KR20120011623A - Tow layer solid lubrication ptfe plate and the manufacturing thereof - Google Patents

Abstract

PURPOSE: A method for fabricating a fluoroplastic solid lubrication substrate of dual thin film is provided to enhance strength and abrasion resistance and to prolong lifetime. CONSTITUTION: A method for fabricating a fluoroplastic solid lubrication substate of dual thin film comprises: a step of decomposing pure ammonia gas by heat under the presence of decomposition catalyst; a step of preparing reductive gas containing 75% of hydrogen and 25% of nitrogen; a step of performing reduction/thermal treatment of the reductive hydrogen gas on a bronze net; a step of preparing a bronze net-fused metal substrate without deformation of the bronze net; a step of stirring PEFE resin powder, natural graphite powder, glass fiber powder, distilled water, and non-ionic dispersion agent in a glass container to prepare alkaline water dispersion liquid; a step of evaporating moisture to prepare PTFE oligomers with high viscosity; a step of pressing using a heated pressing roller to prepare a solid lubrication substrate of half-finished goods.

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 for manufacturing the same, and to strongly attach a bronze network on a metal substrate by using a high temperature reduction method. Or a thin film fluorine resin-based solid lubrication substrate for depositing iron and tin metal on the metal substrate by chemical plating or electroless plating method, and evaporating tin metal by high temperature reduction method to strongly attach the reduced iron film having fine pores to the metal substrate; It relates to a manufacturing method.

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.

Therefore, 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 poly to a metal mesh strongly attached to a metal substrate or a composite metal substrate having a reduced iron coating formed with fine pores. When the tetrafluoroethylene (PTFE) 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 having fine pores, and the high temperature is fired to increase the degree of polymerization. The double thin PTFE fluororesin-based solid lubrication layer strongly adhered to the metal substrate increases the lubricity, wear resistance, and strength of the lubricating film. Significantly extend the life of the product When, as well as to increase the thickness of the PTFE solid lubricant layer to provide a second of the thin film which can stand the 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.

Still another object of the present invention is to use a double thin film method to strongly adhere to a pure PTFE resin to a metal substrate to increase the lubricity, wear resistance and compressive strength can be used for a long time, and to prevent noise or vibration during driving To provide a thin-film 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-layer 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 coming out when the vaporization of the liquid ammonia in the high pressure cylinder slowly A reducing gas production step of heating and decomposing ammonia to 900 ° C. to 920 ° C. under a decomposition catalyst mainly composed of chromium oxide to prepare a reducing gas having a hydrogen content of 75% hydrogen and 25% nitrogen having a dew point of -10 ° C. or less, and 40 mesh of 0.23mm bronze sand (Cu-Sn 6%) on a 0.25mm thick metal substrate using a high-temperature reducing atmosphere in which a reducing hydrogen gas containing little moisture was produced in the reducing gas manufacturing process was injected into a core tube. A reduction heat treatment step of placing a bronze wire woven with a reduction heat treatment at 970 ° C. to 1000 ° C. for 35 to 45 minutes, and the reduction heat treatment step Bronze mesh fusion metal substrate manufacturing step of manufacturing a bronze mesh fusion metal substrate in which the bronze mesh is strongly fused to the metal substrate without changing the shape of the bronze mesh (2) in the bronze network fusion metal substrate manufacturing step After that, 58.5% by weight of the PTFE resin powder of the fine solid lubricant with a particle size of 0.15 to 0.5 μm, 2.5% by weight of the fine natural graphite powder having the particle size of 0.15 to 0.30 μm as the inorganic solid lubricant and 8.0% by weight of the glass fiber powder with 0.25 μm of distilled water 30 An aqueous dispersion preparation step of preparing an alkaline stable aqueous dispersion having a pH of 9.0 by adding 0.2% by weight of ammonia water in a glass container by adding 0.8% by weight and a nonionic dispersant in a glass container, and the aqueous dispersion prepared in the aqueous dispersion preparation step. The rubbery semi-solid which the degree of polymerization was increased by evaporating the heat by evaporating water while stirring slowly for 180 to 240 minutes in a water bath maintained at a temperature of 80 to 100 ℃ The PTFE oligomer manufacturing step of preparing a high molecular viscosity PTFE oligomer, and the rubber-like semi-solid type high viscosity PTFE oligomer prepared in the PTFE oligomer manufacturing step is the bronze network fused metal substrate manufacturing step High temperature compression of PTFE resin polymer at a speed of 12 cm / sec while applying a pressure of 550 to 610 kg / ㎠ using a compression roller heated to 100 to 120 ° C. on a bronze mesh fused metal substrate having a bronze mesh attached to a metal substrate. Semi-finished PTFE solid lubrication substrate for producing semi-finished solid lubrication substrate with the polymerization of bronze mesh fused metal substrate and PTFE polymer, and semi-finished product combined with bronze network fused metal substrate and PTFE polymer in the semi-finished solid lubrication substrate manufacturing step Half of double-layer thin film strongly bonded to bronze mesh fused metal substrate and PTFE solid lubrication layer The PTFE solid lubrication substrate is heated and calcined in a kiln 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 cure, thereby achieving a uniform thickness of 0.75 mm. It characterized in that it comprises a double thin film PTFE-based solid lubrication substrate manufacturing step for producing a thin film PTFE-based solid lubrication substrate.

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 prepare a mixed solution to the step, and the mixed solution prepared in the step of preparing the mixed solution step by step to add a small amount of 1.5 mol sodium hypophosphite aqueous solution as a reducing agent step by step to clean the surface of the metal substrate (10) When immersed in the mixed solution at 80-90 ° C, activated hydrogen is generated and Fe ⁺³ and Sn ⁺² ions in the mixed solution are reduced, and the iron / tin metal precipitation step of depositing iron and tin metal on the metal substrate by electroless plating is performed. In the iron / tin metal precipitation step, a metal substrate on which iron and tin metals were deposited by electroless plating was heated at a temperature of 1120 ° C. using a high temperature reduction path of a hydrogen reducing atmosphere stream. After the reduction heat treatment for 35 minutes, all the tin precipitated on the metal substrate is evaporated, and the reduced iron film having fine pores is strongly adhered onto the metal substrate. The reduced iron film having 20 to 30% of fine pores is formed on the metal substrate by using an electroless plating method. Particle size of 0.15 to 0.5 μm to produce a double-layer PTFE solid lubrication substrate using an electroless plating step of manufacturing a composite metal substrate, and a porous substrate strongly attached to the metal substrate in the electroless plating step. PTFE resin powder 67.5% by weight of fine solid lubricant and 3.5% by weight of fine natural graphite powder having particle size of 0.15-0.30 μm, which is an inorganic solid lubricant, 28% by weight of distilled water and 0.8% by weight of nonionic dispersant were placed in a glass container and stirred with PTFE resin. , Natural graphite powder, distilled water and nonionic dispersant, followed by adding 0.2% by weight of ammonia The aqueous dispersion preparation step of preparing an alkaline stable aqueous dispersion of 9.0 and the aqueous dispersion prepared in the aqueous dispersion preparation step were evaporated while slowly stirring for 180 to 240 minutes in a water bath maintained at a temperature of 80 to 100 ℃. The step of preparing a PTFE oligomer for producing a rubber semi-solid high viscosity PTFE oligomer with increased degree of polymerization, and the PTFE high polymer of the rubber semi-solid high viscosity prepared in the manufacturing step of the PTFE oligomer PTFE resin polymer at a speed of 12 cm / sec while applying a pressure of 550 to 610 kg / cm 2 using a compression roll heated to 100 to 140 ° C. on a composite metal substrate with a reduced iron film having fine pores formed in the plating step. When high temperature compression polymerization is carried out, PTFE resin is completely embedded in the fine pores formed in the reduced iron film and is not pushed to the side. By the molding, the degree of polymerization of the PTFE polymer is greatly increased, and the semi-finished PTFE solid lubrication substrate is manufactured to form a PTFE solid lubrication substrate with a uniform and uniform thickness. The double-layered thin solid lubrication substrate on which the porous metal-bonded composite metal substrate and the PTFE solid lubrication polymer layer strongly adhered was cured by heating and baking for 20 to 25 minutes in the firing furnace of the conveyor system maintained at 360 to 380 ° C. It characterized in that it comprises a step of producing a double-layer PTFE-based solid lubrication substrate for producing a double-layer PTFE-based solid lubrication substrate excellent in lubrication properties further increased the degree of polymerization.

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 allows the metal substrate to be strongly bonded by being fused onto a metal substrate without changing the shape of the bronze network. A fused metal substrate of bronze network can be manufactured, and a fluororesin PTFE polymer is placed on the bronze network fused metal substrate. When high pressure compression molding is performed using a heating compression roller, the PTFE polymer is completely buried in the gap of the bronze mesh attached to the metal substrate, and it is not pushed to the side and formed of the PTFE high polymer by the high temperature compression molding and the high pressure PTFE polymer thereon. Double-layer PTFE solids prepared by sintering / curing PTFE solid lubrication substrate by medium thin film to increase the degree of polymerization and hardness. The advantage of the active board is that it is made of pure PTFE resin with the lowest vapor pressure and the highest melting point among fluorocarbon resins. Metal substrate and solid lubrication substrate are not detached and the thickness of the lubrication layer of the substrate is increased to greatly reduce noise and vibration during operation of the solid lubrication bearing, and the lubrication wear resistance is continuously maintained for a long time, thereby greatly extending the life of the product. And it has the effect that can greatly improve the lubricity, wear resistance, and adhesion resistance.

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 not only general mechanical parts but also sputtering device, plasma, CVD, PVD, ion injection device, etc. 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 dual-layer PTFE solid lubrication substrate formed by forming a composite metal substrate of a metal substrate-porous reduced iron film and a double polymer of PTFE polymer obtained by high-temperature reduction treatment of iron and tin metal obtained in the 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.
Figure 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 coating film is formed with a fine pores in the metal substrate according to the 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 fine pores formed thereon according to a second embodiment 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 the slow evaporation of liquid ammonia is thermally decomposed from 900 ° C to 920 ° C under a decomposition catalyst composed mainly of chromium oxide, thereby reducing hydrogen with 75% hydrogen and 25% nitrogen with almost no water dew point below -10 ° C. (Reducing hydrogen gas manufacturing step) and using a high-temperature reducing atmosphere furnace in which the reducing hydrogen gas produced in the reducing hydrogen gas manufacturing step was injected into a core tube, on a 0.25 mm thick metal substrate (1). Place a bronze mesh woven with 40 mesh of bronze yarn (Cu-Sn 6%) having a thickness of 0.23mm and reduced heat treatment at 970 ℃ to 1000 ℃ 35 minutes to 45 minutes (reduction heat treatment step), the A bronze mesh fused metal substrate was manufactured in which the bronze mesh 2 was strongly fused to the metal substrate 1 without changing the shape of the bronze mesh 2 in the original heat treatment step. ).

After the bronze mesh fusion metal substrate manufacturing step, 2.5 wt% of fine natural graphite powder having a particle size (particle size) of 0.15 to 0.5 μm of PTFE resin powder of fine solid lubricant and 58.5 wt% of inorganic solid lubricant particle size of 0.15 to 0.30 μm An alkaline stable aqueous dispersion having a pH of 9.0 (8.0% by weight of 0.25 µm glass fiber powder, 30% by weight of distilled water and 0.8% by weight of a nonionic dispersant) was added to a glass vessel while stirring and 0.2% by weight of ammonia water (PTFE resin in water , A natural graphite powder, a glass fiber powder and a solution of a nonionic dispersant) were prepared (water dispersion production step).

Evaporating moisture 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 obtain a rubber semi-solid high viscosity PTFE polymer having an increased polymerization degree Manufacturing (PTFE oligomer manufacturing step),

Bronze net with a bronze net (2) attached to the metal substrate (1) prepared in the bronze net fusion metal substrate manufacturing step of the rubber semi-solid high viscosity PTFE oligomer prepared in the PTFE oligomer manufacturing step Bronze network fusion metal substrate and PTFE polymer while high temperature compression polymerization of PTFE resin polymer at a speed of 12 cm / sec using pressure roller of 550 to 610 kg / ㎠ using a compression roller heated to 100 to 120 ° C. To prepare a solid lubrication substrate of the semi-finished product is bonded (Semifinished PTFE-based solid lubrication substrate manufacturing step).

At this time, 550 to 610kg / cm using a compression roller heated to 100 to 120 ℃ a rubber semi-solid solid viscosity of the semi-solid type prepared in the PTFE oligomer manufacturing step prepared in the PTFE oligomer manufacturing step ^When hot compression molding at a pressure of 2, the lubrication layer is completely buried in the gaps of the bronze mesh 2 constituting the bronze mesh fusion metal substrate fused at the step of manufacturing the bronze mesh fusion metal substrate, and is not pushed to the side. And a PTFE solid lubrication layer 4 formed by hot-high compression in the gap between the bronze mesh 2 and the PTFE solid lubrication layer 5 polymerized at a high pressure laminated on the PTFE solid lubrication layer 4. Semi-finished PTFE solid lubrication substrate is formed by a double thin film consisting of.

In the step of manufacturing the semi-finished PTFE-based solid lubrication substrate, the bronze-bonded metal substrate and the PTFE solid lubrication layer (5) having the bronze fused metal substrate and the PTFE polymer bonded to the semi-finished solid lubrication substrate by the double thin film method are strongly reinforced. The semi-finished PTFE solid lubrication substrate of the semi-bonded thin film was heated and calcined for 20 to 25 minutes in the firing furnace of the conveyor system maintained at a temperature of 360 to 380 ° C to finally increase the degree of polymerization and harden to a thickness of 0.75 mm. A uniform double-layer PTFE-based solid lubrication substrate of the present 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 strongly adhered to the metal substrate without deformation.

By strongly fusion of the bronze mesh 2 on the metal substrate 1, in this case, a bronze woven with 40 mesh of 0.23 mm bronze yarn (Cu-Sn 6%) on a 0.25 mm metal substrate 1 The thickness of the solid lubrication substrate is 0.75 to 0.80 mm, and the thickness of the metal substrate 1 is greater than that of the metal substrate 1 by attaching the net 2 to the high temperature reduction method and then buried the PTFE polymer and forming a lubrication substrate thereon. Since a solid lubricant layer having a double precision can be formed, a solid lubrication substrate having a thickness of 1.5 mm to 2,0 mm may be manufactured by adjusting the thickness of the metal substrate 1 and the thickness of the bronze mesh 2.

According to Example 1 of the present invention, by using a pure PTFE resin having the lowest vapor pressure and the highest melting point among the fluorine resin, compression molding at a high pressure and firing at a high temperature to increase the degree of polymerization, excellent lubricity, wear resistance, heat resistance, chemical resistance Even under high loads, the metal substrate and the solid lubricating film do not detach and maintain lubricating wear resistance continuously 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, 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, so that the solid lubrication substrates manufactured in mass production without cutting into dies are cut to a suitable size. It is economical because it can be manufactured very cheaply because it is used in the form.

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, PTFE solid lubrication layer polymerized at high pressure.

  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).

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 fine pores formed thereon in a metal substrate according to Embodiment 2 of the present invention. In the preparation method, 500 ml of ferric chloride aqueous solution at 0.5 mole concentration and 500 ml of ferrous chloride solution at 0.1 molar concentration are mixed to prepare a mixed solution (mixing solution preparing step), and the mixed solution prepared in the preparing step When 120 ml of 1.5 mol concentration sodium hypophosphite aqueous solution as a reducing agent was added stepwise, the metal substrate 10 having a clean surface was immersed in a mixed solution at 80 to 90 ° C., and activated hydrogen was generated to produce Fe in the mixed solution. ⁺³ and Sn ⁺² ions are reduced to precipitate iron and tin metal on the metal substrate by electroless plating (iron / tin metal precipitation step), and electroless in the iron / tin metal precipitation step The metal substrate 10 in which iron and tin metal were deposited by plating was subjected to a reduction heat treatment at a temperature of 1120 ° C. for 35 minutes using a high temperature reduction path of a hydrogen reducing atmosphere airflow, whereby all the tin precipitated on the metal substrate 10 was evaporated and fined. A composite metal having a reduced iron film 12 having fine pores of 20 to 30% formed thereon on the metal substrate 10 by using an electroless plating method in which pores are formed on the metal substrate 10. A substrate was prepared (electroless plating step).

67.5% by weight of PTFE resin powder, which is a fine 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 substrate strongly attached to the metal substrate 10 in the electroless plating step. PTFE resin, natural graphite powder, distilled water and nonionic dispersant with 3.5% by weight of fine natural graphite powder having particle size of 0.15 to 0.30㎛ as inorganic solid lubricant and 28% by weight of distilled water and 0.8% by weight of nonionic dispersant. 0.2 wt% aqueous ammonia was added to the mixture to prepare an alkaline stable aqueous dispersion having a pH of 9.0 (water dispersion preparation step),

Evaporating moisture 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 obtain a rubber semi-solid high viscosity PTFE polymer having an increased polymerization degree (PTFE oligomer preparation step).

The rubber semi-solid high viscosity PTFE oligomer prepared in the step of preparing the PTFE oligomer is placed on the composite metal substrate on which the reduced iron film 12 having the fine pores formed in the electroless plating step is attached. When the PTFE resin polymer is subjected to high temperature compression polymerization at a speed of 12 cm / sec using a compression roll heated to 140 ° C. at a rate of 550 to 610 kg / cm 2, the PTFE resin is completely embedded in the fine pores formed in the reduced iron film 12, Due to the high temperature and high compression molding, the polymerization degree of the PTFE polymer is greatly increased, so that a PTFE solid lubrication substrate is formed with a constant and uniform thickness (a semi-finished PTFE-based solid lubrication substrate manufacturing step).

In the manufacturing process of the semi-finished PTFE-based solid lubrication substrate, the composite thin metal substrate having the reduced iron film 12 having fine pores formed thereon by the double thin film method, and the double thin film solid lubrication substrate strongly bonded to the PTFE solid lubrication polymerization layer 360 To prepare a double-layer PTFE-based solid lubrication substrate according to Example 2 of the present invention excellent in the degree of lubrication properties further increased by curing by heating and baking for 20 to 25 minutes in the kiln of a conveyor system maintained at 380 ℃ ( Step of manufacturing double thin PTFE-based solid lubricant substrate).

High-strength PTFE lubrication layer 14 and the high-strength PTFE lubrication layer 14 by the 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 PTFE-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 PTFE lubrication by high temperature high pressure polymerization. Layer, 15 is a PTFE lubrication 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 is strongly attached to the metal substrate 10 of 0.25 mm in the thickness of 0.3 mm of the double-layer PTFE solid lubrication substrate. PTFE resin is embedded in the pores of the reduced iron film 12 with a thickness of 0.01 to 0.02 mm and a thin thickness with a 0.03 mm PTFE lubrication layer 14 attached to facilitate the manufacture of compact and lightweight solid lubrication bearings and bushings. can do.

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. Reduction heat treatment at 1150 ° C. for 35 to 45 minutes causes all the low melting point tin (melting point; 232 ° C.) deposited on the metal network to evaporate and attach the reduced iron film 12 having fine pores on 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 completely buried in the pores of 12), and the fluorine resin-based solid lubrication membrane is formed by double thin film with constant and uniform thickness. Can be prepared.

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 fine porous portion, and forming a solid lubricating substrate, a very thin double thin PTFE of 0.30mm Systemic solid lubrication substrates can be produced and contribute to the manufacture of small, lightweight solid lubricated bearings and bushings.

In the manufacturing method according to Example 2 of the present invention, by using a pure PTFE resin having the lowest vapor pressure and the highest melting point among the fluorine resin, it is compression molded at high pressure and calcined at a high temperature to increase the degree of polymerization, thereby improving lubricity, wear resistance, heat resistance, and chemical resistance. The metal substrate and the solid lubrication layer are not detached even under this excellent and high load, and the lubrication and abrasion resistance are continuously maintained for a long time, thereby greatly extending the life of the product. Also, no diluting solvent or additive additive is used at the manufacturing stage. Because only pure PTFE 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 during long-term use. CVD, PVD, ion implanter It can also be used in clean environment, such as solid lubrication bearings and bushings that are used in the interior of vacuum equipment, foodstuffs, dyeing, weaving machines, driving parts for 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 in Example 2 of the present invention, the electroless solution was prepared by gradually adding a ferric chloride and a tin tin chloride solution gradually as a reducing agent. When the iron and tin metals are precipitated by the plating method, the reaction rate is not preferable when the concentration of ferric chloride is 0.3 mol or less, and the reaction rate is fast when the concentration of ferric chloride is 0.5 mol or more. The surface state of the tin 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 is evaporated, to produce a composite metal substrate with a reduced iron film (12) formed with a fine pores of 20 to 30% by volume, In view of such a phenomenon, by adjusting the molar concentration 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)

Pure gaseous ammonia from the slow evaporation of liquid ammonia in high pressure cylinders was thermally decomposed from 900 ° C to 920 ° C under a decomposition catalyst composed mainly of chromium oxide. Reducing hydrogen gas to produce a reducing gas of 25%,
0.23 thick on a 0.25 mm thick metal substrate (1) using a high temperature reducing atmosphere furnace in which a reducing hydrogen gas produced 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 putting a bronze mesh woven of 40 mm bronze yarn (Cu-Sn 6%) on a mesh of 40 and reducing heat treatment at 970 ° C. to 1000 ° C. for 35 to 45 minutes;
Bronze mesh fusion metal substrate manufacturing step of manufacturing a bronze mesh fusion metal substrate in which the bronze mesh 2 is strongly fused to the metal substrate 1 without changing the shape of the bronze mesh (2) in the reduction heat treatment step Wow,
After the bronze network fused metal substrate manufacturing step, 2.5wt% of fine natural graphite powder and 0.25μm glass having particle size of 0.15 to 0.30μm as inorganic solid lubricant to 58.5 wt% of PTFE resin powder of fine solid lubricant having a particle size of 0.15 to 0.5㎛ An aqueous dispersion preparation step of preparing an alkaline stable aqueous dispersion having a pH of 9.0 by adding 8.0 wt% of fiber powder to 30 wt% of distilled water and 0.8 wt% of a nonionic dispersant into a glass container and adding 0.2 wt% of ammonia water while stirring;
Evaporated water by evaporating the water while gradually 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 increase the degree of polymerization rubber-like semi-solid viscosity PTFE PTFE oligomer manufacturing step of preparing the oligomer,
Bronze mesh fusion metal in which the rubber semi-solid type high viscosity PTFE oligomer prepared in the PTFE oligomer manufacturing step is attached to the metal substrate 1 in the bronze mesh fusion metal substrate in the manufacturing step of the bronze mesh fusion metal substrate. Bronze network fused metal substrate and PTFE polymer are bonded while high temperature compression polymerization of PTFE resin polymer at a speed of 12 cm / sec while applying pressure of 550 to 610 kg / ㎠ using a compression roller heated to 100 to 120 ° C. on a substrate. A semi-finished PTFE-based solid lubrication substrate manufacturing step of manufacturing a solid lubrication substrate of the semi-finished product,
In the step of manufacturing the semi-finished PTFE-based solid lubrication substrate, the bronze-bonded metal substrate and the PTFE solid lubrication layer (5) having the bronze fused metal substrate and the PTFE polymer bonded to the semi-finished solid lubrication substrate by the double thin film method are strongly reinforced. The semi-finished PTFE solid lubrication substrate of the semi-bonded thin film was heated and calcined for 20 to 25 minutes in the firing furnace of the conveyor system maintained at a temperature of 360 to 380 ° C. A method of manufacturing a double thin-film fluororesin-based solid lubrication substrate, comprising the step of preparing a double-thin PTFE-based solid lubrication substrate to produce a double-layered PTFE-based solid lubrication substrate of the present invention. According to claim 1, wherein the high-molecular rubber PTFE semi-polymer prepared in the PTFE oligomer manufacturing step using a compression roller heated to 100 to 120 ℃ high temperature at a pressure of 550 to 610 kg / cm ² When compression molding, the lubrication layer is formed at a constant and uniform thickness without being completely buried in the gaps of the bronze mesh 2 constituting the bronze mesh fusion metal substrate fused in the manufacturing process of the bronze mesh fusion metal substrate and being pushed sideways. A double thin film composed of a PTFE solid lubrication layer (4) formed by hot-high compression in the gap of (2) and a PTFE solid lubrication layer (5) polymerized at a high pressure laminated on the PTFE solid lubrication layer (4). A semi-finished PTFE solid lubrication substrate is formed by the method for producing a double thin film fluorine resin-based solid lubrication substrate. 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 prepared by gradually adding 120 ml of an aqueous 1.5% sodium hypophosphite solution as a reducing agent step by step to the mixed solution at 80 to 90 ° C. When immersed, activating hydrogen is generated and Fe ^{+ 3} and Sn ^{+ 2} ions in the mixed solution are reduced, and the iron / tin metal precipitation step of depositing iron and tin metal on the metal substrate by an electroless plating method,
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. 20% to 30% of fine pores are formed on the metal substrate 10 by using an electroless plating method in which the reduced iron film 12 having fine pores formed by evaporation of all the tin deposited on the metal substrate 10 is strongly attached onto the metal substrate 10. An electroless plating step of manufacturing a composite metal substrate having the reduced iron film 12;
67.5% by weight of PTFE resin powder, which is a fine 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 substrate strongly attached to the metal substrate 10 in the electroless plating step. PTFE resin, natural graphite powder, reduced iron film (12) with 3.5% by weight of fine natural graphite powder having a particle size of 0.15 to 0.30 µm as an inorganic solid lubricant and 28% by weight of distilled water and 0.8% by weight of nonionic dispersant in a glass container. A step of preparing an aqueous dispersion to prepare an alkaline stable aqueous dispersion having a pH of 9.0 by mixing the attached composite metal substrate, distilled water and a nonionic dispersant, and then adding 0.2% by weight of ammonia water;
Evaporating moisture 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 obtain a rubber semi-solid high viscosity PTFE polymer having an increased polymerization degree PTFE polymer manufacturing step
The rubber semi-solid high viscosity PTFE oligomer prepared in the step of preparing the PTFE oligomer is placed on the composite metal substrate on which the reduced iron film 12 having the fine pores formed in the electroless plating step is attached. When the PTFE resin polymer is subjected to high temperature compression polymerization at a speed of 12 cm / sec while applying a pressure of 550 to 610 kg / cm 2 using a compression roller heated to 140 ° C., the PTFE resin is completely embedded in the fine pores formed in the reduced iron film 12. A step of manufacturing a semi-finished PTFE-based solid lubrication substrate, which does not push sideways, thereby greatly increasing the degree of polymerization of PTFE polymer by high temperature and high compression, and forms a PTFE solid lubrication substrate with a constant and uniform thickness;
In the manufacturing step of the semi-finished PTFE-based solid lubrication substrate, the double-layered thin solid lubrication substrate strongly bonded to the composite metal substrate having the porous reduced iron coating film 12 and the PTFE solid lubrication polymerization layer by the double thin film method was 360 to 380 ° C. Step of manufacturing a double-layer PTFE-based solid lubrication substrate for producing a double-layer PTFE-based solid lubrication substrate with excellent lubrication properties by further curing by heating and baking for 20 to 25 minutes in the kiln of the conveyor system maintained in the furnace Method for producing a double-layer PTFE-based solid lubrication substrate, characterized in that. 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 according to claim 1.

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