U.S. patent number 3,918,923 [Application Number 05/382,307] was granted by the patent office on 1975-11-11 for wear resistant sintered alloy.
This patent grant is currently assigned to Riken Piston Ring Industrial Co., Ltd.. Invention is credited to Hiroshi Inoue.
United States Patent |
3,918,923 |
Inoue |
November 11, 1975 |
Wear resistant sintered alloy
Abstract
An iron base sintered alloy having high wear resistance produced
in a feasible and effective way, provided by compounding molybdenum
disulfide or the like metal sulfide having its melting point higher
than the sintering temperature of the alloy. Sulphur in the sulfide
forms iron sulfide which improves wear resisting property of the
alloy, while, metallic component of the sulfide diffuses throughout
the base metal and serves to enhance the strength of matrix. Test
results with apex seals of rotary piston engine revealed that wear
amount of seals made of the alloy according to the present
invention is extremely low as compared with those made of
molybdenum-copper-cast iron, graphite or sintered alloy which is
sintered and thereafter sulphurized by gas sulphurizing
process.
Inventors: |
Inoue; Hiroshi (Kashiwazaki,
JA) |
Assignee: |
Riken Piston Ring Industrial Co.,
Ltd. (Tokyo, JA)
|
Family
ID: |
13745551 |
Appl.
No.: |
05/382,307 |
Filed: |
July 25, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Aug 16, 1972 [JA] |
|
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47-81410 |
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Current U.S.
Class: |
75/230; 75/231;
75/246; 418/178; 419/10; 419/11 |
Current CPC
Class: |
F01C
19/005 (20130101); C22C 33/0221 (20130101) |
Current International
Class: |
C22C
33/02 (20060101); F01C 19/00 (20060101); B22F
001/00 () |
Field of
Search: |
;75/203,204,201,128D,128P ;29/182.5 ;418/178 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Hunt; B. H.
Claims
What is claimed is:
1. A method of preparing a wear-resistant iron-base alloy
comprising the steps of:
preparing a powder mixture comprising 1.0-1.8% carbon, 0.5-2.0%
chromium, 0.5-1.0% nickel, 2.0-8.0% of one or more metal sulfides
selected from a group consisting of aluminum sulfide, cobalt
sulfide, tungsten sulfide, copper sulfide, lead sulfide, and
molybdenum sulfide, and the balance iron;
compressing said powder mixture into a form;
sintering said form at a temperature below the melting point of
said one or more metal sulfides;
maintaining said form at temperatures up to said sintering
temperature to distribute the sulfur of said one or more metal
sulfide substantially in the microstructure of said alloy as iron
sulfides, and the metal of said one or more metal sulfides
substantially uniformly within the matrix of said alloy; and
cooling said form to room temperature.
2. The method as claimed in claim 1, wherein said one or more metal
sulfides comprises molybdenum disulfide.
3. The method as claimed in claim 2, wherein said step of sintering
comprises heating said form at 1,120.degree.C for 30 minutes in a
reducing gas atmosphere.
4. A wear resistant sintered alloy prepared from a mixture of
powders comprising:
1.0-1.8% carbon, 0.5-2.0% chromium, 0.5-1.0% nickel, 2.0-8.0% of
one or more metal sulfides selected from a group consisting of
aluminum sulfide, cobalt sulfide, tungsten sulfide, copper sulfide,
lead sulfide, and molybdenum sulfide, and the balance iron;
said alloy having a sintered microstructure comprsing a pearlite
matrix, free cementite located at grain boundaries, and pores, and
wherein
the sulfur of said one or more metal sulfide is distributed
substantially in said microstructure as iron sulfide inclusions,
and the metal of said one or more metal sulfides is distributed
substantially uniformly within said matrix.
5. The sintered alloy as claimed in claim 4, wherein said one or
more metal sulfides comprises molybdenum disulfide.
6. An apex seal for a rotary piston engine made from the wear
resistant sintered alloy as claimed in claim 4.
Description
BACKGROUND OF THE INVENTION
The present invention relates to wear resistant sintered alloy
suitable for high speed sliding members or the like.
For the members sliding at high speed and in high ambient
temperature, like apex seals of rotary piston engine, which are
mounted on the rotary piston and forced to slide against trochoidal
inner surface of the cylinder under a circumstance where the
breaking of lubricating oil film on that sliding surface is apt to
occur, less hardness decrease during operation and excellent oil
retaining property to hold lubricating oil film on said sliding
surface are required as well as high wear resistance.
Conventionally, cast iron of pearlitic structure has been used
widely as a material of such sliding members. It is considered that
the self-lubricating and oil retaining properties of graphite
itself contained in the cast iron, together with pearlitic
structure of the matrix, make the material wear resistant.
Therefore, wear resistance of such cast iron will be increased by
increasing graphite content, but there is a limit for the carbon
content of cast iron, and it is difficult to make the content of
free graphite more than 3%.
Further, the use of graphite itself for such sliding members has
been tried also, but this is unfavorable because of its rapid
wear.
As is widely known, sintered alloy obtained by the powder
metallurgical process is porous and has good oil retaining or
holding property. Therefore, excellent wear resistant material
would be obtained according to the powder metallurgical process by
adding some of the elements which increase wear resisting property
of the material.
As a method to improve the wear resisting property of iron base
alloys, the gas sulphurizing process, in which sulphur is diffused
and impregnated in the surface layer of iron or steel and thereby
forms iron sulfide, has been known. However, it is difficult to
apply this process to the sintered alloy at present because of such
problems as corrosion of sintering furnace and generation of
harmful gas, and expected results could not been obtained by this
process under our experiments.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a
sintered alloy having high wear resistance produced in a more
feasible and effective process.
Another object of the present invention is to provide a sintered
alloy suitable for apex seals of rotary piston engine.
It has been found that the foregoing and related objects may be
readily attained in a sintered alloy made by a process comprising
the steps of preparing powder mixture by weight of 1.0-1.8% carbon,
0.5-2.0% chromium, 0.5-1.0% nickel, 2.0-8.0% metal sulfide or
sulfides and rest of iron, forming said powder mixture by
compressing, and sintering said formed powder mixture, wherein said
metal sulfide or sulfides having melting point higher than
sintering temperature of said formed powder mixture.
It has been found that sulphur in said metal sulfide or sulfides
combines with iron and forms iron sulfide while sintering which
improves wear resisting property of the alloy.
Metallic component of the sulfide diffuses into the base metal and
serves to enhance the strength of matrix.
It has also been found that the alloy is particularly suitable for
the apex seal of rotary piston engine, and capable of forming to
its shape precisely by machining.
Further objects, features and advantages of the present invention
will be apparent by the following description with reference to the
accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1(A) and 1(B) are micrographs (.times. 400 .times. 1.5)
showing the structures of one example of the sintered alloys
according to the present invention, in which FIG. 1(A) is as
polished and FIG. 1(B) is as polished and etched by 2% HNO.sub.3
alcoholic solution.
FIGS. 2(A)-(D) are photographs taken by the electron microprobe
analysis, in which,
FIG. 2(A) shows absorbed electron image,
FIG. 2(B) shows L.sub..alpha.-characteristic X-ray image of
molybdenum,
FIGS. 2(C) and (D) show K.sub..alpha.-characteristic X-ray images
of sulphur and iron, respectively.
FIG. 3 is a graph illustrating the variation of tensile strength of
the alloy according to the present invention in relationship with
different molybdenum disulfide contents.
FIG. 4 is a graph illustrating the amount of wear of apex seal made
of the alloy according to the present invention in comparison with
those made of molybdenum-copper-cast iron, graphite and sulphurized
sintered alloy respectively, after the actual engine test.
DESCRIPTION OF THE PREFERED EMBODIMENTS
Following kinds of powder were prepared as the raw materials of the
alloy;
iron: under 100 mesh deoxidized mill scale powder,
carbon: 98% purity natural graphite powder of 10 microns in average
size,
nickel: carbonyl nickel powder,
chromium: under 100 mesh ferrochromium containing 60% chromium by
weight,
sulfide: molybdenum disulfide (MoS.sub.2) powder of 10 microns in
average size.
These powders were compounded and mixed thoroughly so as to contain
1.5% carbon, 1.8% chromium, 0.7% nickel, 4% molybdenum disulfide
and rest of iron, each by weight.
The mixture was compressed under 4 ton/cm.sup.2 pressure to form 75
.times. 10 .times. 6 mm size specimens with density of 6.6
gram/cm.sup.3.
The formed specimens were then sintered at 1,120.degree.C for 30
minutes in a prepared atmosphere of RX gas of 24% CO, 31% H.sub.2
and 45% N.sub.2 in average composition and 0.degree.C dew point.
The RX gas here means reducing gas mixture obtained by modifying
hydrocarbon gases.
Thereafter, the specimens were cooled to 500.degree.C over 40
minutes, and then cooled in furnace to room temperature.
Density of the sintered specimens was 6.0 gram/cm.sup.3.
Microstructures of the specimen are shown in FIG. 1.
FIG. 1(A) is a micrograph of specimen as polished, and FIG. 1(B) is
a micrograph of the same specimen etched by 2% HNO.sub.3 alcoholic
solution, wherein black portions indicate pores, grey portions
indicate sulfides, white portions located at the grain boundaries
indicate free cementites and matrix is pearlite.
FIGS. 2 show photographs taken by the electron microprobe analysis,
wherein FIG. 2(A) indicates absorbed electron image showing the
region including sulfide, FIG. 2(B) indicates L.sub..alpha.
characteristic X-ray image of molybdenum, FIG. 2(C) indicates
K.sub..alpha. characteristic X-ray image of sulphur and FIG. 2(D)
indicates K.sub..alpha. characteristic X-ray image of iron.
From these photographs, it will be seen that the sulfide formed is
iron sulfide and molybdenum does not remain in the sulfide, but
diffuses uniformly into the matrix.
FIG. 3 is a graph indicating tensile strength of the sintered alloy
made by the process mentioned above, but changing the amount of
molybdenum disulfide addition.
The tensile strength decreases with an increase of amount of
molybdenum disulfide, but it will retains about 13 kg/mm.sup.2 at
8% molybdenum disulfide addition, which strength would be enough
for the practical use.
Samples obtained by the above mentioned process were machined to
the shape of apex seal for rotary piston engine and mounted on a
rotary piston and assembled in the center housing having a chromium
plated trochoidal inner surface, and subjected to 300 hours actual
engine test.
No. 1 in FIG. 4 shows the wear amount of the tested apex seals.
Seals made of different materials were also tested for
comparison.
No. 2 and No. 3 show the wear amount of seals each made of
molybdenum-copper-cast iron and graphite respectively, both were
tested for 100 hours.
No. 4 shows the wear amount of apex seals made by the similar
process as No. 1, except that in this case molybdenum was added in
the form of ferromolybdenum containing 60% molybdenum and the
sintered alloy was thereafter gas sulphurized. Running test in this
case was performed for 300 hours.
Test results show that the apex seals according to the present
invention is extremely excellent in wear resistance as compared
with those of the other three materials. Wear of the cylinder wall
after the test was practically negligible small except the case of
No. 2 in which wavelike wears of about 8 micron depth were observed
on the wall surface.
Referring now to each component of the alloy, carbon is a basic
element which imparts wear resistance and mechanical strength to
the alloy. It makes the matrix pearlitic, further precipitates free
cementite to make the alloy endurable against hard sliding mating
parts.
Carbon content of less than 1% will not be sufficient for such
purposes, but the content of more than 1.8% would rather
deteriorate the mechanical properties because of the precipitation
of excessive cementite.
Chromium increases mechanical strength and wear resistance of the
alloy, but it is not preferable to contain chromium more than 2%,
because the alloy becomes too hard due to increase of chromium
carbide content.
Nickel improves the alloy structure and increases mechanical
strength and wear resistance. However, it requires considerably
high temperature to diffuse nickel into the matrix uniformly.
Therefore, it is preferable to limit nickel content to less than 1%
for the present sintering temperature.
As for the metal sulfide, which is considered as a carrier of the
sulphur into the alloy, sulfide or sulfides of such metals as
aluminium, chromium, cobalt, tungsten, copper, lead and molybdenum
may be recommended for the use in consideration of its melting
point, affinity of each metal to sulphur comparing to that of iron,
and the effect of each metal on the mechanical properties of the
alloy.
If melting point of a metal sulfide is lower than the sintering
temperature, sulphur may come out of the alloy and cause not only
decrease of sulphur content but contamination of the sintering
atmospheric gases, so that it is necessary that the melting point
of metal sulfide is higher than the sintering temperature of usual
iron base sintered alloy which is approximately 1050.degree. -
1150.degree.C.
It is preferable to limit the quantity of metal sulfide to be added
to less than 8% from the reason mainly of the adverse effect on
mechanical strength of the alloy as shown in FIG. 3, but in case of
less than 0.5%, it has little effect on wear resisting property,
and it is recommended to add more than 2% to retain remarkable
effect even when mechanical parts are used under severe
conditions.
As aforementioned, the alloy of the present invention is porous and
has good oil retaining property. Moreover, a higher proportion of
iron sulfide of high wear resisting property is easily formed
within the base metal which itself is wear resistant, without any
problems of such as harmful gas generation. Further, metallic
component of the metal sulfide diffuses into the base metal and
serves to enhance the strength of matrix.
Therefore, according to the present invention, the alloy of high
wear resistance and good oil retaining property and still retaining
enough mechanical strength may be obtained in a feasible and
effective way.
The alloy is not only suitable in use for the ordinary sliding
mechanical parts, but is also particularly usable for the members
used under severe conditions, like the apex seal of rotary piston
engine, in which the breaking of lubricating oil film may occur due
to very high speed sliding at high ambient temperature.
Further, like molybdenum disulfide, many of the metal sulfides used
in the present invention have excellent selflubricating property,
so that the products of high compressed density may be obtained
with such sulfides even under less compressive load and with less
additional lubricant at the step of forming, and this may also
enable the use of existing equipments. The sulfide may also improve
the machinability of sintered alloy which heretofore has been
considered as inferior.
* * * * *