ptfe plate and the manufacturing thereof - Google Patents

Abstract

An object of the present invention is to form a porous bronze metal mesh or pores formed by compressing a pure polytetrafluoroethylene (PTFE) resin at a high temperature and high pressure on a metal substrate attached to a metal substrate or a metal with a porous reduced iron film (12). Buried PTFE resin at high temperature, and fired at high temperature, the metal substrate and PTFE resin are attached.The double-layer PTFE fluorine resin-based solid lubrication layer attached to the metal substrate increases the wear resistance and the strength of the lubricating film. Since the metal substrate and the solid lubrication layer do not detach and maintain lubrication and abrasion resistance for a long time, it can not only prolong the life of the product drastically, but also increase the thickness of the PTFE solid lubricant layer to prevent vibration and noise when driving the bearing. The double thin PTFE-based solid lubrication substrate which can be prevented and its manufacturing method There in the ball.

Description

Double-layer fluorine resin-based solid lubrication substrate and its manufacturing method {TOW LAYER SOLID LUBRICATION PTFE PLATE AND THE MANUFACTURING THEREOF}

The present invention relates to a double-layer polytetrafluoroethylene fluorine resin (hereinafter referred to as PTFE; Poly Tetra Fluoro Ethylene) -based solid lubrication substrate and a method of manufacturing the same, and to attaching a bronze network on a metal substrate using a high temperature reduction method or A double thin film fluorine resin-based solid lubrication substrate for depositing iron and tin metal on the metal substrate by electroless plating method and attaching a reduced iron film having pores by evaporating tin metal by high temperature reduction method to the metal substrate, and a manufacturing method thereof will be.

Fluorine resins, which are widely used in the related art, have excellent lubricity, heat resistance, chemical resistance, and are used as self-lubricating materials for sliding solid lubrication bearings.

However, PTFE resin in the fluorocarbon resin has a higher melting point than other resins, and thus has excellent heat resistance. However, injection molding by melt processing has a narrow melting point (327 ° C) and decomposition temperature (387 ° C). It is not possible, but only a heat compression molding method is applied, there is a problem in that the production of a product is greatly restricted.

In addition, it is excellent in chemical resistance but has no solvents and adhesives. Therefore, there are many limitations in the molding process and use, such as special processing is required for the manufacture of solid lubrication substrate made by attaching PTFE lubricating thin film to solid metal surface. PTFE resin polymer used as a lubricant has a problem of high lubricity but high abrasion because it is an elastic rubbery solid.

Therefore, in order to reduce abrasion, various methods are used to increase the degree of polymerization to increase compressive strength, to mix natural graphite powder, molybdenum disulfide powder and bronze metal powder as inorganic lubricants, or to increase the thickness of the lubricating film. However, when the solid lubrication substrate has a large load with the shaft, the metal substrate and the solid lubrication layer are detached, and there is a problem in that there is a limit in increasing the thickness of the solid lubrication layer.

Conventionally, a method of manufacturing a solid lubrication substrate using fluorine resin is to strongly fuse the bronze powder on the metal substrate by powder metallurgy to form a bronze sintered layer having a high porosity. The solid lubrication substrate was manufactured by attaching a resin lubricating layer. However, the solid lubrication substrate thus prepared has various problems such as cracks on the surface and uneven thickness, complicated manufacturing processes, and very high manufacturing costs. there was.

In addition, a large amount of solid lubricant was impregnated in the space between the metal meshes of 0.18 to 0.50 mm in diameter made of bronze or stainless steel and interwoven with the crosswise length of the metal mesh, followed by compression molding, followed by high temperature baking to fix the metal mesh and the solid lubricant layer. Metal mesh-reinforced solid lubrication substrates are being manufactured, but the tensile strength and mechanical strength of the substrate are weak, and there is a limitation in compression molding due to the deformation of the metal network during compression molding, and the lubrication substrate is damaged. Tetrafluoroethylene-nuclear propylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), etc. may be used. There is a problem that the characteristics of the solid lubrication substrate is lowered and the structural strength is weak, so there is a limit to the use for a long time.

Recently, the metal-reinforced solid lubrication substrate and the metal substrate are attached to each other and the thickness of the solid lubricant layer can be increased to maintain lubrication and abrasion resistance for a long time to extend the life of the product, and the vibration when the solid lubrication bearing is operated And a composite fluorine resin-based solid lubrication substrate that can remove the noise has been developed.

However, perfluoropolyether (PEFE), a fluorinated polymer having a highly viscous functional group, for bonding metal mesh reinforced solid lubrication substrates and metal substrates, ETFE and polyimide resins, which are copolymers of tetrafluoroethylene and ethylene, and epoxy Resin is used, but when friction heat between lubrication board and shaft is high or when it is used for a long time, oscillation or generating gas is generated from these resins, which weakens the adhesion strength between metal substrate and metal network reinforced solid lubrication substrate and detaches the attachment site. This appears, the situation is limited to use in a clean environment, such as a device that uses a vacuum inside the home appliances.

Accordingly, the present invention has been made to solve various problems of the prior art as described above, and an object of the present invention is pure polytetrafluoroethylene in a composite metal substrate having a metal mesh attached to a metal substrate or a reduced iron film having pores formed thereon. (PTFE) When the resin is compression molded at high temperature and high pressure, the PTFE resin is buried in the porous bronze metal net or the reduced iron film in which the pores are formed, and the high temperature is fired to increase the degree of polymerization so that the metal substrate and the PTFE resin are attached to the metal substrate. Double-layer PTFE fluororesin-based solid lubrication layer increases lubricity, wear resistance, and lubrication film strength and prolongs the life of the product by maintaining metallurgy and abrasion resistance for a long time without detachment of metal substrate and solid lubrication film even under high load. PTFE solid lubricant layer as well as When increasing the thickness to provide a thin film 2 of which can prevent vibration and noise during operation of the bearing lubricating PTFE-based solid substrate and a method of manufacturing the same.

In addition, another object of the present invention is to use a lubricating fluorine resin used in the manufacture of a solid lubrication substrate using a double thin film using only a PTFE resin having the lowest vapor pressure and the highest melting point among the fluorine resin, and adhering with a dilution solvent or a metal substrate. Since no auxiliary resin is used at all, it does not generate oscillation and generating gas even if it is used for a long time or there is frictional heat.Therefore, it provides a double thin PTFE-based solid lubrication substrate and a method of manufacturing the same, which can be used in a vacuum or a clean environment. It is.

Another object of the present invention is to attach a pure PTFE resin to the metal substrate by using the double thin film method to increase the lubricity, wear resistance and compressive strength can be used for a long time, the double thin film that can prevent noise or vibration during driving The present invention provides a PTFE-based solid lubrication substrate and a method of manufacturing the same.

[ Challenge to be solved ]

The present invention has been made to solve the above various problems, the double thin film fluorine resin-based solid lubrication substrate according to the first embodiment of the present invention and a method for producing the same is pure gas ammonia when vaporizing the liquid ammonia in the high-pressure cylinder And a reducing gas prepared under a chromium oxide decomposition catalyst to produce a reducing gas of 75% hydrogen and 25% nitrogen having a dew point of -10 ° C. or lower by thermal decomposition at 900 ° C. to 920 ° C., and the reducing hydrogen prepared in the reducing gas manufacturing step. Using a high temperature reducing atmosphere furnace in which gas was injected into the core tube, a bronze mesh woven with 40 mesh of 0.23mm bronze yarn (Cu-Sn 6%) was placed on a 0.25mm thick metal substrate, and then heated at 970 ℃ to 1000 ℃. A reduction heat treatment step of reduction heat treatment for 35 to 45 minutes, and the shape of the bronze mesh is not changed in the reduction heat treatment step. Inorganic bronze to 58.5% by weight of a PTFE resin powder of a solid lubricant having a particle size of 0.15 to 0.5 μm after the bronze mesh fused metal substrate manufacturing step of manufacturing a bronze mesh fused metal substrate in which the bronze mesh is fused. 2.5 wt% of natural graphite powder having a particle size of 0.15 to 0.30 μm as a solid lubricant and 8.0 wt% of glass fiber powder having 0.25 μm, 30 wt% of distilled water and 0.8 wt% of nonionic dispersant were added to a glass container, and 0.2 wt% of ammonia water was added. To prepare an aqueous dispersion having an alkaline aqueous dispersion having a pH of 9.0, and evaporate the water while stirring the prepared aqueous dispersion for 180 to 240 minutes in a water bath maintained at a temperature of 80 to 100 ° C. PTFE oligomer manufacturing step of preparing a rubber-like semi-solid PTFE oligomer having an increased polymerization degree by thermal evaporation, and a rubber phase prepared in the PTFE oligomer manufacturing step The semi-solid PTFE oligomer was placed on the bronze mesh fused metal substrate with the bronze mesh attached to the metal substrate in the step of manufacturing the bronze mesh fused metal substrate and 550 to 610 kg / using a compression roller heated to 100 to 120 ° C. Semi-finished PTFE solid lubrication substrate manufacturing step of manufacturing a semi-finished solid lubrication substrate combined with bronze mesh fused metal substrate and PTFE polymer while high-temperature compression polymerization of PTFE resin polymer at a rate of 12 cm / sec while applying a pressure of cm 2; Double-layer semi-finished PTFE bonded to a bronze mesh fused metal substrate and PTFE solid lubrication layer attached to the semi-finished solid lubrication substrate bonded by bronze mesh fused metal substrate and PTFE polymer at the stage of solid lubrication substrate The solid lubrication substrate was heated and calcined for 20 to 25 minutes in a firing furnace of a conveyor system maintained at a temperature of 360 to 380 ° C. to finally increase the degree of polymerization. To cure thereby characterized in that the thickness of the thin film comprises a PTFE based solid lubricant substrate manufacturing steps of the thin film 2 for preparing the two of the PTFE based solid lubricant substrate of the present invention by a uniform 0.75mm.

In addition, according to the second embodiment of the present invention, the method for manufacturing a double-layer thin film fluorine resin-based solid lubrication substrate is prepared by mixing 500 ml of ferric chloride aqueous solution at 0.5 molar concentration with 500 ml of 0.1 mol ferric chloride aqueous solution. To a mixed solution prepared in the step of preparing and the mixed solution prepared in the step of preparing a mixed solution of 120 mol of sodium hypophosphite aqueous solution of 1.5 mol concentration as a reducing agent step by step to 80 to 90 ℃ When immersed in the mixed solution of the Fe ^{+ 3} , Sn ^{+ 2} ions in the mixed solution is generated and the iron / tin metal precipitation step of depositing iron and tin metal on the metal substrate by electroless plating method, and the iron / The metal substrate on which iron and tin metal were precipitated by electroless plating in the tin metal precipitation step was used for 35 minutes at a temperature of 1120 ° C. using a high temperature reduction furnace of a hydrogen reducing atmosphere stream. Electroless plating method for producing a composite metal substrate having a reduced iron film having 20 to 30% of pores formed thereon on the metal substrate by using an electroless plating method in which tin deposited on the metal substrate is evaporated by reduction heat treatment to deposit a pored reduced iron film on the metal substrate. 67.5% by weight of PTFE resin powder, which is a solid lubricant having a particle size of 0.15 to 0.5 μm, in order to manufacture a double-layer PTFE solid lubrication substrate using a porous plating step attached to a metal substrate in the electroplating step and the electroless plating step. Mixing PTFE resin, natural graphite powder, distilled water and nonionic dispersant by mixing 3.5% by weight of natural graphite powder having an inorganic solid lubricant particle size of 0.15 to 0.30 µm with 28% by weight of distilled water and 0.8% by weight of nonionic dispersant in a glass container while stirring. Water solution production step to prepare an alkaline stable water dispersion having a pH of 9.0 by adding 0.2% by weight of ammonia water And, to prepare a rubber semi-solid PTFE oligomer of the polymerization degree is increased by evaporating the water while stirring the aqueous dispersion prepared in the aqueous dispersion preparation step for 180 to 240 minutes in a water bath maintained at a temperature of 80 to 100 ℃ The PTFE oligomer manufacturing step and the rubbery semi-solid PTFE oligomer prepared in the PTFE oligomer manufacturing step are placed on a composite metal substrate having a reduced iron film having pores formed in the electroless plating step, and then subjected to 100 to 140 ° C. When the PTFE resin polymer is subjected to high temperature compression polymerization at a rate of 12 cm / sec while applying a pressure of 550 to 610 kg / cm 2 using a heated compression roll, the PTFE resin is embedded in pores formed in the reduced iron film and is not pushed to the side, thereby causing high temperature compression. Semifinished PTFE Solid Lubricator which increases the degree of polymerization of PTFE polymer to form a PTFE solid lubrication substrate with uniform, uniform thickness In the manufacturing step and the semi-finished PTFE solid lubrication substrate manufacturing step, a double thin film solid lubrication substrate, to which a composite metal substrate having a reduced iron film adhered and a PTFE solid lubrication polymerization layer was fixed by a double thin film method, was maintained at 360 to 380 ° C. And a double thin-film PTFE-based solid lubrication substrate manufacturing step of producing a double-thin PTFE-based solid lubrication substrate having an increased degree of polymerization by curing by heating and firing for 20 to 25 minutes in a calcination furnace of the system.

According to the double-layered thin film fluorine resin-based solid lubrication substrate according to the first embodiment of the present invention and a method for manufacturing the same, a bronze network is placed on a metal substrate and a high temperature reduction furnace having a hydrogen reduction atmosphere having a very low dew point (-10 ° C) is used. Reduction heat treatment can produce a bonded metal substrate and a fused metal substrate of a bronze network fused on a metal substrate without changing the shape of the bronze network, and heating the fluororesin-based PTFE polymer on the bronze network fused metal substrate. When high-temperature high-pressure molding using a compression roller is carried out by the PTFE polymer embedded in the gap of the bronze mesh attached to the metal substrate and is not pushed to the side. The advantages of the double thin PTFE solid lubrication substrate prepared by baking / curing the PTFE solid lubrication substrate at high temperature to increase the degree of polymerization and hardness Among the fluorocarbon resins, pure PTFE resin, which has the lowest vapor pressure and the highest melting point, is compression molded at high pressure and fired at high temperature to increase the degree of polymerization, thereby increasing lubricity, abrasion resistance, heat resistance, chemical resistance, and the like. It does not detach and increases the thickness of the lubrication layer of the substrate to reduce noise or vibration during operation of the solid lubrication bearing and maintains lubricating wear resistance continuously for a long time, thereby significantly extending the life of the product. There is an effect that can improve the sex.

In addition, the double thin film fluorine resin-based solid lubrication substrate and its manufacturing method according to Example 1 of the present invention use only a pure PTFE resin in the manufacturing process of the solid lubrication substrate, and use only pure PTFE resin, so that the solid lubrication during operation It does not generate heat of friction between layers and shafts, and does not generate oscillation or gas generated from these lubricants when used for a long time, so it is a device that uses the inside as a vacuum such as sputtering device, plasma, CVD, PVD, ion implantation device as well as general mechanical parts. In addition, there is an effect that a PTFE-based solid lubrication substrate that can be used in a clean environment, such as solid lubrication bearings or bushings used in driving parts of foodstuffs, dyeing, weaving and home appliances, and passenger cars, can be manufactured.

In addition, according to the double-layer thin-film fluorine resin-based solid lubrication substrate according to Example 2 of the present invention and a method for producing the same, the electroless plating method using the ferric chloride and the first tin chloride solution using a sodium hypophosphite solution as a reducing agent The thin film PTFE solid lubrication substrate formed by forming a double metal film of PTFE and a composite metal substrate of a porous reduced iron film and a PTFE polymer by high temperature reduction treatment of the obtained iron and tin metal in a high temperature reduction furnace has excellent lubrication characteristics. In addition, since a thin PTFE solid lubrication substrate of about 0.3 mm can be manufactured, it can be used for miniaturization and weight reduction.

1 is a perspective view schematically showing a solid lubrication bearing manufactured using a double thin film fluorine resin-based solid lubrication substrate prepared by fusing a bronze network to a metal substrate according to Example 1 of the present invention.
FIG. 2 is a longitudinal cross-sectional view schematically shown along the longitudinal direction in FIG. 1.
FIG. 3 is a flowchart illustrating a manufacturing procedure of a double thin film fluorine resin-based solid lubrication substrate manufactured by fusing a bronze network to a metal substrate according to Example 1 of the present invention.
4 is a longitudinal cross-sectional view of a double thin film fluorine resin-based solid lubrication substrate using a composite metal substrate having a reduced iron film having pores formed thereon according to a second embodiment of the present invention.
FIG. 5 is a manufacturing flowchart of a double thin-film fluorine resin-based solid lubrication substrate using a composite metal substrate having a reduced iron film having pores formed thereon according to Example 2 of the present invention.

Hereinafter, a method of manufacturing a double thin film fluorine resin-based solid lubrication substrate manufactured by fusing a bronze network to a metal substrate according to Example 1 of the present invention will be described in detail with reference to the accompanying drawings.

As shown in Figures 1 to 3, the manufacturing method of the double thin film fluorine resin-based solid lubrication substrate prepared by fusing a bronze net to the metal substrate according to the first embodiment of the present invention is contained in a high pressure cylinder (high pressure vessel) Pure gaseous ammonia from vaporizing liquid ammonia was thermally decomposed from 900 ° C to 920 ° C under a chromium oxide decomposition catalyst to prepare a reducing gas of 75% hydrogen and 25% nitrogen having a dew point of -10 ° C or lower (reducing hydrogen gas production step). ), 0.23 mm bronze yarn (Cu-Sn 6%) on a 0.25 mm thick metal substrate (1) using a high temperature reducing atmosphere furnace in which the reducing hydrogen gas prepared in the step of producing the reducing hydrogen gas was injected into a core tube. Put a bronze mesh woven with 40 mesh and reduce heat treatment at 970 ° C. to 1000 ° C. for 35 minutes to 45 minutes (reduction heat treatment step), and the phase of the bronze network 2 is not changed in the reduction heat treatment step. The bronze foil (2) bronze mesh fused metal substrate is welded to the metal substrate 1 was produced (bronze mesh fused metal substrate fabrication step).

After the bronze mesh fusion metal substrate manufacturing step, 2.5% by weight of natural graphite powder having 0.255% by weight of PTFE resin powder of the solid lubricant having a particle size (particle size) of 0.15 to 0.5㎛ and inorganic particles having a particle size of 0.15 to 0.30㎛ Alkaline aqueous dispersion having a pH of 9.0 by adding 8.0% by weight of glass fiber powder to 30% by weight of distilled water and 0.8% by weight of nonionic dispersant into a glass container and adding 0.2% by weight of ammonia water while stirring (PTFE resin, natural graphite Powder, glass fiber powder and a solution of the nonionic dispersant) were prepared (water dispersion preparation step).

Evaporating water while stirring the aqueous dispersion prepared in the aqueous dispersion manufacturing step at a temperature of 80 to 100 ℃ for 180 to 240 minutes to prepare a rubber-like semi-solid PTFE oligomer of increased polymerization degree (PTFE Oligomer manufacturing step),

Bronze network fusion metal substrate with a bronze network (2) attached to the metal substrate (1) prepared in the bronze network fusion metal substrate manufacturing step of the rubber semi-solid PTFE oligomer prepared in the PTFE oligomer manufacturing step Bronze network fused metal substrate and PTFE polymer were combined while high temperature compression polymerization of PTFE resin polymer at a speed of 12 cm / sec using pressure roller of 550 to 610 kg / cm 2 using a compression roller heated to 100 to 120 ° C. A solid lubrication substrate of a semifinished product was prepared (manufacturing step of semifinished PTFE-based solid lubrication substrate).

At this time, when the rubber semi-solid PTFE oligomer prepared in the PTFE oligomer manufacturing step using a compression roller heated to 100 to 120 ℃ high temperature compression molding at a pressure of 550 to 610kg / cm ² fusion of the bronze network Bronze network fused at the stage of metal substrate manufacturing A lubrication layer is formed at a constant and uniform thickness without being buried by being buried in the gap of the bronze network 2 constituting the fused metal substrate and having a high temperature in the gap of the bronze network 2. Semi-finished PTFE solid lubrication substrate by double thin film composed of PTFE solid lubrication layer 4 formed by high compression and high pressure polymerized PTFE solid lubrication layer 5 laminated on the PTFE solid lubrication layer 4 Is formed.

Fixing the bronze mesh fused metal substrate and the PTFE solid lubrication layer (5) attached to the bronze fusion metal substrate and the semi-finished solid lubrication substrate combined with the PTFE polymer by the double-film method in the manufacturing step of the semi-finished PTFE-based solid lubrication substrate The double-layered semi-finished PTFE solid lubrication substrate was heated and calcined in a firing furnace of a conveyor system maintained at a temperature of 360 to 380 ° C. for 20 to 25 minutes to finally increase the degree of polymerization and to harden, thereby obtaining a uniform thickness of 0.75 mm. A double thin film PTFE-based solid lubrication substrate of the invention was prepared (double layer PTFE-based solid lubrication substrate manufacturing step).

Accordingly, the double-layered PTFE-based solid lubrication substrate of the present invention uses a high-temperature reduction furnace of a hydrogen reduction atmosphere airflow having a very low dew point (below -10 ° C) to place a bronze mesh (2) on the metal substrate (1). Reduction heat treatment at 35 ° C. to 40 ° C. at 1000 ° C. to 1000 ° C. causes the bronze mesh to be fused and attached onto the metal substrate without deforming the shape of the bronze mesh.

By fusing the bronze mesh 2 on the metal substrate 1, at this time, a bronze mesh woven with 40 mesh of 0.23 mm bronze yarn (Cu-Sn 6%) on the 0.25 mm metal substrate 1 2) by high temperature reduction method, the thickness of the solid lubrication substrate by the double thin film in which the PTFE polymer was embedded and the lubrication substrate formed thereon is 0.75 to 0.80mm, which is about twice the thickness of the metal substrate (1). Since the solid lubricant layer can be formed, by adjusting the thickness of the metal substrate 1 and the thickness of the bronze mesh 2, a solid lubrication substrate having a thickness of 1.5 mm to 2,0 mm may be manufactured.

According to Example 1 of the present invention, the pure PTFE resin having the lowest vapor pressure and the highest melting point among the fluorine resins is compression molded at high pressure and calcined at a high temperature to increase the degree of polymerization, thereby providing excellent lubricity, abrasion resistance, heat resistance, chemical resistance and high load. The metal substrate and the solid lubricating film are not detached and maintain the lubricity and wear resistance for a long time, thereby greatly extending the life of the product.

In addition, since only pure PTFE resin is used without using a diluting solvent or adhesion additive in the manufacturing stage, there is no frictional heat between the solid lubrication membrane and the shaft during operation or no oscillation or gas is generated from these resins for long time use. It can be used in a clean environment such as plasma, CVD, PVD ion implanter, etc., which uses the inside as a vacuum, solid lubrication bearings and bushings used in the interior of foodstuffs, dyeing, weaving machines, home appliances and passenger cars.

In addition, the sliding solid lubrication bearings and bushings used in the drive parts of industrial equipment in various fields are different in size and shape according to the use, so that the solid lubrication substrates manufactured by mass production without cutting into dies are cut into suitable sizes. Since the form is manufactured and used, it can be manufactured very cheaply and it is economical.

1 and 2, 1 is a metal substrate, 2 is a bronze mesh, 3 is a fusion welded portion of the metal substrate 1 and the bronze mesh 2, and 4 is PTFE lubrication by high pressure-high polymerization. Layer, 5 is a high pressure polymerized PTFE solid lubrication layer and 100 is a solid lubrication bearing.
The 0.75 mm thick double-layer PTFE solid lubrication layer 5 manufactured as described above has a metal substrate 1 of 0.25 mm thick, and a bronze mesh 2 and a PTFE resin buried in the gap are about 0.25 mm thick. On the PTFE lubrication layer 4 by high pressure-high polymerization, the thickness of the PTFE solid lubricant layer 5 was about 0.25 mm, which was about twice that of the metal substrate (0.25 mm).

delete

The reducing atmosphere when the hydrogen-reducing atmosphere air stream of Example 1 was placed on a 0.25 mm-thick metal substrate in a high temperature reducing atmosphere furnace connected to a low-core tube by placing a bronze mesh woven with 40 mesh of 0.23 mm thick bronze yarn on the substrate and heat-treating the same. When the furnace temperature was below 950 ° C., the fusion was not fused to each other. When the furnace temperature was 1120 ° C. or more, all of the bronze mesh melted and changed into a lump state on the metal substrate without a shape.

In addition, when the heat treatment time is 30 minutes or less, complete fusion is not formed, and when the heat treatment is performed at a temperature of 50 minutes or more, the shape of the metal film is changed.

Therefore, the state when the temperature to the reducing atmosphere was heat-treated for 35 minutes to 45 minutes at 970 ℃ to 1000 ℃ was the best.

In addition, the welding properties of Cu-Sn 6%, which is the most commonly used alloy among Cu-Sn 2%, Cu-Sn 4%, Cu-Sn 6%, Cu-Sn 8%, and Cu-Sn 10% Was the best.

Next, a method of manufacturing a double thin film fluorine resin-based solid lubrication substrate manufactured using a composite metal substrate having a reduced iron film having fine pores formed thereon in a metal substrate according to Example 2 of the present invention will be described in detail. .

4 and 5, a double thin film fluorine resin-based solid lubrication substrate manufactured using a composite metal substrate having a reduced iron film 12 having pores formed thereon in a metal substrate according to Embodiment 2 of the present invention. The method is prepared by mixing 500 ml of ferric chloride aqueous solution of 0.5 molar concentration and 500 ml of 0.1 mol ferric chloride aqueous solution to prepare a mixed solution (mixing solution preparing step), and reducing the mixed solution prepared in the mixed solution manufacturing step Fe ⁺³ in the solution is mixed with the active hydrogen when immersed generation 1.5 molar concentration of the hypophosphite second metal substrate 10, a cleaning treatment of a surface with step-by-step addition of the aqueous solution of sodium hydrogen 120ml in a mixture of 80 to 90 ℃, Sn ⁺² ions are reduced as electroless deposition of tin and iron metal on the metal substrate by plating and (iron / tin metal precipitation stage), an electroless plating method with iron in the iron / tin metal precipitation stage A reduced iron film in which pores were formed by evaporating all the tin precipitated on the metal substrate 10 by heat-treating the metal substrate 10 on which the tin metal was precipitated at a temperature of 1120 ° C. for 35 minutes using a high-temperature reduction path of a hydrogen reducing atmosphere stream. Using the electroless plating method (12) attached on the metal substrate 10, a composite metal substrate having a reduced iron film 12 having 20 to 30% of pores formed on the metal substrate 10 was prepared (electroless plating). step).

67.5% by weight of PTFE resin powder and inorganic solids having a particle size of 0.15 to 0.5 μm in order to manufacture a double-layer PTFE solid lubrication substrate using a porous substrate attached to the metal substrate 10 in the electroless plating step. 3.5% by weight of natural graphite powder having a particle size of 0.15 to 0.30 μm as a lubricant, 28% by weight of distilled water and 0.8% by weight of a nonionic dispersant were mixed in a glass container, and then mixed with PTFE resin, natural graphite powder, distilled water and a nonionic dispersant. 0.2 wt% aqueous ammonia was added to prepare an alkaline aqueous dispersion having a pH of 9.0 (water dispersion preparation step),

Evaporating water while stirring the aqueous dispersion prepared in the aqueous dispersion preparation step in a water bath maintained at a temperature of 80 to 100 ℃ for 180 to 240 minutes to prepare a rubber-like semi-solid PTFE oligomer of increased polymerization degree. (PTFE oligomer preparation step).

The rubber semi-solid PTFE oligomer prepared in the manufacturing step of the PTFE oligomer is placed on the composite metal substrate to which the reduced iron film 12 having pores formed in the electroless plating step is attached and heated to 100 to 140 ° C. When the high temperature compression polymerization of the PTFE resin polymer at a speed of 12cm / sec while applying a pressure of 550 to 610kg / cm2 using the compressed roll, the PTFE resin is embedded in the pores formed in the reduced iron film 12 and is not pushed to the side. As a result, the degree of polymerization of the PTFE polymer is increased to form a PTFE solid lubrication substrate with a uniform and uniform thickness (semi-finished PTFE-based solid lubrication substrate manufacturing step).

360 to 380 ° C., a double thin film solid lubrication substrate on which a composite metal substrate having a reduced iron film 12 having pores formed thereon by a double thin film method and a PTFE solid lubrication polymerization layer were fixed to the semi-finished PTFE-based solid lubrication substrate manufacturing step. A double thin-film fluorine resin (PTFE-based) solid lubrication substrate was prepared according to Example 2 of the present invention to increase the degree of polymerization by curing by heating and baking for 20 to 25 minutes in a firing furnace of a conveyor system maintained at Resin-based solid lubrication substrate manufacturing step).

High-strength PTFE lubrication layer 14 and high-strength PTFE lubrication layer 14 by high-temperature high-pressure compression polymerization embedded in the pores of the reduced iron film 12 by the double-film method in the manufacturing step of the double-film fluorine resin-based solid lubrication substrate A double thin film PTFE lubrication layer composed of a high pressure polymerized PTFE lubrication layer (15) is formed.

In FIG. 4, 10 is a metal substrate, 12 is a reduced iron film by electroless plating, 13 is a fusion welded metal plate and a reduced iron film 12 by high temperature reduction, and 14 is a high-strength PTFE by high temperature high pressure polymerization. Lubricating layer, 15 is a PTFE lubricating layer polymerized at high pressure.

As described above, the thickness of the double-layer PTFE solid lubrication substrate manufactured by Example 2 of the present invention was 0.3 mm, and the reduced iron attached to the metal substrate 10 having a thickness of 0.25 mm was 0.3 mm of the thickness of the double-layer PTFE solid lubrication substrate. PTFE resin embedded in the pores of the coating 12 is 0.01 to 0.02mm thick and 0.03mm PTFE lubrication layer 14 is attached to the thickness of the thin and thin solid lubrication bearing and bushing can be easily manufactured Can be.

In the double-layered PTFE-based solid lubrication substrate prepared in Example 2 of the present invention, a mixed solution of ferric chloride and stannous chloride was added with sodium dihydrogen hypophosphite solution as a reducing agent, and the mixed solution at 80 ° C to 90 ° C. When the metal substrate is immersed in 10 minutes to 15 minutes, the iron and tin metal by electroless plating method is reduced and precipitated on the metal substrate 10, and the reduced and precipitated metal substrate is 1120 ° C. to the high temperature reduction furnace of the hydrogen reducing atmosphere stream. When the reduction heat treatment is performed at 1150 ° C. for 35 to 45 minutes, all of the low melting point tin (melting point; 232 ° C.) deposited on the metal network is evaporated and the reduced iron film 12 having pores is attached onto the metal substrate.

Thus, when the high-pressure-compression molding of rubber-like PTFE polymer on the metal substrate 10 to which the reduced iron film 12 having many pores by the electroless plating method is applied using a roller, the porous reduced iron film by the electroless plating method and the high temperature reduction ( The fluorine resin is buried in the pores of 12), and the fluorine resin-based solid lubrication membrane is formed by a double thin film with a constant and uniform thickness. The PTFE-based solid lubrication substrate has a very high adhesion when the polymerization degree is increased by high temperature / firing. It can manufacture.

In addition, when forming a porous reduced iron film 12 of 0.01 to 0.02mm by electroless plating on a 0.25mm metal substrate, embedding a PTFE-based solid lubricant in a porous area, and forming a solid-lubricated substrate, a 0.30mm ultra-thin double-thin PTFE-based Solid lubrication substrates can be produced and contribute to the manufacture of small, lightweight solid lubricated bearings and bushings.

According to the second embodiment of the present invention, the pure PTFE resin having the lowest vapor pressure and the highest melting point among the fluorine resins is compression molded at high pressure and calcined at high temperature to increase the degree of polymerization, thereby providing excellent lubricity, wear resistance, heat resistance, chemical resistance and high The metal substrate and the solid lubrication layer do not detach even under the load, and the lubrication and abrasion resistance are continuously maintained for a long time, thereby greatly extending the life of the product.In addition, pure PTFE is not used in the manufacturing process without using a diluting solvent or an attachment resin. Since only the resin is used, it does not generate frictional heat due to friction between the solid lubrication layer and the shaft during operation, and does not generate oscillation or gas generated from these resins when used for a long time. Therefore, sputtering equipment, plasma, CVD, PVD as well as general mechanical parts The inside of vacuum It can be used in clean environment, such as solid lubrication bearings and bushings, which are used in the equipment used in home appliances, foodstuffs, dyeing, weaving machines, home appliances, and passenger cars.

In addition, sliding solid lubrication bearings and bushings used in driving parts of industrial equipment in various fields are different in size and shape depending on the use. Therefore, the solid lubrication substrate manufactured by mass production without cutting into dies is cut into a suitable size. It is very economical because it is manufactured and used.

In the preparation of the double-layered PTFE-based solid lubrication substrate prepared according to Example 2 of the present invention, the electroless plating method is carried out by adding a ferric chloride and a tin tin chloride solution in a stepwise manner with a sodium dihydrogen hypophosphite solution as a reducing agent. When precipitated iron and tin metal, the reaction rate is not preferable if the concentration of ferric chloride is 0.3 mol or less, and iron and tin precipitated while the reaction rate is fast if the concentration of ferric chloride is 0.5 mol or more The surface condition of the metal was rough.

The ratio of iron and tin metal precipitated by the electroless plating method was precipitated in a molar ratio of 0.5 mol of ferric chloride solution and 0.1 mol of stannous chloride when reacted, and the precipitated iron metal was 28 g (0.5 mol). And tin metal were in the ratio of 11.8 g (0.1 mol).

In addition, when the reduction heat treatment for about 35 minutes at 1120 ℃ using a high temperature reduction furnace, all the precipitated tin was evaporated, and a composite metal substrate having a reduced iron film 12 having pores of 20 to 30% by volume was prepared. In view of the same phenomenon, by adjusting the molarity of the ferric chloride solution and the tin tin chloride, it was possible to control the volume of the micropores present in the reduced iron film 12.

In addition, in Examples 1 and 2 of the present invention, containing more than 0.8% by weight of the nonionic dispersant may uniformly disperse the PTFE resin, natural graphite powder, glass fiber powder, but a lot of bubbles are not preferable, If it contained less than 0.8 weight% of nonionic dispersing agents, foam | bubble did not generate but it was not able to disperse | distribute uniformly.

In the above description, the specific embodiments have been shown and described, but the present invention is not limited thereto, for example, by those skilled in the art without departing from the concept of the present invention. Not only can the design be changed in various ways, but the design change is included in the scope of the present invention.

1: metal substrate 2: bronze network
3: Fusion part 4: PTFE lubrication layer by high pressure-high compression polymerization
5: PTFE solid lubrication layer polymerized at high pressure
10: metal substrate 12: reduced iron film
13: Fusion part 14: PTFE lubrication layer by high temperature high pressure polymerization
15: high pressure polymerized PTFE lubrication layer

Claims (4)

Reducible gaseous gaseous ammonia from vaporizing liquid ammonia in high pressure cylinders is thermally decomposed from 900 ° C to 920 ° C under a chromium oxide decomposition catalyst to produce reducing gas of 75% hydrogen and 25% nitrogen with dew point below -10 ° C. Hydrogen gas manufacturing step,
A bronze yarn having a thickness of 0.23 mm on a 0.25 mm thick metal substrate 1 using a high temperature reducing atmosphere furnace in which a reducing hydrogen gas prepared in the reducing hydrogen gas manufacturing step prepared in the reducing hydrogen gas manufacturing step was injected into a core tube. A reduction heat treatment step of placing a bronze mesh woven with 40 mesh of (Cu-Sn 6%) and reducing heat treatment at 970 ° C to 1000 ° C for 35 to 45 minutes;
A bronze mesh fusion metal substrate manufacturing step of manufacturing a bronze mesh fusion metal substrate in which the bronze mesh 2 is fused to the metal substrate 1 without changing the shape of the bronze mesh 2 in the reduction heat treatment step;
2.5 wt% of natural graphite powder and 0.25 μm of glass fiber powder having a particle size of 0.15 to 0.30 μm to 58.5 wt% of PTFE resin powder of a solid lubricant having a particle size of 0.15 to 0.5 μm after the bronze mesh fusion metal substrate manufacturing step An aqueous dispersion preparation step of preparing an alkaline stable aqueous dispersion having a pH of 9.0 by adding 8.0% by weight of 30% by weight of distilled water and 0.8% by weight of a nonionic dispersant into a glass container and adding 0.2% by weight of ammonia water while stirring;
Evaporating the water while evaporating the water while stirring the aqueous dispersion prepared in the aqueous dispersion manufacturing step in a water bath maintained at a temperature of 80 to 100 ℃ for 180 to 240 minutes to prepare a rubber-like semi-solid PTFE oligomer of increased polymerization degree PTFE oligomer manufacturing step
The rubber semi-solid PTFE oligomer prepared in the PTFE oligomer manufacturing step is placed on the bronze mesh fused metal substrate having the bronze mesh 2 attached to the metal substrate 1 in the bronze mesh fusion metal substrate manufacturing step. Of a semi-finished product combined with a bronze mesh fused metal substrate and a PTFE polymer while high-temperature compression polymerization of a PTFE resin polymer at a speed of 12 cm / sec using a compression roller heated to 100 to 120 ° C. at a pressure of 550 to 610 kg / cm 2. A semi-finished PTFE-based solid lubrication substrate manufacturing step of manufacturing a solid lubrication substrate,
Fixing the bronze mesh fused metal substrate and the PTFE solid lubrication layer (5) attached to the bronze fusion metal substrate and the semi-finished solid lubrication substrate combined with the PTFE polymer by the double-film method in the manufacturing step of the semi-finished PTFE-based solid lubrication substrate The double-layered semi-finished PTFE solid lubrication substrate was heated and calcined in a firing furnace of a conveyor system maintained at a temperature of 360 to 380 ° C. for 20 to 25 minutes to finally increase the degree of polymerization and to harden, thereby obtaining a uniform thickness of 0.75 mm. A method of manufacturing a double thin film fluororesin-based solid lubrication substrate, comprising the step of manufacturing a double thin film PTFE-based solid lubrication substrate to prepare a double thin film PTFE-based solid lubrication substrate. According to claim 1, wherein the high-pressure compression molding of the rubber semi-solid PTFE oligomer prepared in the PTFE oligomer manufacturing step at a pressure of 550 to 610kg / cm ² using a compression roller heated to 100 to 120 ℃ The lubrication layer is formed with a constant and uniform thickness without being buried sideways by being buried in the gap of the bronze mesh 2 constituting the bronze mesh fusion metal substrate fused in the manufacturing process of the bronze mesh fusion metal substrate. Semi-finished PTFE by double thin film composed of PTFE solid lubrication layer 4 formed by high temperature-high compression in the gap and high pressure polymerized PTFE solid lubrication layer 5 laminated on the PTFE solid lubrication layer 4. A solid lubrication substrate is formed. A mixed solution preparation step of preparing a mixed solution by mixing 500 ml of a 0.5 mol ferric chloride aqueous solution and 500 ml of a 0.1 mol tin ferric chloride aqueous solution;
The mixed solution prepared in the step of preparing the mixed solution was added to 120 ml of a 1.5 molar sodium hypophosphite aqueous solution as a reducing agent in stages, and the metal substrate 10 having a clean surface was immersed in a mixed solution at 80 to 90 ° C. The iron / tin metal precipitation step of depositing iron and tin metal on the metal substrate by electroless plating while reducing the active hydrogen and reducing Fe ⁺³ and Sn ⁺² ions in the mixed solution;
In the iron / tin metal precipitation step, the metal substrate 10 in which iron and tin metal were precipitated by electroless plating was subjected to reduction heat treatment for 35 minutes at a temperature of 1120 ° C. using a high-temperature reduction furnace of a hydrogen reducing atmosphere stream. The reduced iron film 12 in which 20 to 30% of pores are formed on the metal substrate 10 by using an electroless plating method in which all of the tin precipitated on the evaporated evaporation is attached onto the metal substrate 10. Electroless plating step of manufacturing a composite metal substrate with a),
In order to manufacture a PTFE thin lubrication substrate of a double thin film using a porous substrate attached to the metal substrate 10 in the electroless plating step, 67.5% by weight of PTFE resin powder and inorganic solids having a particle size of 0.15 to 0.5㎛ 3.5 wt% of natural graphite powder having a particle size of 0.15 to 0.30 μm as a lubricant, 28 wt% of distilled water and 0.8 wt% of a nonionic dispersant were put into a glass container, and the PTFE resin, the natural graphite powder, and the reduced iron film 12 were attached while stirring. An aqueous dispersion preparation step of preparing an alkaline stable aqueous dispersion having a pH of 9.0 by mixing a metal substrate, distilled water and a nonionic dispersant, and then adding 0.2% by weight of ammonia water,
PTFE low polymer to prepare a rubbery semi-solid PTFE oligomer having an increased degree of polymerization by evaporating water while stirring the aqueous dispersion prepared in the aqueous dispersion preparation step at a temperature of 80 to 100 ° C. for 180 to 240 minutes. Polymer manufacturing step,
The rubber semi-solid PTFE oligomer prepared in the step of preparing the PTFE oligomer is placed on the composite metal substrate having the reduced iron film 12 having pores formed in the electroless plating step and heated to 100 to 140 ° C. When the high temperature compression polymerization of the PTFE resin polymer at a speed of 12 cm / sec while applying a pressure of 550 to 610 kg / ㎠ using a compressed roller, the PTFE resin is embedded in the pores formed in the reduced iron film 12 and does not push to the side The step of producing a semi-finished PTFE-based solid lubrication substrate to increase the degree of polymerization of the PTFE polymer, to form a PTFE solid lubrication substrate with a uniform and uniform thickness,
In the manufacturing step of the semi-finished PTFE-based solid lubrication substrate, the composite thin metal substrate with the porous reduced iron film 12 and the PTFE solid lubrication polymer layer adhered to each other by the double thin film method are maintained at 360 to 380 ° C. A double-layer PTFE-based solid lubrication substrate comprising the step of producing a double-layer PTFE-based solid lubrication substrate with a high degree of polymerization by heating and curing for 20 to 25 minutes in a firing furnace of a conventional conveyor system Method for producing a thin film fluorine resin-based solid lubricant substrate. A double thin film fluorine resin-based solid lubrication substrate, which is prepared by the method for producing a double thin film fluorine resin-based solid lubrication substrate of claim 1.

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