U.S. patent number 3,790,352 [Application Number 05/217,031] was granted by the patent office on 1974-02-05 for sintered alloy having wear resistance at high temperature.
Invention is credited to Kametaro Hashimoto, Kunizo Imanishi, Seishu Mitani, Itaru Niimi, Yoichi Serino, Kenzi Ushitani.
United States Patent |
3,790,352 |
Niimi , et al. |
February 5, 1974 |
SINTERED ALLOY HAVING WEAR RESISTANCE AT HIGH TEMPERATURE
Abstract
The present invention relates to iron-base sintered alloys
having excellent wear resistance at high temperatures, and more
particularly to alloys adapted for fabricating valve seat rings of
internal combustion engines. The alloys of the present invention
are characterized by infiltrating selected metals having
lubricating properties or the alloys thereof into the pores of
iron-chromium-carbon base sintered alloys having significant
mechanical strength and heat resistance.
Inventors: |
Niimi; Itaru (Chigusa-ku,
Nagoya, JA), Hashimoto; Kametaro (Toyota,
Aichi-prefecture, JA), Ushitani; Kenzi (Toyota,
Aichi-prefecture, JA), Serino; Yoichi (Toyota,
Aichi-prefecture, JA), Mitani; Seishu (Anshubaba,
Yamashina, Higashiyama-ku, Kyoto, JA), Imanishi;
Kunizo (Mizuho-ku, Nagoya, JA) |
Family
ID: |
12762736 |
Appl.
No.: |
05/217,031 |
Filed: |
January 11, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Jun 28, 1971 [JA] |
|
|
46-046994 |
|
Current U.S.
Class: |
428/568;
29/888.44; 75/247; 75/246 |
Current CPC
Class: |
F01L
3/02 (20130101); C22C 33/0242 (20130101); C22C
33/02 (20130101); Y10T 428/12167 (20150115); Y10T
29/49306 (20150115) |
Current International
Class: |
C22C
33/02 (20060101); F01L 3/02 (20060101); C22c
001/04 (); B22f 007/00 (); B22f 005/00 (); B21k
001/24 () |
Field of
Search: |
;29/182.1,156.7A ;75/200
;123/188 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Schafer; R. E.
Attorney, Agent or Firm: Connolly and Hutz
Claims
1. A wear resistant metal comprising a sintered skeleton consisting
essentially of iron having 0.2 to 15 percent by weight chromium and
0.2 to 1.0 percent by weight carbon, and an infiltrant selected
from the group consisting of 10 to 30 percent by weight copper, 10
to 30 percent by weight copper-base alloy, 1 to 25 percent by
weight lead, 1 to 25 percent
2. A valve seat for an internal combustion engine fabricated of the
wear
3. The wear resistant metal of claim 1 in which the copper-base
alloy infiltrant includes at least one metal selected from the
group consisting
4. A valve seat for an internal combustion engine fabricated of the
wear
5. The wear resistant metal of claim 1 in which the lead-base alloy
infiltrant includes at least one metal selected from the group
consisting
6. A valve seat for an internal combustion engine fabricated of the
wear
7. A wear resistant metal comprising a sintered skeleton consisting
essentially of iron having 0.2 to 15 percent by weight chromium and
0.2 to 1.0 percent by weight carbon, and an infiltrant consisting
of 5 to 30
8. A valve seat for an internal combustion engine fabricated of the
wear
9. The wear resistant metal of claim 7 in which the copper-lead
base alloy
10. A valve seat for an internal combustion engine fabricated of
the wear
11. The wear resistant metal of claim 7 in which the copper-lead
base alloy infiltrant includes at least one metal selected from the
group consisting
12. A valve seat for an internal combustion engine fabricated of
the wear resistant metal of claim 11.
Description
BACKGROUND OF THE INVENTION
The present invention relates to sintered alloys having wear
resistance at high temperatures.
Materials such as special cast iron and heat resistant steel have
commonly been used for constructing valve seat rings of internal
combustion engines. The use of these materials does not adversely
affect the engines when leaded gasoline is used as fuel because
lead tetrachloride added to the fuel as an antiknock agent forms
lead oxide at combustion which adheres to the surface of valve seat
rings. The lubricating action offered by lead oxide is quite useful
in preventing the valve seat rings from wearing away, thus
maintaining full performance of the engine. However, when engines
are fueled by LPG (Liquefied Propane Gas) containing no lead or
lead-free gasoline, the lubricating action by lead oxide is lost
and the valve seat rings made of the above materials are remarkably
worn away during engine operation. This results in decreased engine
output and abnormal engine operation.
In order to overcome the above-mentioned disadvantages, the
sintered alloys of the present invention exhibit superior wear
resistance at high temperatures. As a result, the valve seat rings
made of the present alloy do not wear away even when LPG or
lead-free gasoline is used as fuel. The engines are therefore
maintained at normal working conditions. Also, the alloys of the
present invention are suitable for use in fabricating bearings for
hot rollers and other parts that are exposed to or reach high
temperatures during use thereof.
SUMMARY OF THE INVENTION
Accordingly, the primary object of the present invention is to
provide alloys having excellent wear resistance at elevated
temperatures.
In accordance with the present invention sintered alloys having
excellent wear resistance at high temperatures are obtaine by
infiltrating selected metals having lubricating action or the
alloys thereof into the pores of iron-chromium-carbon base sintered
skeletons which, by weight percentage, are composed of 0.2 to 1.0
percent carbon, 0.2 to 15 percent chromium and the remainder iron.
The selected metals or alloys thereof for this purpose include:
copper (or copper-base alloys added with one or two or more metals
selected from tin, zinc and chromium) which is used for
infiltration by 10 to 30 percent of the total alloy weight;
copper-lead alloys (or copper-lead base alloys added with one or
two or more metals selected from tin, zinc and chromium) which is
used for infiltration by 5 to 30 percent; and lead or antimony (or
lead-base alloys added with one or two or more metals selected from
antimony, bismuth and cadmium) which is used for infiltration by 1
to 25 percent.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to sintered alloys having excellent
wear resistance at high temperatures. These alloys are
characterized by infiltrating selected metals having lubricating
properties or the alloys thereof into the pores of
iron-chromium-carbon sintered skeletons having high mechanical
strength and heat resistance.
The effect of each constituent element and the reason for defining
the content of each element is explained below. First, the
description refers to each element added to the sintered
skeletons.
Carbon forms pearlite in combination with iron which increases the
strength and the wear resistance of the alloys. However, at less
than 2 percent content there is only insufficient strength and wear
resistance, while addition of more than 1.0 percent of carbon
results in precipitating cementite which makes the alloys fragile
and difficult, if not impossible, to machine properly. Since both
cases are undesirable, the carbon content is between 0.2 and 1.0
percent.
Chromium melts into iron in the form of a solid solution and makes
iron tough by forming composite carbides such as (Fe.sub.3
C).sub.18 Cr.sub.4 C, (Fe.sub.3 C).sub.9 Cr.sub.4 C and Fe.sub.3
C.Cr.sub.4 C. These carbides are coexistent with Fe.sub.3 C, and
quite useful in increasing the hardness of the steels and their
wear resistance. Furthermore, chromium remains stable at high
temperatures. It diminishes the deterioration of the materials
caused by a rise in temperature and increases their heat
resistance. However, at less than 0.2 percent content there is
little if any effect, while at more than 15 percent very little
effect results when compared with the amount added. The
machinability of the resulting alloys is also poor. Both cases
should be avoided. Thus, the chromium content is between 0.2 and 15
percent.
The description explains each element to be added for the purpose
of infiltration.
When copper is added a portion melts into iron in the form of a
solid solution and is effective in strengthening the alloys. The
remaining portion fills the pores of the sintered skeletons and
brings about increased heat conductibility which in turn lowers the
heat load by the alloys. At the same time, copper forms a thin film
of its oxide on the surface and increases the wear resistance of
the alloys through the lubricating action of this oxide film.
However, at less than 10 percent copper the effect of infiltration
is very small, while at more than 30 percent the strength of the
sintered skeletons deteriorates. Accordingly, the preferred copper
content is between the above two percentages.
Lead used for infiltration turns into lead oxide during actual use
of the alloys. The lead oxide adheres in a thin layer on the
surface of the alloys, and thereby produces a lubricating action
which increases the wear resistance of the alloys. The secondary
effect of lead is to remarkably increase the machinability of the
alloys. However, at less than 1 percent the effect is very slight
and a uniform distribution of lead is unobtainable. At more than 25
percent of the amount for infiltration the strength of the alloys
drops. Therefore, the preferred range of lead is 1 to 25
percent.
The affect of antimony is similar to lead. Since the melting point
of antimony is higher than that of lead (melting point of antimony
is 630.degree. C., lead 327.degree. C.), antimony is suitable for
alloys used at higher temperatures when compared with the alloys
infiltrated with lead. As in the case of lead infiltration, at less
than 1 percent antimony the effect is slight, while at more than 25
percent the strength of the alloys drops. Therefore, the preferred
range of antimony is 1 to 25 percent.
As shown in Example 2, a 70 percent copper -- 30 percent lead alloy
(Kelmet) is used for infiltration. In this case, in addition to the
above-mentioned individual effect of copper and lead, copper
improves the wettability of lead towards iron and gives lead a
promoted lubricating action which increases the wear resistance.
However, at less than 5 percent the effect by infiltration is
slight, while at more than 30 percent the strength of the sintered
skeletons drops. The preferred range of the above alloy types is 5
to 30 percent.
As shown in Example 4, a copper-lead base alloy added with tin is
used for infiltration. The tin has the effect of partly melting
into copper in the form of a solid solution and increasing the
strength and the wear resistance of copper. Tin also has the effect
of dispersing lead in a fine and uniform state in copper and
further increasing the wear resistance of the alloys.
Zinc added to copper reacts similar to tin. Moreover, zinc forms a
film of its oxide at high temperature during practical use of the
alloys and lowers the coefficient of friction which increases the
wear resistance.
In Example 3 infiltration with a copper-chromium alloy is
explained. A portion of the chromium melts into copper in the form
of a solid solution and strengthens the copper, while the remaining
portion forms a film of its oxide on the surface at high
temperature and gives the alloy a reduced coefficient of friction
which increases the wear resistance of the alloys even more.
Infiltration with a 90 percent lead - 10 percent bismuth alloy is
explained in Example 6. The bismuth reduces the melting tendency of
lead, and increases the lubricating action by lead in cases where
lower temperature and load are employed with valve seats or
bearings.
Cadmium is effective in restraining lead from its expansion at
melting whereby lead may be more captured.
As described hitherto, the sintered alloys according to the present
invention are provided with greatly increased wear resistance at
high temperatures by infiltrating metals or alloys thereof having
significant lubricating properties into the pores of
iron-chromium-carbon base alloys having superior strength and wear
resistance at high temperature. The metals or alloys thereof used
for infiltration are: copper, lead; antimony; copper-base alloys
added with one or two or more metals selected from tin, zinc, lead
and chromium; lead-base alloys added with one or two or more metals
selected from antimony, bismuth and cadmium.
It should be noted that according to the conventional method of
producing iron-carbon base sintered alloys, lead is premixed with
iron powder and graphite powder as a means of adding lead. In such
mixing methods, it is difficult to achieve uniform distribution of
lead or other elements or alloys thereof, and the lead is scattered
in the air during the sintering process whereby lead is less
captured. On the other hand, the infiltration according to the
present invention has the advantage of obtaining a uniform
distribution and a satisfactory capture of lead and other
substances. Therefore, alloys of uniform quality are obtained in
mass production.
The present invention is described below with reference to its
various embodiments.
EXAMPLE 1
Reducing iron powder of minus 100 mesh, iron-chromium alloy powder
of minus 100 mesh and graphite powder are mixed to provide a
composition of 99.4 percent iron, 5 percent chromium and 0.6
percent carbon, each by weight percentage. After this mixture is
formed under a forming pressure of 5 t/cm.sup.2 to a density of 6.7
g/cm.sup.3, the formed mass is sintered at 1,300.degree. C. for one
hour and a half in a reducing gas atmosphere to obtain a sintered
skeleton. The sintered skeleton is then infiltrated at
1,130.degree. C. for one hour and a half in a reducing gas
atmosphere using a material composed of 90 percent copper, 5
percent iron and 5 percent manganese. A sintered alloy of the
present invention is obtained.
EXAMPLE 2
Using the sintered skeleton of Example 1, the pores of the skeleton
are infiltrated with a 70 percent copper -- 30 percent lead alloy
(Kelmet) at 1,050.degree. C. for one hour in a reducing gas
atmosphere. A sintered alloy of the present invention is
obtained.
EXAMPLE 3
Using the sintered skeleton of Example 1, the pores of the skeleton
are infiltrated with a 95 percent copper - 5 percent chromium alloy
at 1,130.degree. C. for one hour in a reducing gas atmosphere. A
sintered alloy of the present invention is obtained.
EXAMPLE 4
Using the sintered skeleton of Example 1, the pores of the skeleton
are infiltrated with a 60 percent copper -- 30 percent lead -- 10
percent tin alloy at 1,050.degree. C. for one hour in a reducing
gas atmosphere. A sintered alloy of the present invention is
obtained.
EXAMPLE 5
Reducing iron powder of minus 100 mesh, iron-chromium alloy powder
of minus 100 mesh and graphite powder are mixed to provide a
composition of 93.2 percent iron, 6 percent chromium and 0.8
percent carbon, each by weight percent. The mixture is formed under
a forming pressure of 6 t/cm.sup.2 to a density of 7.1 g/cm.sup.3.
Thereafter, the formed mass is sintered at 1,300.degree. C. for one
hour and a half in a reducing gas atmosphere, and a sintered
skeleton is obtained. The pores of the sintered skeleton are
infiltrated with lead at 1,000.degree. C. for 45 minutes in a
reducing gas atmosphere. A sintered alloy of the present invention
is obtained.
EXAMPLE 6
Using the sintered skeleton of Example 5, the pores of the skeleton
are infiltrated with a 90 percent lead -- 10 percent bismuth alloy
at 1,000.degree. C. for 45 minutes in a reducing gas atmosphere. A
sintered alloy of the present invention is obtained.
EXAMPLE 7
Using the sintered skeleton of Example 5, the pores of the skeleton
are infiltrated with antimony at 1,100.degree. C. for one hour and
a half in a reducing gas atmosphere. A sintered alloy of the
present invention is obtained.
Next, the alloys of the present invention as obtained in Examples 1
through 7 are tested for their properties and quantities of wear at
high temperature. The results are shown in the following table. In
the table, quantities of wear are indicated by the worn away
quantities in millimeters in the direction of the height of the
specimens measured after the testing has been continued for 100
hours by a so-called "sliding high-cycle impact tester" wherein
2500 shocks a minute are given to the angular specimens under a
surface pressure of 30 kg/cm.sup.2 by means of a jig made of heat
resistant steel. The angular specimens fixed to cast iron are
rotated 10 times a minute at an elevated temperature of 500 to
550.degree.C.
TABLE
__________________________________________________________________________
Composition (% by weight) Tensile strength (Kg/mm.sup.2) Hardness
(Hv.0.2) Quantity of wear
__________________________________________________________________________
(mm) Alloys of the Present Invention Example 1 (Fe-5Cr-0.6C)-14 Cu
infiltrated 72 327-354 0.51 Example 2 (Fe-5Cr-0.6C)-14(70Cu-30Pb)
infiltrated 70 315-342 0.32 Example 3 (Fe-5Cr-0.6C)-14(95Cu-5Cr)
infiltrated 72 327-366 0.44 Example 4
(Fe-5Cr-0.6C)-14(60Cu-30Pb-10Sn) infiltrated 67 310-353 0.32
Example 5 (Fe-6Cr-0.8C)-9Pb infiltrated 58 250-322 0.40 Example 6
(Fe-6Cr-0.8C)-9(90Pb-10Bi) infiltrated 60 262-321 0.37 Example 7
(Fe-6Cr-0.8C)-9Sb infiltrated 62 276-329 0.38 Comparison Examples
Special Cast Iron (Fe-3.5C-2.5Si-1Mn-0.5P-0.5Cr-0.5Mo-0.1V) 40
250-300 7.42 Heat Resisting Steel (Fe-0.4C-2Si-15Cr-15Ni-2W-0.5Mn)
90 290-310 6.88
__________________________________________________________________________
* * * * *