U.S. patent number 3,863,318 [Application Number 05/336,945] was granted by the patent office on 1975-02-04 for high temperature-resistant wearproof sintered alloys.
This patent grant is currently assigned to Toyota Jidosha Kogyo Kabushiki Kaisha. Invention is credited to Kametaro Hashimoto, Kunizo Imanishi, Seishu Mitani, Itaru Niimi, Yoichi Serino, Tetsuya Suganuma, Kenji Ushitani.
United States Patent |
3,863,318 |
Niimi , et al. |
February 4, 1975 |
High temperature-resistant wearproof sintered alloys
Abstract
This invention relates to iron base sintered alloys which excel
in high temperature resistance and wear resistance and are
especially suited for use in the valve seats of an internal
combustion engine. These high temperature-resistant, wear resistant
sintered alloys are characterized by the fact that they contain Fe
as their main component, together with Mo 3-20%, C 0.5-1.5%, Co
3-25% and Pb 1-15% by weight; and that the Fe matrix has very hard
particles, which contain intermediate phase .epsilon., and Pb
dispersed therein.
Inventors: |
Niimi; Itaru (Nagoya,
JA), Hashimoto; Kametaro (Toyota, JA),
Ushitani; Kenji (Toyota, JA), Serino; Yoichi
(Toyota, JA), Suganuma; Tetsuya (Toyota,
JA), Mitani; Seishu (Kyoto, JA), Imanishi;
Kunizo (Nagoya, JA) |
Assignee: |
Toyota Jidosha Kogyo Kabushiki
Kaisha (Aichi-ken, JA)
|
Family
ID: |
12097392 |
Appl.
No.: |
05/336,945 |
Filed: |
March 1, 1973 |
Foreign Application Priority Data
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|
|
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Mar 6, 1972 [JA] |
|
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47-22969 |
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Current U.S.
Class: |
75/243; 75/246;
75/231; 419/11 |
Current CPC
Class: |
C22C
33/0285 (20130101); C22C 33/0257 (20130101); C22C
33/0278 (20130101) |
Current International
Class: |
C22C
33/02 (20060101); B22f 001/00 () |
Field of
Search: |
;75/200
;29/182,182.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Bain et al., Alloying Elements in Steel, ASM 2nd Ed. (1966), p. 72
& 73..
|
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Hunt; B. H.
Attorney, Agent or Firm: Brisebois & Kruger
Claims
What is claimed is:
1. High temperature resistant, wear-resistant sintered alloy
consisting essentially of:
3-20% by weight of molybdenum,
0.5-1.5% by weight of carbon,
3-25% by weight of cobalt,
1-15% by weight of lead, and
balance mainly iron,
said alloy being in the form of particles consisting essentially of
molybdenum and iron, said particles being several tens of microns
in size and having a Vickers hardness of 600-1,300, and lead,
dispersed in an iron-based matrix softer than said molybdenum-iron
particles.
2. Alloy as claimed in claim 1 in which said molybdenum-containing
particles comprise an .epsilon. phase.
3. Alloy as claimed in claim 1 in which said matrix contains less
than 3% molybdenum.
4. Alloy as claimed in claim 3 containing from 5-15%
molybdenum.
5. Alloy as claimed in claim 1 containing from 1-15% nickel.
6. Alloy as claimed in claim 1 containing 3-25% chromium.
7. Alloy as claimed in claim 1 containing nickel and chromium in a
total amount lying between 2 and 30%.
8. Alloy as claimed in claim 1 containing molybdenum and chromium
in a total amount of at least 18%.
9. Alloy as claimed in claim 1 in which said alloy has a Vickers
hardness lying between 150 and 330.
10. Alloy as claimed in claim 1 consisting essentially of the
constituents claimed in claim 1, and at least one additional
ingredient selected from the group consisting of 1-15% nickel and
3-25% chromium.
Description
BACKGROUND OF THE INVENTION
Conventionally, valve seats have been made mostly of special cast
iron or heat-resistant steel. These materials perform well when the
gasoline contains an anti-knock agent such as tetraethyl lead, but
perform poorly when lead-free gasoline is used. In the first case,
various organic leads added to the gasoline for anti-knock purposes
become lead oxides when the gasoline burns and are deposited on the
working surfaces of valves and valve seats, thereby serving to
protect or lubricate the surface of the valve seats or absorb the
impact energy of the valves, thus preventing wear of the valve
seats. When, however, the gasoline is lead-free, the anti-wear
effect of lead is lost and, in consequence, valve seats of
conventional material suffer heavy wear, resulting in a poor fit
between the valve and valve seat, which leads to a drop in the
output of the internal combustion engine and a failure to operate
normally. After much research to eliminate the above-mentioned
drawback, the present inventors have successfully perfected the
present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an optical microscopic composition photograph
illustrating a sintered alloy of the present invention,
FIG. 2 is an optical microscopic composition photograph
illustrating a reference alloy,
FIG. 3 is an explanatory diagram illustrating the wear resistance
structure of an invented sintered alloy.
SUMMARY OF THE INVENTION
The present invention relates to high temperature-resistant, wear
resistant sintered, iron-based alloys containing Mo 3-20%, C 0.5-
1.5%, Co 3-25%, and Pb 1-15% by weight. These alloys are
characterized by the fact that the Fe matrix has very hard
particles and Pb dispersed therein. If Ni 1-15% or Cr 3-25% or both
Ni and Cr totaling 2-30% by weight are added, further improvement
of the heat resistance and wearproof resistance will be
achieved.
DETAILED DESCRIPTION OF THE INVENTION
The object of the present invention is to provide high
temperature-resistant, wear resistant sintered alloys, suitable for
use as valve seat material, which assure the good performance of an
internal combustion engine which burns non-lead gasoline or light
oil or LPG, which is orginally free from organic lead, which are
suitable as wear resistant materials for bearings and siding parts
to be used under high temperature conditions.
The sintered alloys according to the present invention are high
temperature-resistant wear resistant sintered iron-based alloys
comprising Mo 3-20%, Co 3-25%, C 0.5-1.5% and Pb 1-15% by weight,
characterized by the fact that their relatively soft iron matrix
has dispersed evenly therein a phase mainly composed of Fe and Mo
with a particle size of several tens of microns and a hardness of
Hv 600-1300, and Pb.
If in these sintered alloys the above composition is modified by
the further addition of Ni 1-15% or Cr 3-25% or both Ni and Cr
totaling 2-30% by weight, their heat resistance and wear resistance
will be still further enhanced.
Some examples of the present invention will now be described:
The present invention is characterized by restricting the range of
components as well as by suitably controlling the sintering period
and temperature. Generally, it is preferable that the production of
Fe--base sintered alloys containing a considerable amount of Mo and
Co is processed by sintering at a temperature of 1,300.degree.C for
comparatively long periods of time to sufficiently diffuse alloy
atoms into Fe.
The present invention, however, is characterized in that even in
case a considerable quantity of Mo is added into the alloy,
sintering can be made at temperatures ranging from 1,130.degree. to
1,180.degree.C for a comparatively short period of time, such as 25
- 45 minutes in order to diffuse Mo or Cr into the Fe--matrix as
well as to control diffusion of Fe into Mo powder, and further
characterized in that the content of Mo in the Fe matrix is less
than 3%, Mo concentration in Mo powder is within 40 - 80% and the
hardness of the alloy is Hv (10) 600 - 1,300. The characteristic
features of the present invention will be concretely described
below with reference to the Figures.
FIG. 1 shows an optical microscopic composition photograph for the
specimen manufactured under the conditions given above, which
obviously shows the Mo-phases scattered in particles. FIG. 2 shows
another optical microscopic photograph for the specimen which
contains ingredients identical to those of specimen 4 and sintered
for 1 hour at a temperature of 1,300.degree.C, but the Mo--phases
as in FIG. 1 can not be seen and .epsilon. phases are significantly
precipitated on the grain boundary. With such a structure as shown
in FIG. 2, the alloy itself becomes fragile and moreover,
improvement in wear-resistance is hopeless due to peeling of the
phases precipitated on the grain boundary. As an example, the
wear-loss of the alloy presented in FIG. 2 is 5.74mm.
FIG. 3 is an explanatory diagram showing wear-resistance structure
at high temperature of the alloys according to the present
invention, and numbers 1, 2 and 3 in the FIG. indicate the Fe--base
matrix, hard Mo particles and Pb, respectively. At the start of
using the alloys according to the present invention, comparatively
soft surfaces of the Fe--base matrix are abraded, but hard Mo
particles form (.alpha. + .epsilon.) or Mo + .epsilon.) phases
which are stable at high temperature and highly wear-resistable
thereby lumpy and pitted surfaces are produced. Pb melted at high
temperature, permeates into the pitted portions, becomes lead oxide
and adheres.
FIG. 3 shows the above state, and the sintered alloys according to
the present invention demonstrate superb wear-resistance at high
temperature due to wear-resistance of hard Mo particles themselves
and also, due to the lubricating ability of lead oxide adhered to
the pitted portions.
Below, concrete descriptions are given by referring to the
embodiment according to the present invention.
In principle, reduced -100 mesh (less than 147.mu.) Fe--powder,
reduced -200 mesh (less than 74.mu.) Co--powder, nickel carbonyl
powder in 3.mu. average granularity, pounded -200 mesh Cr--powder,
flaky graphite powder and pounded -100 mesh Pb-powder were used.
For speciments No. 1,4,5,6,7,8 and 9, the alloys containing 63
percent of pounded -200 mesh Fe--Mo alloy powder and the balance of
Mo powder were used, and for specimens 2 and 3, reduced Mo--powder
with 3 - 6 granularity were employed and admixed to obtain
compositions given in Table 1. For admixing, a V-type power mixer
was used by adding 0.5 percent zinc stearate to each specimen as
lubricant.
Each of the admixed specimens was compressed and shaped at the
density of 6.8g/cm.sup.2 by means of a hydraulic press. For
specimens 1 - 5, sintering was made in a decomposed ammonium gas
atmosphere, and specimens 6 - 9 were sintered in a vacuum greater
than 10.sup.-.sup.3 mmHg in order to prevent oxidization due to the
content of Cr.
The sintering temperature was set within a range from 1,130.degree.
to 1,180.degree.C for restricting diffusion of Mo into the Fe
matrix at less than 3%.
Specimen 3 was made by adding and mixing pounded Pb--powder and
other ingredient powders at the same time, but for other specimens,
addition was processed by heating at a temperature of 900.degree.C
for 30 minutes in the decomposed ammonium gas atmosphere and
subjecting the specimens to Pb infiltration after sintering.
In this table, the amount of wear is expressed in terms of a
decrease (mm) in the height of a square speciment mounted in cast
iron after 100 hours of testing on a so-called "sliding high-cycle
impact" wear testing machine which rotates the specimen at 10 rpm
under a high temperature of 500.degree.-550.degree.C, and subjects
it to 2,500 impacts per minute with a contact pressure of 30
kg/cm.sup.2, using a jig made of heat-resistant steel.
TABLE
__________________________________________________________________________
Hardness Tensile Specimen Chemical composition Room 600.degree.C
strength Wear No. by weight (%) temperature (600.degree.C) Hv(10)
Hv(5) Kg/mm mm
__________________________________________________________________________
Example 1 (Fe-10% Mo-10% Co 240 180 29 0.73 1.2%C) -12%Pb Example 2
(Fe-3%Mo-3%Co-0.5%C) 150 120 13 0.61 15%Pb Example 3
Fe-20%Mo-25%Co-1.5%C 250 180 21 0.67 1%Pb Example 4
(Fe-10%Mo-10%Co-1%Ni 290 185 23 0.64 1.2%C) -12%Pb Example 5
(Fe-10%Mo-10%Co-15%Ni 340 220 37 0.51 1.2%C) -12%Pb Example 6
(Fe-10%Mo-10%Co-3%Cr 280 210 30 0.62 1.2%C) -12%Pb Example 7
(Fe-10%Mo-10%Co 320 230 46 0.48 35%Cr-1.2%C) -12%Pb Example 8
(Fe-10%Mo-10%Co-1%Ni 300 205 28 0.60 1%Cr-1.2%C) -12%Pb Example 9
(Fe-10%Mo-10%Co-5%Ni 330 240 54 0.46 25%Cr-1.2%C) -12%Pb Control 1
Fe,-3.5%C,-25%Si,-1%Mn, 280 220 30 7.42 (Cast iron)
0.5%P,-0.5%Cr,-0.5%Mo,-0.1%V Control 2 Fe,-0.4%C,-2%Si,-15%Cr, 300
260 45 6.88 (Heat-resist- 15%Ni,-2%W,-0.5%Mn ant steel)
__________________________________________________________________________
As seen from this Table, the amount of wear in the invented
sintered alloys is considerably less than that in the conventional
valve seat materials, i.e., cast iron and heat-resistant steel; and
if necessary, the high temperature strength can be further improved
through addition of Ni and Cr.
Next, the effects and the reasons for limiting the amounts of the
component elements in the sintered alloys according to the present
invention will be described.
In the sintered alloys according to the present invention, carbon
permeates into the iron in the form of a solid solution thereby
forming a perlite, and has the effect of increasing the hardness
and wear resistance of the alloy as well as improving its
mechanical properties and, combining with Mo to form carbides of
the Mo.sub.2 C or MoC type, it has the effect of increasing the
wear resistance of the alloy. When the carbon content is less than
0.5% however, the effect is unsatisfactorily small, and when it is
more than 1.5%, the carbides and cementite are precipitated so
excessively as to substantially impair the machinability of the
alloy to a great extent. For this reason, the carbon content should
be limited to 0.5-1.5%.
Both molybdenum and lead are basic elements in the sintered alloys
according to the present invention. In these alloys the Mo is not
diffused evenly in the Fe matrix, but it is scattered as grains of
several tens of microns in size. Meanwhile, by controlling the
Fe--diffusion into the Mo, the Mo included is in the .alpha.+
.epsilon. or (Mo + .epsilon.) phase, thereby making the hardness
equal to Hv 600-1,300.
The (Mo + .epsilon.) or (.alpha. + .epsilon.) phase thus obtained
retains its hardness even at 600.degree.C and exhibits high wear
resistance at high temperature. When the Mo--content is less than
3%, namely, the number of particles of (.alpha. + .epsilon.) or (Mo
+ .epsilon.) are insufficient, the wear resistance is still
insufficient and accordingly, an Mo--content of over 3% is
desirable. On the contrary, an Mo--content of over 20% is not so
effective as expected in improving the wear resistance and it even
lowers the mechanical properties of the alloy. Therefore the
Mo--content should lie within the 3-20% range. Meanwhile, Mo in
partial solid solution in Fe has the effect of increasing its
resistance to temper-softening at high temperatures and improving
its anti-impact properties. On the other hand, the precipitated or
quasi-precipitated Mo, forming Mo oxides at high temperatures,
contributes to the improvement of wear resistance through a
decrease in the coefficient of friction. Mo may be employed either
in the form of Mo--powder or in the form of an Fe--Mo alloy powder.
Co is also added to the sintered alloys of the present invention.
Co, as a total solid solution in Fe, has the effect of inhibiting
the growth of ferrite crystal grains, preventing a drop in hardness
at high temperatures progressively as the Co content increases, and
thereby improving the mechanical properties. This effect, coupled
with the effect of strengthening the bond between the Fe--matrix
and Mo grains, results in an improvement of wear resistance at high
temperatures. However, the effect attributable to Co for
solid-solution hardening the ferrite is small; and since it does
not cause a great increase in the hardness of the alloy at room
temperature, Mo has the advantage of not deteriorating the
machinability so much as it increases the heat resistance. This
advantage will not become practically available at a Co--content of
less than 5%, but when the content exceeds 25%, the advantage will
not be as great as would be expected from the increased content.
Moreover, at 36-69%, a super-lattice is partially formed, resulting
in an embrittlement of the alloy. Thus, the addition of Co should
be limited to 5-25%.
During service of the alloy lead is thinly deposited on the surface
of the alloy to form a lead oxide, which acts as a lubricant and
has the effect of improving the wear resistance of the alloy. The
remarkable increase in wear resistance at high temperatures of the
invented sintered alloys is the result of the combined effects of
Pb to provide lubrication, Mo to increase the wear resistance and
Co to increase the heat resistance. Also, Pb has the effect of
substantially improving the machinability, but this effect is low
at a Pb content of less than 1%, while at over 15% the high
temperature strength of the alloy obtained is inadequate.
Therefore, the content of Pb should be 1-15%.
Thus, according to the present invention, through adequate
combination of Fe, Mo. Co, C and Pb and effective utilization of
the obtained wear resistance, heat resistance and lubrication, an
improved high temperature wear resistance can be achieved as an
overall effect, and if necessary, the heat resistance and the wear
resistance associated with it can be further increased by adding Ni
and Cr either singly or in combination, without sacrificing the
above-mentioned effect.
The additional element Ni, which, like Co, can enter into a solid
solution with Fe in any ration, has the effect of increasing the
hardness and toughness of the alloy; and if Ni is added in great
quantity, it also has the effect of improving the heat
resistance.
Meanwhile, Mo, which can enter into a solid solution with Ni
containing up to 20% Mo, even at room temperature, has the effect
of strengthening the bond between the Fe-matrix and Mo and of
further enhancing the wear resistance of the sintered alloy
according to the present invention. This effect, however, is poor
when the Mo content is less than 1%. From the stand point of wear
resistance 5% will suffice but, depending on the required degree of
wear resistance, the content may be increased. At over 15%,
however, the effect of increased content in terms of heat
resistance will not be so great. Thus, its addition is normally
limited to less than 15%.
As for the Cr content, this element, as a solid solution in Fe,
makes Fe strong and tough; and in coexistence with Fe.sub.3 C it
forms 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 . CrC, which improve
the hardness and wear resistance of the alloy. Also, it has the
effect of minimizing the deterioration of material due to
temperature rise and enhancing the heat resistance. At less than
3%, its effect is not great, and at over 25% its effect is less
than might be expected from the increased content; rather it
aggravates embrittlement of the material. Therefore the preferred
Cr content is less than 25%.
When Ni and Cr are added at the same time, the desirable total
addition is 2-30%. If either Ni or Cr is singly added the effect of
simultaneous addition will not fully appear unless each content is
more than 0.5%.
According to the present invention grains several tens of microns
in size of (Mo + .epsilon. ) phase with Hv 600-1,300, which is
stable even at high temperatures, are evenly dispersed in the
matrix of a heat resistant sintered alloy of a relatively soft
Fe--Co--C system, thereby increasing the wear resistance of the
alloy. Pb is added to provide lubrication, and through the overall
effect of these additions, an excellent wear resistance at high
temperatures is secured in the alloy obtained. Depending on the
need therefore, Ni or Cr singly or in combination may be added to
further increase the heat resistance and wear resistance. For this
reason, the sintered alloys of the present invention are
particularly suitable for use as materials for valve seats in an
internal combustion engine which burns the fuel which is free from
anti-knock agents, such as non-leaded gasoline, LPG (liquefied
propane gas) or light oil; and equally suitable for use as
materials for bearings to operate under unlubricated and high
temperature conditions such as bearings in hot press rolls.
* * * * *