JPS62196351A - Solid lubricative composite material and its production - Google Patents

Abstract

PURPOSE:To lower the specific wear rate of a composite material and the coefft. of friction and to improve the strength by forming a prescribed massive phase contg. a lubricative substance as the principal component in the composite material and by feeding the lubricative substance in the form of a film to the contact surface of the composite material to be brought into contact with an opposite material. CONSTITUTION:Power of <30mum particle size contg. a lubricative substance as the principal component is granulated to form composite granules. The composite granules are mixed with powder for forming a binding phase and the mixture is compacted and sintered in a nonoxidizing atmosphere to obtain a sintered body consisting of 10-80wt% massive phase and the balance metal- base binding phase. The massive phase is composed of plural particles of <30mum particle size contg. the lubricative substance as the principal component has 30-1,000mum size.

Description

Detailed Description of the Invention (Industrial Application!?) The present invention relates to a solid-liquid composite material suitable for bearing materials or sliding materials used as various mechanical parts.

(Prior art) Conventionally, sintered bodies made of one substance and various metals or alloys have been used for lubricating purposes such as tungsten disulfide, molybdenum disulfide, graphite, graphite fluoride, and calcium fluoride.
It is used as a sex material. Representative examples of these conventional solid lubricating materials include JP-A No. 49-7108 (, 3) and JP-A-50-3 published by one of the present inventors.
0706, JP-A-53-58910-A, and JP-A-53-122059.

OR,, IF that Ming tries to solve, l X point) - 111 such as tungsten sulfide, molybdenum dioxide or graphite
1. What is a solid lubricating material consisting of a lubricating substance and a binder phase of various metals or alloys? llI appearance as a lubricant9. The raw material 1 powder and the starting raw material powder as a binder phase are simultaneously mixed and then sintered. I? (Lubricating substances have poor dispersibility, especially 1) As the content of lubricating substances increases, this tendency becomes worse, resulting in lower strength of solid lubricating materials and increased wear. Therefore, there is a problem that the service life is significantly reduced.

The present invention solves the problems mentioned in 1-1, and consists of a lumpy phase whose Y component is a slippery substance with increased bonding strength, and It is a solid 11tl slippery composite material consisting of a binder phase that holds and has a particularly low coefficient of friction and specific wear, and a solid +1 that has extremely high mechanical strength.
? 1. The purpose of the present invention is to provide a slippery composite material and its manufacturing capacity υ.

(1st step to solve the problem) Unreleased+! 11 people were investigating how to increase the strength of solid 4-gassing materials; The present invention was achieved by obtaining the knowledge that the strength of a solid lubricating material composed of a substance and a binder phase varies significantly depending on the microstructure of the sintered body, and that the specific wear rate and wear coefficient are low as well as the strength is high. It took 15 to complete.

In other words, the solid lubricating composite material of the present invention comprises lubricating substances in a lumpy phase containing an IE acid component of io tunzhou% to 80 tunzhou% or less, and the remaining metal and/or alloy as a binder phase containing an IE acid component. A solid lubricating material consisting of a solid lubricating material, wherein the lumpy phase is formed by a plurality of solid crystal grains with a particle size of 30 μLm or more.

It is characterized in that it includes particles with a size of μm or less. The lumpy phase whose F component is a lubricating substance mentioned here includes, for example, - molybdenum sulfide, tungsten disulfide, graphite, boron aoride, graphite fluoride, - lead oxide, molybdenum dioxide, cobalt oxide, zinc oxide. , tin oxide, copper oxide, calcium fluoride, barium fluoride, silicon nitride, and telluride, selenide, etc., containing at least one substance with a low coefficient of friction, and containing at least 60% by weight of +[l]. It is something that This massive phase is
Multiple crystal grains with a grain size of less than 30 μm gather together to form a volume of 30 μm.
! It is formed to a particle size of ~1000 μm or less, and in particular, the particle size of 5 is used to increase the strength of solid lubricating materials.
It is preferable that a plurality of crystal grains of μm or less F are formed in a concentrated manner. The optimal size of this lumpy phase differs depending on the relationship between the size of the lumpy phase and the size of the binder phase surrounding the lumpy phase. As a result, it becomes difficult for the binder phase to surround the lumpy phase, making it difficult to form a granular structure. Conversely, when the size of the lumpy phase increases beyond 11,000 jL, the thickness of the binder phase increases, leading to an increase in the coefficient of friction and wear hk. For this reason, the size of the massive phase is
The thickness is defined as 30 μm or more and 1000 μm or less.

Massive phase Xt formation! 1;-Although it depends on the relationship between the composition of the binder phase and the stars, the size of the lumpy phase in particular is 50 μm or more.
It is preferable that it is 500 pLm or less.

The bulk phase mainly composed of a lubricating substance only needs to contain a substance with a low Pl friction coefficient, and in particular, a substance with a low friction coefficient that facilitates the formation of a film on the friction surface of the material during use. It is preferably made of at least one of tungsten sulfide, molybdenum disulfide, and graphite, and furthermore, 261i
1. At least one lubricating substance among tungsten, molybdenum disulfide, and graphite is added in an amount of 60% or more, and the remainder is C.
u.

A g, W, T a, M o, N b
In the case of a lumpy phase consisting of at least one type of bonding auxiliary substance in the alloy of these two inserts, the bonding auxiliary substance envelops the fine grains of the lubricating substance, and the machine This layer is preferred because it improves mechanical strength and abrasion resistance.

In the case of a lumpy phase containing a binding auxiliary substance, the binding auxiliary substance assists in the binding of lubricating substances, resulting in lubricity.

It has the effect of increasing deformation resistance and strength, especially Cu or A
A binding aid containing g has a remarkable effect. In addition, the bonding auxiliary substance has the effect of trapping gas generated during sintering and increasing densification, and in particular W, Ta or N
A binding auxiliary substance containing b exhibits a remarkable effect. Therefore, a bonding auxiliary material containing Ag and/or Cu and at least one of W, Ta, and Nb is preferable from the viewpoint of various properties such as strength, lubricity, stability, and compactness.

In addition, boron nitride, graphite fluoride, -lead oxide, molybdenum trioxide, cobalt # oxide, lead oxide, tin oxide, copper oxide, fluoride, and at least one of tungsten disulfide, molybdenum disulfide, and graphite. Calcium chloride, barium fluoride, silicon nitride, telluride, selenide, etc.
By forming a lumpy phase of a lubricating substance containing 1 or a lumpy phase consisting of these lubricating substances and a binding auxiliary substance, it is possible to create a lumpy phase that can respond to environmental conditions such as temperature or atmosphere during use. can.

■-In addition to the above-mentioned lumpy phase, lubricating substances and periodic table 4a,
Carbides and nitrides of Group 5a and 6a metals.

A lumpy phase consisting of at least one high melting point metal compound among carbonate nitrides, nitride oxides, borides, sulfides, and mutual solid solutions thereof, or a lubricating substance, a binding auxiliary substance, and a high melting point metal compound. In the case of a lumpy phase, it is preferable because use in a high-temperature region improves Irr performance and the allowable temperature during use is widened.

The binder phase surrounding these lumpy phases holds the lumpy phases and suppresses the lubricating substance in the lumpy phases from changing in quality and disappearing during sintering. This binder phase can have various configurations depending on the components of the bulk phase and the environmental conditions yg during use. In particular, the binder phase for increasing the strength of the solid lubricating composite material of the present invention includes Cu, Ag, Sn, Pb, Bi, Fe, and Ni.

Co, Mn, Cr, Mo, W,
Nb, Ta.

Preferably, the material is made of at least one of Ai, Zn, P, B, and alloys of two or more of these. In addition, if more corrosion resistance is required depending on the environmental conditions during use, copper alloys such as Monel or copper alloy +11. If strength and heat resistance are required, use iron-based alloys such as stainless steel or high speed steel, or Hastelloy.

Cobalt alloys such as stellite and nickel-based alloys such as I/Conel or Waspaloy can also be used as the binder phase.

Furthermore, during the bonding phase, periodic table items 4a and 5a.

Group 6a metal carbides, nitrides, carbonates, nitrides,
It is preferable to disperse borides, sulfides, and at least one high-melting point metal compound among these phases/Z solid H bodies because heat resistance is excellent.

The solid lubricating composite material of the present invention and the method for producing the same are characterized in that a starting raw material powder having a lubricating substance as the L component and having a particle size of less than 30 uLm is made into composite granules through a granulation process, and the composite granules and a starting material for forming a binder phase are formed into composite granules. After mixing and molding the powder, pressureless sintering or pressure sintering is performed in a non-oxidizing atmosphere to create a lubricating substance.
E, 10% of a lumpy phase with a size of 30 μm or more, ~100 μm or more, formed by a plurality of crystal grains with a grain size of less than 30 μm as a component; i5x% or more ~80% rj
It is characterized by forming a sintered body consisting of 10% of the total amount and the remaining binder phase.

The starting raw material powder used in the method for producing a solid lubricating composite material of the present invention has a particle size of less than 30 μm, but from the viewpoint of strength, particles as fine as possible are preferable, particularly 5 μm or less. The starting raw material powder, which preferably has a particle size of 100 ml, having a lubricating substance as component F, is mixed and pulverized as necessary, and then formed into composite granules through a granulation process.

The granulation process is usually 1. Normally, all processes used in the production of granules used in powder metallurgy can be used. (2) A granulation process in which a lubricant such as lithium, paraffin, resin, or camphor is added, and then an organic solvent such as hexane, acetone, or alcohol is added to form composite granules in a rotating drum. A granulation treatment method in which a lubricant is added as necessary to the mixed powder, followed by pressure molding, first crushing and sieving to form composite granules, (
■After adding a lubricant as necessary to the mixed powder containing a lubricating substance as the -L component, it is press-molded and then heat-treated at 700°C to 1200°C in a Jl oxidizing atmosphere, then crushed and sieved. There are methods to make composite grains. Although granulation treatment alone may be used during granulation, it is particularly important to add heat treatment in addition to granulation treatment during granulation because the lubricating substance
This is preferable because acid 7, nitrogen, etc. contained in the starting material powder and attached or fixed therein can be expelled as a gas, and highly stable composite grains can be obtained. Furthermore, if the heat treatment is performed using a real press, pressure forming and heat treatment can be carried out simultaneously, which is a time-consuming process.

Cu and Ag are added to the composite grains obtained through the granulation process.

Sn, Pb, Bi, Fe, Ni, Co, Mn.

Cr, Mo, W, Nb, Ta, AM, Zn, P.

Starting material powders for forming a binder phase such as B and various alloys are added and mixed, and after molding,
in a vacuum higher than 4 g or in a non-oxidizing atmosphere such as hydrogen,
The solid lubricating composite material of the present invention can be manufactured by performing pressureless sintering or pressure sintering at a temperature of 00°C to 1200°C.

In particular, when heat treatment is performed in the granulation process, the size of the lumpy phase can be kept stable if the sintering temperature in pressureless sintering or pressure sintering is slightly lower than the heat treatment temperature. This is a good thing.

(Function) The solid lubricating composite material of the present invention is particularly characterized by a lumpy phase in which a binding auxiliary substance is present at the grain boundaries of a lubricating substance and enveloping the lubricating substance, and a binder phase surrounding this lumpy phase. As a result, the brittle lubricating substance is strongly bonded to form a sintered body, and the strength of the sintered body is extremely high. In addition, the solid lubricating composite material of the present invention contains a large lumpy phase of 30 um to 1000 μm, and the lubricating substance contained in this lumpy phase forms a film on the contact surface with the material during use. As a result, both specific wear and wear coefficient are extremely low.

Example 1 Predetermined products were blended using various starting original powders shown in Table 1, and various granulation steps were performed using this blended powder to obtain granulated powder.

Granulation-L step: (1) Add 1% by weight of paraffin to the blended powder, and then mix and granulate in a rotating drum while adding hexane little by little (hereinafter referred to as the tumbling method). A method of heat-treating this granulated powder in a vacuum if necessary, or
■ Mix the blended powder and apply this mixed powder to about 5 layers of IC.
This was carried out by pressing with a bonfire 2, heat-treating in the pressed state or after pressing, and then crushing and sieving (hereinafter referred to as the crushing method).

Table 2 shows the composition of each granulated powder, the granulation process, and the particle size after granulation.

The starting raw material powder for forming the binder phase, which becomes the binder phase, is blended with the granulated powder shown in Table 2 in a predetermined film, and this is mixed, molded and sintered to form the solid lubricating composite material of the present invention and the solid lubricant composite material of the present invention. A lubricating material was obtained. Table 3 shows the compounding composition and sintering conditions of the product of the present invention thus obtained, and Table 4 shows the compounding composition and sintering conditions of the product of the present invention before comparison. The previous compounding composition and sintering conditions are shown in Table 5.

The hardness, radial crushing strength, friction coefficient, and specific wear (l) of each sintered body obtained from Tables 3, 4, and 5 were measured, and the results are shown in Tables 6 and 7. and shown in Table 8.

Among the properties shown in Tables 3, 4, and 5, radial crushing strength is determined by applying external pressure perpendicularly to the outer circumference of a cylindrical sintered body with dimensions of 15φ x 8φ x 8. It was determined by breaking the pipe, using a method equivalent to the pressure resistance test of concrete pipes or the crush test of high-pressure gas container pipes.

In addition, the friction coefficient was 5K2 (18φ×
14φX l 6 Mj method) at a speed of 60 m/+
*The specific wear rate was determined by contacting the end surfaces under the conditions of a surface pressure of 50 kg/cm2 and a pressure of 100 kg/cm2 using the same sample and phase F material as those used to determine the friction coefficient.
This was determined using a friction distance g of 1500 m.

Example 2 The starting raw material powder shown in Table 1 used in Example 1 and the granulated powder H shown in Table 2 were used.

WS2- (Cu -10wt%Sn) system composition, WS
A product of the present invention in which the ratio of 2 and (Cu-10wt%Sn) was changed and a comparative product corresponding to a conventional product were prepared. The radial crushing strength and specific wear rate were measured in the same manner as in Example 1 using a pre-comparison sintered body having the same composition as the product of the present invention, and the results are shown in FIGS. 1 and 2.

Margin (Effects of the Invention) The solid lubricating composite material of the present invention has a low specific wear rate and a low coefficient of friction, and has extremely high strength.
In particular, the specific wear rate is 10 to 30 times lower than conventional products, and the strength is 3 to 4.5 times higher. For this reason, places that are considered difficult to use due to their shape or purpose due to their lifespan based on specific wear rate or strength, such as centrifuges, cameras, ball bearings, needle bearing glue retainers, and seal rings. It is a suitable material for industries that can be used as various sliding materials and various bearing materials.

[Brief explanation of drawings]

FIG. 1 is a photograph of sample NO2 among the products of the present invention in Example 1 taken with a metallurgical microscope. FIG. 2 is a photograph of the Ml weave of sample Mail, which is a comparative product corresponding to the conventional product of Example 1, taken with a metallurgical microscope. FIG. 3 is a diagram showing the relationship between jj- of l1l (lubricating substance (WS7)) and radial crushing strength in the inventive product and the comparative product determined in Example 2. (In the figure, the curve (fL) Unreleased 11
The curve (b) represents the comparative amount. FIG. 4 shows +71. − and Hima↓
It is a relationship diagram with the L rate, in which the curve (a) represents the product of the present invention, and the curve (b) represents the comparative amount. Patent applicant: Toshiba Tungaloy Corporation No. 11″4゜Figure 2Figure 3 0 10 2030 Do050 Go 10 80W
S2 (-years old) Figure 4 0 10 20 30 40 50 Go 70
80WSz CwtX)

Claims (1)

[Scope of Claims] (1) A solid lubricating material consisting of 10% to 80% by weight of a lumpy phase whose main component is a lubricating substance, and the remainder a binder phase whose main component is a metal and/or alloy. A solid lubricating composite material, characterized in that the massive phase includes a plurality of crystal grains with a particle size of less than 30 μm and a size of 30 μm or more and 1000 μm or less. (2) The solid lubricating composite material according to claim 1, wherein the massive phase is formed of a plurality of crystal grains having a particle size of 5 μm or less. (3) The solid lubricating composite material according to claim 1 or 2, wherein the bulk phase contains 50% or more of particles having a size of 50 μm or more and 500 μm or less. (4) The solid lubricant according to claim 1, 2 or 3, wherein the bulk phase is composed of at least one lubricating substance selected from tungsten disulfide, molybdenum disulfide and graphite. Composite material. (5) The massive phase contains at least one lubricating substance among tungsten disulfide, molybdenum disulfide, and graphite.
0% by weight or more and the rest Cu, Ag, W, Ta, Mo, N
3. The solid lubricating composite material according to claim 1, 2 or 3, characterized in that the solid lubricating composite material comprises at least one bonding auxiliary substance selected from the group consisting of B and an alloy of two or more of these. (6) The above bonded phase includes Cu, Ag, Sn, Pb, Bi,
Fe, Ni, Co, Mn, Cr, Mo, W, Nb, Ta
, Al, Zn, P, B, and alloys of two or more of these. Solid lubricating composite material described in Section 1. (7) Claims 1, 2, 3, 4, or 4, wherein the binder phase is made of a copper alloy, an iron alloy, a nickel alloy, or a cobalt alloy. The solid lubricating composite material according to item 5. (8) Powder containing a lubricating substance as a main component and having a particle size of less than 30 μm is made into composite granules through a granulation process, and after mixing and molding the composite granules and binder phase forming powder, no additives are added in a non-oxidizing atmosphere. 30 formed by performing pressure sintering or pressure sintering to form a plurality of crystal grains with a grain size of less than 30 μm and containing a lubricating substance as a main component.
Solid lubricity characterized by forming a sintered body consisting of 10% by weight or more and 80% by weight or less of a lumpy phase with a size of μm or more and 1000 μm or less, and the remaining binder phase whose main component is metal and/or alloy. A method for producing a composite material, (9) the solid lubricating composite according to claim 8, wherein the lubricating substance is at least one of tungsten disulfide, molybdenum disulfide, or graphite. Method of manufacturing the material. (10) The method for producing a solid lubricating composite material according to claim 8 or 9, wherein the granulation step is performed by granulation treatment and heat treatment. (11) The above heat treatment is carried out at 700°C in a non-oxidizing atmosphere.
11. The method for producing a solid lubricating composite material according to claim 10, wherein the manufacturing method is carried out at a temperature of 1200° C. or higher and 1200° C. or lower. (12) Claims 8, 9, 10, or 11, characterized in that the pressureless sintering or pressure sintering is performed at a temperature of 400°C or higher and 1200°C or lower. A method for producing the solid lubricious composite material described above.