U.S. patent application number 13/822444 was filed with the patent office on 2013-07-18 for mixed powder for powder metallurgy and manufacturing method thereof.
This patent application is currently assigned to Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.). The applicant listed for this patent is Hironori Suzuki. Invention is credited to Hironori Suzuki.
Application Number | 20130180359 13/822444 |
Document ID | / |
Family ID | 46050780 |
Filed Date | 2013-07-18 |
United States Patent
Application |
20130180359 |
Kind Code |
A1 |
Suzuki; Hironori |
July 18, 2013 |
MIXED POWDER FOR POWDER METALLURGY AND MANUFACTURING METHOD
THEREOF
Abstract
This mixed powder for powder metallurgy, the powder having
excellent fluidity and minimal graphite powder scattering, can be
obtained relatively conveniently by mixing fine graphite having an
average grain diameter of 4 .mu.m or less with an iron based
powder. The process is performed without the addition of a binder
and while shearing force is applied. It is preferable that the fine
graphite have an average grain diameter of 2.4 .mu.m or less and be
wet-milled. A portion of the fine graphite is preferably added in
place of at least one constituent selected from the group
consisting of carbon black, fullerene, carbon compounds carbonized
by baking, and graphite having an average grain diameter of 5 .mu.m
or more.
Inventors: |
Suzuki; Hironori;
(Takasago-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Suzuki; Hironori |
Takasago-shi |
|
JP |
|
|
Assignee: |
Kabushiki Kaisha Kobe Seiko Sho
(Kobe Steel, Ltd.)
Kobe-shi
JP
|
Family ID: |
46050780 |
Appl. No.: |
13/822444 |
Filed: |
October 24, 2011 |
PCT Filed: |
October 24, 2011 |
PCT NO: |
PCT/JP2011/074418 |
371 Date: |
March 12, 2013 |
Current U.S.
Class: |
75/252 ;
241/30 |
Current CPC
Class: |
B22F 1/0059 20130101;
C22C 2026/001 20130101; B22F 2999/00 20130101; B22F 1/007 20130101;
B22F 2999/00 20130101; B22F 1/0059 20130101; B22F 2301/35 20130101;
B22F 1/0081 20130101 |
Class at
Publication: |
75/252 ;
241/30 |
International
Class: |
B22F 1/00 20060101
B22F001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 9, 2010 |
JP |
2010-250867 |
Claims
1. A mixed powder, obtained by a process comprising mixing a fine
graphite having a mean particle size of 4 .mu.m or less with an
iron based powder without adding a binder while applying a shear
force.
2. The mixed powder according to claim 1, wherein the mean particle
size of the fine graphite is 2.4 .mu.m or less.
3. The mixed powder according to claim 1, wherein the fine graphite
is obtained by wet crushing.
4. The mixed powder according to claim 1, wherein the fine graphite
is partially replaced with at least one selected from the group
consisting of carbon black, fullerene, a carbon compound to be
carbonized by burning, and a graphite having a mean particle size
of 5 .mu.m or more, to be added.
5. The mixed powder according to claim 4, wherein a ratio of the
fine graphite to a total amount of the fine graphite, the graphite,
the carbon black, the fullerene, and the carbon compound is 15 mass
% or more.
6. The mixed powder according to claim 5, wherein the total amount
of the fine graphite, the graphite, the carbon black, the
fullerene, and the carbon compound is from 0.1 part to 3 parts by
mass per 100 parts by mass of the iron based powder.
7. The mixed powder according to claim 1, comprising at least one
selected from the group consisting of a lubricant, a strength
improver, an abrasion resistance improver, and a machinability
improver.
8. A mixed powder obtained by a process comprising mixing a fine
graphite having a mean particle size of 4 .mu.m or less with an
iron based powder with an addition of a binder in a ratio of 0.1
part by mass or less per 100 parts by mass of the iron based powder
while applying a shear force.
9. A method for manufacturing a mixed powder for powder metallurgy,
comprising: preparing a fine graphite having a mean particle size
of 4 .mu.m or less, and mixing the fine graphite with an iron based
powder without adding a binder while applying a shear force.
10. A method for manufacturing a mixed powder, the method
comprising: preparing a fine graphite having a mean particle size
of 4 .mu.m or less, adding a binder to the fine graphite in a ratio
of 0.1 part by mass or less per 100 parts by mass of an iron based
powder, thereby obtaining a mixture of the fine graphite and the
binder and mixing the mixture with the iron based powder while
applying a shear force.
11. The method according to claim 9, wherein the mixing is with a
mixer comprising moving stirring vanes.
12. The method according to claim 10, wherein the mixing is with a
mixer comprising moving stirring vanes.
13. The mixed power according to claim 2, wherein the mean particle
size of the fine graphite is 2.0 .mu.m or less.
14. The mixed powder according to claim 5, wherein the ratio of the
fine graphite to the total amount of the fine graphite, the
graphite, the carbon black, the fullerene, and the carbon compound
is 25 mass % or more.
15. The mixed powder according to claim 6, wherein the total amount
of the fine graphite, the graphite, the carbon black, the
fullerene, and the carbon compound is from 0.3 part to 2.0 parts by
mass per 100 parts by mass of the iron based powder.
16. The method according to claim 10, wherein, in the adding, the
binder is added in the ratio of 0.05 part by mass or less per 100
parts by mass of the iron based powder.
Description
TECHNICAL FIELD
[0001] The present invention relates to a powder metallurgy
technology of forming and sintering an iron based powder, and
manufacturing a sintered body. More particularly, it relates to a
mixed powder for powder metallurgy, which causes less scattering of
a graphite powder, and is excellent in flowability, and a
manufacturing method thereof.
BACKGROUND ART
[0002] In powder metallurgy by which a sintered body is
manufactured using an iron powder or a copper powder as a main raw
material, generally, there is used a mixed powder including a
powder of the main raw material, a sub raw material powder (such as
a graphite powder or an alloy component) for improving the physical
properties of the sintered body, a lubricant, and the like.
Particularly, in order to improve the mechanical physical
properties (such as strength and hardness) of the sintered body,
generally, carbon supplying component (carbon source) such as
graphite is added, and the mixture is formed, followed by diffusion
and carburization of the carbon source into the iron powder during
a heat sintering treatment.
[0003] However, a graphite is smaller in specific gravity and
smaller in particle diameter than an iron powder. For these
reasons, mere mixing thereof results in that the graphite and the
iron powder are largely separated from each other, and that the
graphite segregates. Thus, uniform mixing thereof unfavorably
cannot be achieved. With the powder metallurgy method, sintered
bodies are mass-produced. For this reason, generally, a mixed
powder is previously stored in a storage hopper. In the storage
hopper, a graphite having a small specific gravity tends to
segregate at the upper layer part of the hopper. Accordingly, when
the mixed powder is discharged from the hopper, the concentration
of the graphite increases in the end of hopper discharge. Thus, in
the portion having a high graphite concentration in the sintered
body, a cementite structure precipitates, resulting in the
reduction of the mechanical characteristics. When a variation is
caused in the content of carbon in the sintered body due to the
segregation of graphite, it becomes difficult to manufacture
components with stable qualities. Further, in the mixing step or
the forming step, the segregation of graphite causes dust emission
of the graphite powder. This unfavorably results in the problems of
the aggravation of the workplace environment and the reduction of
the handling property of the mixed powder. The foregoing
segregation also similarly occurs not only for graphite but also
for other various powders to be mixed with the iron powder. This
has created a demand for prevention of the segregation.
[0004] In order to prevent the segregation and the dust emission of
graphite, broadly classified three methods have been proposed in
the related art. The first method is a method for adding a liquid
additive such as tall oil to a mixed powder (e.g., Patent Documents
1 and 2). This method has an advantage of enabling manufacturing
with simple facilities. However, when a liquid additive is added in
an amount necessary for the segregation preventive effect to be
observed, a liquid cross-linking force acts on among iron powder
particles. This unfavorably results in extreme aggravation of
flowability. The second method is a method in which a solid binder
such as a high molecule polymer is dissolved in a solvent, and is
uniformly mixed therein, followed by the evaporation of the
solvent, thereby to allow graphite to adhere to the surface of an
iron powder (Patent Documents 3, 4, and the like). This method has
advantages of being capable of surely allowing graphite to adhere
thereto, and also having a wide choice of options for lubricants to
be used. However, the flowability of the mixed powder may be
insufficient according to the composition. The third method is a
so-called hot melt method characterized by heating and melting a
relatively lower molecular weight lubricant such as fatty acid
during mixing with an iron powder (e.g., Patent Document 5). The
molten lubricant is uniformly fixed on the iron powder surface. For
this reason, the temperature control during mixing is very
important. Further, there is also a deficiency that the options for
usable lubricants are restricted. With any of the first to third
methods, an organic binder is added, which must result in a
complicated step. This has created a demand for a more simple
method.
[0005] Incidentally, although irrelevant to the segregation
prevention, there is also proposed a technology of controlling the
particle size of graphite. In Patent Document 6, a 0.1- to 2-.mu.m
graphite and an iron powder are mixed in a vibration mill with
adding additives in a specific atmosphere such as ammonia. Thus,
the iron powder particle surface is covered with graphite
particles. In Patent Documents 7 and 8, the particle size of
graphite is controlled, and using an organic binder, the iron
powder surface is covered with graphite.
PATENT DOCUMENTS
[0006] [Patent Document 1] JP-A No. 60-502158 [0007] [Patent
Document 2] JP-A No. 6-49503 [0008] [Patent Document 3] JP-A No.
5-86403 [0009] [Patent Document 4] JP-A No. 7-173503 [0010] [Patent
Document 5] JP-A No. 1-219101 [0011] [Patent Document 6] JP-A No.
54-90007 [0012] [Patent Document 7] JP-A No. 2005-330547 [0013]
[Patent Document 8] JP-A No. 2009-263697
DISCLOSURE OF THE INVENTION
[0014] It is an object of the present invention to relatively
easily provide a mixed powder for powder metallurgy which causes
less scattering of a graphite powder, and is excellent in
flowability, and a manufacturing method thereof.
[0015] The mixed powder for powder metallurgy of the present
invention which achieved the foregoing object is characterized by
being obtained by mixing a fine graphite with a mean particle size
of 4 .mu.m or less with an iron based powder without adding a
binder and while applying a shear force. It is preferable that the
fine graphite has a mean particle size of 2.4 .mu.m or less, and
has been subjected to wet crushing.
[0016] For the mixed powder for powder metallurgy of the present
invention, it is also preferable that the fine graphite has been
partially replaced with at least one selected from the group
consisting of carbon black, fullerene, a carbon compound to be
carbonized by burning, and a graphite with a mean particle size of
5 .mu.m or more, to be added. In this case, it is preferable that
the total amount of all the graphites, carbon black, fullerene, and
the carbon compound to be carbonized by burning is 0.1 part by mass
or more and 3 parts by mass or less per 100 parts by mass of the
iron based powder. Further, the mixed powder for powder metallurgy
of the present invention preferably includes at least one selected
from the group consisting of a lubricant, a strength improver, an
abrasion resistance improver, and a machinability improver.
Alternatively, for mixing of the graphite and the iron based
powder, a small amount of binder may be added. The mixed powder for
powder metallurgy obtained by mixing a fine graphite with a mean
particle size of 4 .mu.m or less with an iron based powder with
adding a binder in a ratio of 0.1 part by mass or less per 100
parts by mass of the iron based powder and while applying a shear
force is also embraced in the present invention.
[0017] In accordance with the present invention, the mean particle
size of graphite is refined, and mixing with an iron based powder
is performed while applying a shear force. For these reasons, it is
possible to obtain a mixed powder for powder metallurgy excellent
in adhesive force between the graphite and the iron based powder
even without adding a binder. As a result, it is possible to
suppress the segregation of graphite. Further, the mixed powder for
powder metallurgy of the present invention is also excellent in
flowability. The mixed powder for powder metallurgy of the present
invention does not require the addition of a binder, and hence can
be manufactured at a low cost, and also has an advantage of high
productivity.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a cross-sectional view of an apparatus for use in
measurement of the scattering ratio of graphite in examples;
and
[0019] FIG. 2 is a SEM photograph when the surface of a mixed
powder in an example is observed by a SEM (scanning electron
microscope).
DISCLOSURE OF THE INVENTION
[0020] A mixed powder for powder metallurgy of the present
invention is characterized by being obtained by mixing a fine
graphite with an iron based powder while applying a shear
force.
[0021] For the fine graphite in the present invention, the mean
particle size according to the measuring method by the Microtrac
method is 4 .mu.m or less. The mechanism in which graphite is
refined to the foregoing range, thereby to increase the adhesive
force with an iron powder is not fully elucidated. However, a
decrease in particle size of graphite results in an increase in
specific surface area. Thus, adhesion by a physical force such as
static electricity is conceivable. Further, it is conceivable that
a chemical force also acts. Namely, it is considered that the
crushed surface of the finely crushed graphite includes large
quantities of functional groups such as a hydrogen group. Thus,
presumably, an intermolecular force occurs between the iron powder
and graphite via the functional groups, so that graphite adheres
onto the iron powder surface. The presence or absence of the
functional groups and the contents thereof can be grasped to a
certain degree by heating graphite in a nitrogen atmosphere, and
measuring the mass change ratio at from room temperature to
950.degree. C. The temperature rising rate for raising the
temperature from room temperature up to 950.degree. C. is desirably
set at about 10.degree. C./min. Generally, the kind of a gas
generated from graphite varies from one heating temperature region
to another. The kind of the functional group removed within the
temperature range can be estimated from the kind of the generated
gas. As generally known, at 150 to 500.degree. C., a carboxyl group
(--COOH) and a hydroxy group (--OH) are removed; at 500 to
900.degree. C., an oxo group (.dbd.O) is removed; and at
900.degree. C. or more, a hydrogen group (--H) is removed. By
checking the weight loss amount at 150 to 950.degree. C., it is
possible to remove the effect of the decrease in weight of the
moisture removable at a lower temperature than 150.degree. C.
Accordingly, it is possible to know the kind and the content of
each functional group included in graphite.
[0022] The mean particle size of the fine graphite is preferably
2.4 .mu.m or less, more preferably 2.2 .mu.m or less, and further
preferably 2.0 .mu.m or less. Although the lower limit of the mean
particle size of the fine graphite has no particular restriction,
it is generally about 1.0 .mu.m. In order to set the mean particle
size of the fine graphite within the foregoing range, a
commercially available natural graphite or an artificial graphite
may desirably be crushed using a crusher. The atmosphere for
crushing has no particular restriction. Crushing may be performed
by a dry process, or crushing may be performed by a wet process.
However, wet crushing is preferable. When wet crushing is
performed, water, alcohol, or the like can be used as a solvent. As
a crusher, a general crusher can be used. Examples thereof are roll
crusher, cutter mill, rotary crusher, hammer crusher, vibration
mill, pin mill, wing mill, ball mill, and planetary mill.
[0023] It is important that the fine graphite and the iron based
powder in the present invention are mixed while being applied with
a shear force. The mixing method whereby a shear force is applied
is a different method from a convection mixing method as
represented by a V type mixer or a double corn mixer. Mixing while
applying a shear force enables mixing while minimizing the distance
between the iron powder and the fine graphite. As a result, it is
possible to effectively exhibit the adhesive force improving effect
due to the refinement of graphite.
[0024] Mixing providing a shear force can be achieved by using, for
example, a mixer equipped with stirring vanes moving in such a
manner as to cut the powder. As the shapes of the stirring vanes,
mention may be made of paddle, turbine, ribbon, screw, multi-stage
vane, anchor type, horseshoe type, gate type, and the like. As long
as the mixer includes the stirring vanes, the container of the
mixer may be of a fixed type, or may be of a rotary type. As the
mixers equipped with the stirring vanes, specifically, mention may
be made of high speed mixers (manufactured by Henschel Co., and the
like), plow type mixers, nauta mixers, and the like. Although the
mixing time depends upon the type of the mixer to be used, the
amount of mixed powders, and the like, it is roughly 1 to 20
minutes.
[0025] Mixing of the fine graphite and the iron based powder may be
performed by a wet process, or may be performed by a dry process.
Further, the mixing procedure of the fine graphite and the iron
based powder has no particular restriction. In other words, the
powders may be charged into a mixer at the same time.
Alternatively, it is also acceptable that one powder is charged
into the mixer first, and the other powder is added later.
[0026] Mixing of the fine graphite and the iron based powder is not
performed by being heated to a temperature enough for a lubricant
and the like to be molten, or higher as with the so-called hot melt
method, but may be performed, for example, at ordinary
temperatures. Further, although the atmosphere for mixing has no
particular restriction, it may be the air.
[0027] In the present invention, as the carbon source, only the
fine graphite may be used. Alternatively, for the purpose of
reducing the manufacturing cost, the fine graphite may be partially
replaced with one or more of general graphite (generally, having a
mean particle size of 5 .mu.m or more), carbon black, fullerene,
and a carbon compound which is carbonized by burning, to be used.
The powders may be desirably added during the mixing of the fine
graphite and the iron based powder. The adding order has no
particular restriction. However, for example, the fine graphite,
the iron based powder, and other carbon sources than the fine
graphite may be simultaneously added to a mixer and mixed.
Alternatively, the following may be adopted: the fine graphite and
the iron based powder are mixed first; and then, while mixing them
(for example, while operating stirring vanes), other carbon sources
than the fine graphite are added one by one, or in combination of
two or more thereof. In this case, the ratio of the fine graphite
is preferably 15 mass % or more, more preferably 20 mass % or more,
and further preferably 25 mass % or more based on the total mass of
the carbon sources (i.e., all the graphites (the fine graphite and
common graphite), and one or more of carbon black, fullerene, and
the carbon compound to be carbonized by burning). The carbon
compound to be carbonized by burning may be derived from a plant or
may be derived from an animal, and is, for example, active carbon,
charcoal, or anthracite.
[0028] The content of the carbon sources is generally 0.1 part by
mass or more and 3 parts by mass or less per 100 parts by mass of
the iron based powder. The lower limit of the content of the carbon
sources is preferably 0.2 part by mass or more, and more preferably
0.3 part by mass or more per 100 parts by mass of the iron based
powder. Whereas, the upper limit of the content of the carbon
sources is preferably 2.5 parts by mass or less, and more
preferably 2.0 parts by mass or less (particularly, 1.3 parts by
mass or less) per 100 parts by mass of the iron based powder.
[0029] The mixed powder for powder metallurgy of the present
invention may further include at least one selected from the group
consisting of a lubricant, and physical property improving
additives (e.g., a strength improver, an abrasion resistance
improver, and a machinability improver). The powders may be added
when the fine graphite and the iron based powder are mixed. The
adding order has no particular restriction. For example, the fine
graphite and the iron based powder may be simultaneously added to a
mixer and mixed. Alternatively, the following may be adopted: the
fine graphite and the iron based powder are mixed first; and then,
while mixing them (for example, while operating the stirring
vanes), the lubricant and the physical property improving additives
are added one by one, or in combination of two or more thereof to
the mixer.
[0030] As the lubricants, mention may be made of metallic soap,
alkylenebis fatty acid amide, fatty acid, and the like. These may
be used alone, or may be used in combination of two or more
thereof. The metallic soap includes therein fatty acid salts, for
example, fatty acid salts having 12 or more carbon atoms. Zinc
stearate is preferably used. As the fatty acid of the alkylenebis
fatty acid amide, for example, a compound exemplified as
R.sub.1COOH can be used. As the alkylenebis fatty acid amide,
specifically, mention may be made of C.sub.2-6 alkylenebis
C.sub.12-24 carboxylic acid amide. Ethylenebis stearylamide is
preferably used. As the fatty acids, for example, a compound
exemplified as R.sub.1COOH can be used, and is preferably
carboxylic acid having about 16 to 22 carbon atoms. Particularly,
stearic acid and oleic acid are preferably used. The content of the
lubricant is, for example, 0.3 part by mass or more and 1.5 parts
by mass or less, and more preferably 0.5 part by mass or more and
1.0 part by mass or less per 100 parts by mass of the iron based
powder.
[0031] As the strength improvers, mention may be made of, for
example, powders including at least one of copper, nickel,
chromium, molybdenum, manganese, and silicon. Specifically, they
are a copper powder, a nickel powder, a chromium-containing powder,
a molybdenum powder, a manganese-containing powder, a
silicon-containing powder, and the like. The strength improvers may
be used alone, or may be used in combination of two or more
thereof. The amount of the strength improver to be added is, for
example, 0.2 part by mass or more and 5 parts by mass or less, and
more preferably 0.3 part by mass or more and 3 parts by mass or
less per 100 parts by mass of the iron based powder.
[0032] As the abrasion resistance improvers, mention may be made of
hard particles of carbide, silicide, nitride, and the like. These
may be used alone, or may be used in combination of two or more
thereof.
[0033] As the machinability improvers, mention may be made of
manganese sulfide, talc, calcium fluoride, and the like. These may
be used alone, or may be used in combination of two or more
thereof.
[0034] The mixed powder for powder metallurgy of the present
invention is excellent in adhesive force between graphite and an
iron based powder even when a binder is added thereto. However, the
present invention also embraces a mode in which a binder is added
within the range of 0.1 part by mass or less per 100 parts by mass
of the iron based powder. The binder amount is more preferably 0.08
part by mass or less, and further preferably 0.05 part by mass or
less.
[0035] The iron based powder for use in the present invention may
be any of a pure iron powder and an iron alloy powder. The iron
alloy powder may be a partial alloy powder in which an alloy powder
(e.g., copper, nickel, chromium, or molybdenum) is diffused and
adheres to the surface of an iron based powder, or may be a
prealloy powder obtained from molten iron (or molten steel)
including alloy components (the same components as those of the
alloy powder). The iron based powder is generally manufactured by
subjecting molten iron or steel to an atomizing treatment.
Alternatively, the iron based powder may be a reduced iron powder
manufactured by reducing an iron ore or a mill scale. The mean
particle size of the iron based powder is, for example, 30 to 150
.mu.m, and preferably 50 to 100 .mu.m. The mean particle size of
the iron based powder means the particle size at a cumulative
undersize amount of 50% when the particle size distribution is
measured according to Japan Powder Metallurgy Association standard
JPMA P 02-1992 (testing method for sieve analysis of metal
powder).
[0036] For the mixed powder for powder metallurgy of the present
invention, as described above, the particle size of graphite is
controlled, and as a mixing method thereof, a proper one is
adopted. For these reasons, the adhesive force between the graphite
and the iron based powder can be enhanced without adding a binder
(such as an organic bonding agent). As a result, it is possible to
suppress the segregation of graphite. Thus, the graphite scattering
ratio obtainable by a method described later can be set at, for
example, 20% or less, and can be set at preferably 15% or less, and
more preferably 10% or less. Further, in the mixed powder of the
present invention, a binder is not added. Alternatively, even when
a binder is added, it is added in a small amount (0.1 part by mass
or less). For this reason, as compared with the one including a
binder added therein, the density of a formed body when the formed
body is formed under the same forming pressure, and the density of
a sintered body obtained by sintering the formed body become
higher, resulting in an enhancement of the strength of the sintered
body. Further, for the mixed powder of the present invention, it is
possible to omit or simplify the dewaxing step to be performed
between the forming step and the sintering step. This contributes
to the improvement of the productivity of sintered components and
also the environmental measures.
[0037] Further, it is possible to implement the stabilization of
the quality such as minimization of the dimensional changes by the
refinement of graphite. Thus, it is also possible to implement
energy saving and cost reduction in manufacturing of sintered
components such as reduction of the sintering temperature or the
shortening of the sintering time. The mixed powder of the present
invention is applicable to sintered components for mechanical
structures, and the like. Particularly, it is also applicable to
components in the complicated and thin-walled shapes. Then, weight
reduction can be achieved, and hence the mixed powder of the
present invention is also suitable for high strength materials.
EXAMPLES
[0038] Below, the present invention will be described more
specifically by way of examples. The present invention is not
limited by the following examples. It is naturally understood that
the present invention can be practiced by adding appropriate
changes thereto within the scope applicable to the gist described
above and later. Any of these are included in the technical range
of the present invention.
[0039] For each example, the scattering ratio of graphite, the
apparent density and the flowability of the mixed powder were
measured by the following methods.
(1) Scattering Ratio of Graphite
[0040] As shown in FIG. 1, in a glass tube 2 (inner diameter: 16
mm, height 106 mm) with a funnel shape at its lower part, a
nuclepore filter 1 (mesh 12 .mu.m) was set. Thereon, 25 g of a
mixed powder P was charged. From the lower part of the glass tube
2, a N.sub.2 gas was passed at a rate of 0.8 l/min for 20 minutes.
Thus, the graphite scattering ratio was determined by the following
equation (1). In other words, graphite not adhering to the iron
powder scatters by the N.sub.2 gas circulated from under. For this
reason, it is possible to determine the graphite scattering ratio
by the following equation (1). Incidentally, the amounts of carbon
of the mixed powder before and after N.sub.2 gas circulation can be
measured by the combustion method.
Graphite scattering ratio(%)=(1-Carbon amount after N.sup.2 gas
circulation/Carbon amount before N.sub.2 gas circulation).times.100
(1)
(2) Apparent Density of Mixed Powder
[0041] According to JIS Z2504 (metal powder-apparent density
testing method), the apparent density (g/cm3) of the mixed powder
was measured.
(3) Flowability of Mixed Powder
[0042] According to JIS Z2502 (flowability testing method of metal
powder), the flowability of (sec/50 g) of the mixed powder was
measured. Namely, the time (sec) until 50 g of the mixed powder
flowed out through an orifice with a diameter of 2.63 mm was
measured. The time (sec) is referred to as the flowability of the
mixed powder.
Example 1
[0043] A commercially available natural graphite (manufactured by
Nippon Graphite Ltd., JCPB, mean particle size 5.0 .mu.m) was
subjected to wet type bead mill crushing (solvent: water), then,
was dried, and further was crushed by a dry type jet mill,
resulting in a graphite with a mean particle size of 2.1 .mu.m (the
particle size of graphite was measured by a Microtrac 9300-X100).
Per 100 parts by mass of an iron powder (manufactured by KOBE STEEL
Ltd., Atmel 300M, particle side 180 .mu.m or less, mean particle
size 70 .mu.m), 0.8 part by mass of the graphite was simultaneously
charged into a high speed mixer without adding a binder or a
lubricant, and without applying a heat thereto, and the mixture was
mixed for 5 minutes, resulting in a mixed powder. The graphite
scattering ratio of the resulting mixed powder was 1%. Further, the
results obtained from observation under a SEM are shown in FIG. 2.
FIG. 2 indicates that the fine graphite uniformly adheres to the
surface of the iron powder.
[0044] On the other hand, for comparison, a mixed powder was
obtained in the same manner as described above, except that the
JCPB was used as it was without being crushed. As a result, the
graphite scattering ratio was bout 50%. Further, the mixed powder
was observed under a SEM. As a result, it was found that graphite
only partially entered and adhered to the pits of the iron powder,
and that most of the graphite did not adhere thereto.
Example 2
[0045] Graphite powders obtained by adjusting a commercially
available natural graphite (manufactured by Japan Graphite Co.,
Ltd., JCPB, mean particle size 5.0 .mu.m) various particle sizes
according to the methods described in Table 1 (wherein JCPB itself
was used for Nos. 1 and 2 of Table 1), an iron powder (manufactured
by KOBE STEEL Ltd., Atmel 300M, particle side 180 .mu.m or less,
mean particle size 70 .mu.m), and a copper powder (manufactured by
FUKUDA METAL FOIL & POWDER Co., Ltd., CE-20) were
simultaneously added to their respective mixers shown in Table 1 in
a ratio of copper powder: 2 parts by mass and graphite: 0.8 part by
mass per 100 parts by mass of the iron powder, and each mixture was
mixed, resulting in each mixed powder for graphite scattering ratio
measurement. The particle size of each graphite was measured by the
Microtrac 9300-X100 as with Example 1. Further, per 100 parts by
mass of the mixed powder, 0.8 part by mass of an ethylenebisamide
lubricant was mixed using each mixer shown in Table 1, resulting in
each powder for apparent density and flowability measurement.
Incidentally, the solvent for wet crushing performed for Nos. 7 and
8 of Table 1 is ethanol.
TABLE-US-00001 TABLE 1 Mixing Mean particle method of size of
Crushing graphite and Graphite Apparent Experiment graphite method
of the like and scattering density Flowability No. (.mu.m) graphite
iron powder ratio (%) (g/cm.sup.3) (sec/50 g) 1 5.0 -- Convection
65 3.08 No flowing mixing (V type mixer) 2 5.0 -- Shear mixing 55
3.10 No flowing (high speed mixer) 3 3.5 Dry type jet mill
Convection 42 3.12 No flowing mixing (V type mixer) 4 3.5 Dry type
jet mill Shear mixing 18 3.13 29.0 (high speed mixer) 5 2.3 Dry
type mill + Convection 35 3.10 No flowing Dry type jet mill mixing
(V type mixer) 6 2.3 Dry type mill + Shear mixing 6 3.15 24.2 Dry
type jet mill (high speed mixer) 7 1.9 Wet type Convection 28 3.20
27.0 crushing by mixing Star Burst (V type manufactured mixer) by
Sugino Machine Ltd. 8 1.9 Wet type Shear mixing 1 3.25 24.0
crushing by (high speed Star Burst mixer) manufactured by Sugino
Machine Ltd.
[0046] For Experiment Nos. 4, 6, and 8, the mean particle size of
graphite was small, and the graphite and the iron based powder were
mixed by the shear mixing method. Accordingly, the scattering ratio
of graphite was small, and the flowability was also good.
Particularly, for Experiment Nos. 6 and 8, the mean particle size
of graphite was 2.4 .mu.m or less, and both of the scattering ratio
of graphite and the flowability of the mixed powder were better
than those of No. 4.
[0047] On the other hand, for Experiment Nos. 1 and 2, the mean
particle size of graphite was large; and for Experiment No. 1, the
convection mixing method was adopted. Accordingly, in both cases,
it resulted that the scattering ratio of graphite was large, and
that the mixed powder did not flow. For Experiment Nos. 3 and 5,
although the mean particle size of graphite was 4 .mu.m or less,
the convection mixing method was adopted. Accordingly, it resulted
that the scattering ratio of graphite was large, and that the mixed
powder did not flow. For Experiment No. 7, although the mean
particle size of graphite was 2.4 .mu.m or less, and was very fine,
the convection mixing method was adopted. Accordingly, the
scattering ratio of graphite was large.
[0048] Further, from Table 1, there can be known the effects of the
mean particle size and the mixing method of graphite exerted on the
apparent density of the mixed powder. For example, comparison
between Experiment Nos. 1 and 3, or between Experiment Nos. 2 and 4
indicates that a smaller mean particle size results in a larger
apparent density of the mixed powder. Further, respective
comparisons between Experiment Nos. 1 and 2, between 3 and 4,
between 5 and 6, and between 7 and 8 indicate that the shear mixing
method provides a larger apparent density of the mixed powder than
that with the convection mixing method.
Example 3
[0049] Per 100 parts by mass of an iron powder (manufactured by
KOBE STEEL Ltd., Atmel 300M, particle size 180 .mu.m or less, mean
particle size 70 .mu.m), (i) the fine graphite used in Experiment
No. 6 of Example 2, A15 carbon black manufactured by Degussa, and a
commercially available natural graphite (manufactured by Japan
Graphite Co., Ltd., JCPB, mean particle size: 5.0 .mu.m) and, (ii)
2 parts by mass of a copper powder were simultaneously added to a
high speed mixer with vanes, and the mixture was stirred for five
minutes, resulting in a powder for measuring the graphite
scattering ratio. Incidentally, the mixing ratios of the fine
graphite, the carbon black, and the commercially available natural
graphite (the ratios per 100 parts by mass of the iron powder) are
as shown in Table 2. Further, 0.8 part by mass of an
ethylenebisamide lubricant was mixed per 100 parts by mass of a
graphite scattering ratio measuring mixed powder (stirred using a
high speed mixer with vanes for 2 minutes), resulting in a powder
for apparent density and flowability measurement.
TABLE-US-00002 TABLE 2 Fine Carbon graphite black JCPB Graphite
Experi- amount amount amount scattering Apparent Flow- ment (part
by (part by (part by ratio density ability No. mass) mass) mass)
(%) (g/cm.sup.3) (sec/50 g) 9 0.8 0 0 1 3.25 24.0 10 0.4 0.4 0 2
3.11 26.8 11 0.2 0.6 0 0 3.08 27.4 12 0.6 0 0.2 17 3.12 28.9
[0050] Table 2 indicates that, even when the fine graphite is
partially replaced with carbon black and/or commercially available
graphite (JCPB), to be used, the graphite scattering ratio can be
sufficiently suppressed.
Example 4
[0051] Using Experiment Nos. 1 and 8 (powders after addition of the
ethylenebisamide lubricant) of Example 2, and, for comparison, a
conventional mixed powder (the one using a binder), formed bodies
were manufactured under a pressure of 686 MPa each so as to be in a
ring shape with an outer diameter of 30 mm, an inner diameter of 10
mm, and a height of 10 mm. Thus, each formed body density was
measured by a method described later. The formed body was sintered
under an atmosphere of 95% nitrogen, and 5% hydrogen at
1120.degree. C. for 30 minutes. The density, the dimensional change
ratio, the radial crushing strength, and the hardness of the
resulting sintered body were measured by the following methods.
[0052] Incidentally, the manufacturing procedure of the
conventional mixed powder (the one using a binder) is as follows.
First, using a high speed mixer with vanes, 0.8 part by mass of a
commercially available natural graphite (manufactured by Japan
Graphite Co., Ltd., JCPB, mean particle size 5.0 .mu.m) and 2 parts
by mass of a copper powder (manufactured by FUKUDA METAL FOIL &
POWDER Co., Ltd., CE-20) were mixed per 100 parts by mass an iron
powder (manufactured by KOBE STEEL Ltd., Atmel 300M, particle side
180 .mu.m or less, mean particle size 70 .mu.m). Subsequently, 0.2
part by mass of a 10% styrene butadiene copolymer solution (solvent
was toluene) was charged into a mixer per a total amount of 100
parts by mass of the iron powder, the natural graphite, and the
copper powder, and the mixture was mixed for two minutes. Then,
vacuum heating was performed to evaporate the toluene, resulting in
a mixed powder. Per 100 parts by mass of the mixed powder, 0.8 part
by mass of an ethylenebisamide lubricant was mixed (with stirring
using a high speed mixer with vanes for two minutes).
(4) Measurement of Formed Body Density and Sintered Body
Density
[0053] The formed body density and the sintered body density were
determined by measuring respective dimensions of the formed body
and the sintered body, and determining respective volumes, and
measuring respective masses, and dividing the masses by the
volumes, respectively.
(5) Measurement of Dimensional Change Ratio
[0054] The dimensional change ratio (%) was determined by the
following equation (2).
Dimensional change ratio={(outer diameter of sintered body)-(outer
diameter of formed body)}/(outer diameter of formed body).times.100
(2)
(6) Measurement of Radial Crushing Strength
[0055] Radial crushing pressing is performed in the direction of
the forming axis of the sintered body and the vertical direction
thereof. Thus, the strength when the ring was broken was measured,
and the radial crushing strength (MPa) was determined according to
JIS Z2507.
(7) Measurement of Hardness
[0056] Given respective three points (a total of six points) on the
front surface and the back surface of the ring-shaped sintered body
were measured by means of a Rockwell B scale, thereby to determine
the hardness (HRB).
TABLE-US-00003 TABLE 3 Formed Sintered Dimensional Radial body body
change crushing density density ratio strength Hardness
(g/cm.sup.3) (g/cm.sup.3) (%) (MPa) (HRB) No. 1 of 7.10 7.06 0.38
910 82 Example 2 No. 8 of 7.13 7.10 0.30 970 84 Example 2 Related
art 7.10 7.07 0.36 920 83
[0057] Table 3 indicates as follows: for Experiment No. 8 of
Example 2 satisfying the requirements of the present invention, the
mean particle size of graphite was large, and, as compared with
Experiment No. 1 subjected to convection mixing, the formed body
density was higher, and the dimensional change upon sintering was
smaller (expansion was small). Accordingly, the sintered body
density increased, and the radial crushing strength and the
hardness of the sintered body also increased. Further, it is
indicated as follows: even as compared with the related art
technology, for Experiment No. 8 of Example 2, the formed body
density was larger, and the dimensional change ratio was smaller,
thus, the sintered body density increased, and the radial crushing
strength was also very excellent. Incidentally, also for the
related art technology, the graphite scattering ratio was measured.
The result was 1%.
EXPLANATION OF REFERENCE NUMERALS
[0058] 1 . . . Nuclepore filter [0059] 2 . . . Glass tube
* * * * *