Background of the Invention
[0001] This invention relates to a process for producing alloy steel powder, particularly
to a process for producing low-oxygen, low-carbon alloy steel powder, in which the
oxidation of easily oxidizable elements, such as chromium, manganese, etc. has been
suppressed effectively.
[0002] Conventional processes for producing steel powder include water atomization, gas
atomization and oil atomization. They are all well known in the art. However, they
all present problems as mentioned hereinafter when they are used for producing alloy
steel powder which contains easily oxidizable elements such as mentioned above:
Water Atomization:
[0003] This process employs water as an atomizing agent. Therefore, the contamination of
the resulting powder with oxides is inevitable during atomization. The formation of
oxides is so great that the addition of easily oxidizable elements to an alloy system
should be restricted. Thus, in designing the alloy, the addition of easily oxidizable
elements is limited.
[0004] More particularly, when molten steel containing easily oxidizable elements such as
chromium (Cr), manganese (Mn), vanadium (V), niobium (Nb), boron (B), silicon (Si),
etc. is subjected to water atomization, these elements are oxidized, and reduction
of the thus oxidized steel powder will have to be carried out at a succeeding step
to lower the oxygen level of the powder. However, it is extremely difficult to reduce
the proportion of oxygen in steel to a practical level, and it requires complicated
processing.
[0005] For example, if, by specifically adjusting the atomizing conditions and atmosphere,
the oxygen level of as-atomized powder is made as low as 0.5% by weight, it is necessary
to treat the as-atomized powder at a temperature higher than 1150°C for five hours
or longer so as to obtain powder having a practical level of oxygen. However, after
such long time high temperature treatment, the resulting powder having the intended
level of oxygen is sintered and requires a heavy duty disintegration step. And, when
such a strong disintegration process is applied to the powder, the shape and size
of the resulting powder particles will differ very much from those of the as-atomized
powder, and their compressibility, compactibility and sintering applicability will
be impaired.
[0006] Another method of deoxidization of atomized powder has been proposed, in which a
substantial amount of carbon is intentionally added to the molten steel prior to the
water atomization. In this method the resulting atomized powder contains a relatively
large amount of carbon as a reducing agent, which serves to remove the oxygen contained
in the atomized powder in accordance with the reaction shown by the formula: C + 0
---> CO upon heating at a high temperature in vacuo. However, this method also requires
heating of the powder at a temperature higher than 1100°C for a long period of time
in order to reduce the amount of oxygen, resulting in the same problems as mentioned
in the above. In addition, since this method essentially requires the presence of
carbon in a predetermined amount in atomized powder, the apparatus and operation therefor
become very complicated making this method less practical.
Gas Atomization:
[0007] This is a process for producing steel powder by utilizing an inert gas such as N
2, Ar, etc. as an atomizing agent. This method results in less contamination with oxides.
However, with gas cooling the cooling rate of the atomized powder is small, and the
resulting particles tend to become round. Round particles are difficult to compact.
It is, therefore, necessary to compact such powder by means of canning compaction
techniques through cold (or hot) isostatic pressing etc. However, the compaction of
this type is very complicated and is costly, so this method is not often used.
[0008] Furthermore, with gas atomization a large volume of gas is required, so the operating
cost of this method is 10 times that of the water atomization process.
[0009] Thus, though the gas atomization method is practiced for special purposes, it is
rarely used for the production of steel powder to be sintered or sintered-forged,
which is the major application in the field of powder metallurgical technology.
Oil Atomization:
[0010] In this process for producing steel powder oil is used as the atomizing agent. This
process is superior to water atomization in that the oxidation of steel powder does
not occur, i.e. the oxidation of alloying elements does not occur. However, carburization
of the resulting powder, i.e. diffusion of carbon from the oil to the powder occurs
during atomization, and decarburization has to be carried out at a succeeding step.
[0011] If the alloy steel powder contains easily oxidizable elements such as Cr, Mn, V,
Nb, B, Si, etc., it is easier to carry out decarburization than to carry out reduction
on once oxidized steel powder. However, up to now no process has been proposed for
carrying out decarburization in an efficient and continuous manner.
[0012] As a decarburizing gas H
2, H
20, CO-C0
2, etc. are known in the art. Of them H
2 gas is not practical, because the decarburizing rate with H
2 gas is very low. On the other hand, although a decarburizing gas which contains an
oxidizing gas, such as H
20, CO
2, etc. can remarkably accelerate the decarburization, the oxidation of an element,
such as Cr, Mn, V, Nb, B, Si, etc. is inevitable under the decarburizing temperature
and atmospheric conditions under which the decarburization proceeds, because such
conditions put these elements in an oxidizing region defined by thermo-dynamic equilibrium
conditions. Therefore, special care is necessary to control the decarburizing conditions.
[0013] For the above reasons decarburization of oil atomized alloy steel powder has not
yet been worked out.
[0014] Patent document GB-A-20 94 834, however, describes an oil atomized low alloy steel
powder having improved compressibility, compactability and hardenability with a specified
chemical composition after a decarburization process. One specific example described
involves maintaining the "as atomized" steel powder at a temperature of 900°C for
ten minutes in an atmosphere of hydrogen and water vapour of

= 0.03. The composition of the "as atomized" steel powder is unspecified as is whether
the decarburized powder is cooled in an inert or a reducing atmosphere and whether
the powder is prepared in a continuous or discontinuous manner. Document GB-A-1 236
271 teaches a continuous decarburizing treatment for an "as atomized" steel powder
with 0.8% carbon and an unspecified amount of oxygen. The process includes pre-heating
and cooling steps that are carried out in air or by water cooling.
[0015] The present invention, however, provides a process for producing low-oxygen, low-carbon
alloy steel powder, the process including the steps of:
[0016] preparing molten steel which contains at least one easily oxidizable element selected
from the group consisting of chromium, manganese, vanadium, niobium, boron and silicon;
[0017] atomizing said molten steel by means of an atomizing agent containing a non-oxidizing
medium to provide as-atomized alloy steel powder containing 0.2% by weight or less
of oxygen and 0.1 % by weight or more of carbon;
[0018] adjusting the amount of carbon of said as-atomized alloy steel powder by passing
said as-atomized alloy steel powder continuously through a decarburizing zone comprised
of a pre-heated section, a decarburizing section and a cooling section, said pre-heating
and cooling sections being kept in an inert or reduced atmosphere; and maintaining
said powder in the decarburizing section in an atmosphere containing at least H
2 and H
20 gases under either of the below-defined conditions (A) or (B); and cooling the thus
obtained powder to room temperature.
[0019] Condition (A):
Temperature (t°C): 600°C Z t ≦ 950°C
Atmosphere (PH2/PH2O) : 0.5 Z PH2/PH2O ≦ 1000
[0020] Treating Time (8 minute):


[0021] Condition (B):
Temperature (t°C): 950°C < t Z 1250°C
Atmosphere (PH2/PH2O) : PH2/PH2O ≧ 0.5
[0022] Treating Time (8 minute):

[0023] The "P
H2" means a partial pressure of hydrogen gas and the "P
H20" means that of steam.
Brief Description of the Drawings
[0024] In the drawings:
Fig. 1 is graph showing the relationship between decarburizing temperature and changes
in carbon and oxygen content of steel powder with respect to treating period of time;
Figs. 2-7 are graphs showing the relationship between the PH2/PH2O ratio of the atmosphere and the treating time at the indicted temperatures, respectively,
to illustrate the criticality of decarburizing conditons of this invention;
Fig. 8 is a graph showing the relationship between the temperature and the adhesiveness
of particles; and
Fig. 9 is a diagrammatical view in section of a decarburization apparatus for carrying
out the process of the invention.
Detailed Description of Preferred Embodiments
[0025] The reasons for defining the process steps of this invention as in the above will
be described hereinafter.
[0026] Regarding the steps of preparing molten steel, the preparation of molten steel may
be carried out in any conventional manner, and is not limited to a specific one. Since
the molten steel of this invention process contains at least one easily oxidizable
element selected from Cr, Mn, V, Nb, B and Si, the preparation of molten steel is
preferably carried out in such way that the oxidiation of these elements is suppressed
as thoroughly as possible.
[0027] In the atomizing step of this invention, as in the conventional oil atomization,
an atomizing agent which preferably contains a medium selected from mineral oils,
animal oils, vegetable oils and mixtures thereof may be employed. Preferably, according
to this invention a non-oxidizing medium comprised of an oil selected from the above-mentioned
oils may be employed as an atomizing agent. An oxidizing agent such as water may be
incorporated in the atomizing agent so long as the resulting medium is non-oxidizing
in nature as a whole.
[0028] The oils employed in this invention include machine oil, quench oil, turbine oil,
whale oil, rapeseed oil, soybean oil, etc.
[0029] The oxygen content of the atomized steel powder obtained in accordance with this
invention is restricted to 0.2% by weight or less. It may be 0.1 % by weight or less,
preferably 0.05% by weight or less. This is because substantially all the oxygen of
the atomized powder remains in the final decarburized powder, though deoxidization
to some extent can be effected during the following decarburization step. The lower
the oxygen content the better. It is to be noted that it is possible to reduce the
amount of oxygen significantly by effecting the de-oxidization of molten steel prior
to atomization, and by preventing oxidation thereafter, particularly by preventing
oxidation of the molten steel as well as atomized powder during atomization. The carbon
content of the thus obtained atomized steel powder is 0.1% by weight or more. Such
a large amount of carbon comes from carburization of the atomizing agent.
[0030] The thus obtained high carbon alloy steel powder is then passed to the decarburization
step of this invention, where it is subjected to decarburizing conditions defined
by either of Conditions (A) or (B), which will be detailed hereinafter. '
[0031] An atmosphere under which allay steel powder containing 0.1 % by weight or more of
carbon can decarburized to a level of less than 0.1% by weight will be considered.
It will easily be thought of to add as large an amount of H
20 gas as possible, which are easily reacted with carbon in steel, in order to effect
the decarburization of the alloy steel powder. However, the addition of a large amount
of oxidizing gas results in the oxidation of such easily oxidizable elements such
as Cr, Mn, V, Nb, B, Si, etc., which react more easily with oxygen than Fe. On the
other hand, without the addition of such oxidizing gas, substantial decarburization
does not occur and a relatively long period of time will be required for processing
the powder.
[0032] The inventors of this invention noted that though dry hydrogen gas does not exhibit
decarburizing effect, the addition of moisture accelerates the decarburizing reaction.
However, as mentioned hereinbefore, steam itself is oxidative of these oxidizable
elements, so mere addition of steam means that decarburization as well as oxidation
will occur.
[0033] The inventors of this invention found that when the ratio of partial pressure of
hydrogen to partial pressure of steam in an atmosphere containing hydrogen and steam
is suitably adjusted, efficient decarburization takes place without resulting in substantial
oxidation of the before-mentioned easily oxidizable elements or Fe, and the inventors
carried out a series of experiments to determine critical conditions thereof to arrive
at this invention.
[0034] Fig. 1 is a graph summarizing the experimental data of a series of decarburizing
tests with respect to decarburizing temperature. In this series of tests, Cr-Mn low
alloy steel powder (Cr: 1.0% by weight; Mn: 1.5% by weight; C: 0.6% by weight; oxygen:
0.09% by weight), which was obtained by the conventional oil-atomization, was packed
into a stainless steel boat to a depth of 3 mm. The atmosphere comprised H
2, H
20 and N
2, the ratio of P
HZ/P
H2o was 33.3 and P
H2 was 70% of the total pressure of the atmosphere. The boat was heated under the atmosphere
to effect decarburization. Changes in the amounts of carbon in powdered steel (C)
and oxygen in powdered steel (O) were determined with respect to treating period of
time at the indicated temperature.
[0035] From the data shown in Fig. 1, it is apparent that decarburization takes place efficiently
as the temperature of the atmosphere goes up. It is to be noted, however, that oxidation
also takes place. Namely, according to the test results shown in Fig. 1, it may be
said that it is possible to reduce the proportion of carbon to 0.1% by weight or less
in a short period of treating time. No significant degree of oxidation occurs. In
addition, decarburization proceeds rapidly as the temperature of the atmosphere increases,
but oxidation does not proceeds so quickly as decarburization. Thus, it is concluded
that it is an efficient treatment to employ relatively high temperature and short
treating time.
[0036] Next, sample steel powder the steel composition and particle size distribution of
which are shown in Table 1 was packed into a stainless steel boat to a depth of 20
mm, then heated and maintained at the indicated temperatures under pre-determined
atmosphere to effect decarburization. The decarburized powder was then cooled to room
temperature in a dry hydrogen atmosphere.
[0037] The test results of the series of experiments using the steel powders in Table 1
are summarized in graph in Figs. 2-7 at the indicated temperatures respectively.
[0038] The numbers on the abscissa indicate the P
H2/P
H2O ratio, and the treating time is on the vertical axis. The symbol "0" indicates the
case in which the carbon content has been reduced to 0.1 % by weight or less and the
oxygen content to 0.2% by weight or less. The symbol "X" shows the case where the
target values of carbon or oxygen content were not attained. Zone (I) shows the area
where the oxidation occurs, Zone (II) shows the area of this invention and Zone (III)
shows the area where de-carburization is insufficient.
[0039] As is apparent from the series of graphs shown in Figs. 2-7, the ratio of P
H2/P
H2O, temperature and treating time have their own criticality.
[0040] The critical range of each of these processing factors: P
H2/P
H2O ratio, temperature (t°C) and treating time [8 min) can be derived on the basis of
the data given in Figs. 2-7 as follows (wherein the treating time, 8, is a function
of P
H2/P
H2O):
[0041] The minimum treating time required to reduce the carbon content to 0.1% by weight
or less at a temperature of 600-950°C can be given by:

[0042] The maximum treating time required to suppress the oxidation of the powder to 0.2%
by weight or less can be given by:

[0043] Regarding the ratio of P
H2/P
H2O. as is apparent from the graphs shown in Figs. 2-7, satisfactory results are not
obtained as long as the ratio is smaller than 0.5. in the other hand, when the ratio
is over 1000, decarburization to a satisfactory level of carbon content requires a
treating time longer than several hours even when the atmosphere temperature is raised.
Thus, the purpose of this invention cannot be achieved.
[0044] Therefore, one of the critical conditions of this invention can be shown as follows:
[0045] Conditions (A):
Temperature (t°C): 600°C ≦ t ≦ 950°C
Atmosphere (PH2/PH2O) : 0.5 ≦ PH2/PH2O ≦ 1000
[0046] Treating Time (8 min):


[0047] In case where the temperature is over 950°C, the following critical conditons can
be derived:
[0048] Atmosphere (P
H2/P
H2O) : P
H2/P
H2O ≧ 0.5
[0049] Treatinq Time (8 min):

[0050] However, when the temperature is excessively high, welding of the particles will
occur. The temperature should be limited to within a certain range.
[0051] Fig. 8 shows the relationship between the temperature and the adhesiveness of each
particle. As is apparent from the graph, when the temperature goes up beyond 1250°C,
the adhesive force between particles rapidly increases, resulting in welded particles,
in which case a strong disintegrating force is required in a step following decarburization.
[0052] Thus, the following critical conditions can be defined at a temperature range of
higher than 950°C in accordance with this invention:
Temperature (t°C): 950°C < t ≦ 1250°C
[0053] Atmosphere

[0054] Treating Time (8 min):

[0055] In general, in a preferred embodiment of this invention the treating time of decarburization
may be restricted to less than several hours, desirably less than approximately one
hourfrom a practical viewpoint.
[0056] The thus decarburized steel powder is then cooled to room temperature in an inert
or reducing atmosphere. The type of atmosphere is not limited to a specific one so
long as the reoxidation can be prevented, but it is preferable to employ a dry hydrogen
atmosphere.
[0057] Thus, according to the process of this invention, low-oxygen, low-carbon alloy steel
produced in an efficient manner and in a continuous manner. The alloy steel of this
invention includes high alloy steel as well as low alloy steel, as disclosed in the
working examples hereinafer described.
[0058] It is herein to be noted that according to the process of this invention the processing
condition range where the purpose of this invention has been achieved, e.g. Zones
(II) in Figs. 2-7 regarding decarburizing temperature,

ratio and treating time is wide. Therefore, according to this invention it is possible
to continue decarburization regardless of fluctuation in processing conditions, which
is usually experienced during operation. This means that a practical process for continuously
producing decarburized alloy steel powder on an industrial scale can be provided in
accordance with this invention.

[0059] The apparatus which is successfully employed for continuously carrying out the decarburization
process of this invention will be described hereinafter.
[0060] Fig. 9 shows a diagrammatical view of a decarburizing apparatus for carrying out
this invention process, in which the steel powder 1 produced in the oil-atomizing
step is first placed in a hopper 2 and then is continuously charged onto the steel
belt 3 actuated by means of rollers 4. The steel belt 3 is successively passed through
a decarburizing apparatus 5 which comprises a pre-heating chamber 6, a decarburizing
chamber 7 and a cooling chamber 8. While the powder passes through the apparatus,
the steel powder 1 is pre-heated, decarburized and then cooled, successively. After
passing through the apparatus, the decarburized steel powder 9 is discharged out of
the discharge end of the apparatus onto the chute.
[0061] A non-oxidizing gas (H
2 gas, for example) is supplied to the pre-heating chamber 6 and the cooling chamber
8 to keep the atmosphere non-oxidizing. The dotted lines in the drawing show the supply
system of the non-oxidizing gas.
[0062] Gases (H
20 and H
2) are supplied to the decarburizing chamber 7 to adjust the atmosphere. If necessary
N
2 gas may also be supplied to the chamber through lines 11. These gases, each supplied
through its respective supply system (not shown), will be combined in a gas-mixing
tank (not shown) to adjust the gas composition prior to being supplied to the chamber.
The gas discharge out of the chamber through line 12 is collected in a dust separator
13 where solids entrained with the gas is separated. Carbon oxides formed during decarburization
is removed out of a gas-separator 14 through line 15. The recovered gas is then supplied
to the decarburizing chamber through line 11. Further explanation on this gas supply
system will be eliminated since the above explanation will be enough to the person
skilled in the art.
[0063] Thus, in another preferred embodiment of this invention, the as-atomized alloy steel
powder of this invention may be continuously carried out on a conveyor through a decarburizing
zone comprised of the decarburizing apparatus 5 where the as-atomized powder is continuously
decarburized to a level of 0.1% by weight or less of carbon. The decarburizing zone
may comprise a pre-heating section, a decarburizing section and a cooling section.
The pre-heating and cooling sections are kept in an inert or reduced atmosphere.
[0064] This invention will further be described in conjuction with some working examples,
which are presented merely for the purpose of illustrating this invention, not for
limiting it at all.
Example 1
[0065] In this example, Cr-Mn low alloy steel powder, which was produced through atomization
using mineral oil as an atomizing agent, was subjected to decarburuzation using the
decarburization apparatus shown in Fig. 9. The chemical composition and particle size
distribution of the as atomized steel powder are shown in Table 2.
[0066] Decarburizing conditions are summarized in Table 3 and the chemical composition and
particle size distribution of the thus decarburized steel powder are shown in Table
4.
Example 2
[0068] This example treats a low alloy steel powder which contains not only Cr and Mn, but
also other easily oxidizable elements such as V, Nb, B and Si, etc. The steel powder
having a chemical composition and particle size distribution shown in Table 5 was
treated with the decarburizing apparatus shown in Fig. 9.
[0069] Decarburizing conditions are summarized in Table 6, and the chemical composition
and particle size distribution of the thus decarburized steel powder are shown in
Table 7.
Example 3
[0071] In this example stainless steel powder having chemical composition and particle size
distribution as shown in Table 8 was subjected to decarburization using the decarburizing
apparatus shown in Fig. 9.
[0072] The atomized steel powder employed in this example was produced by using mineral
oil containing 5% by weight of water as an atomizing agent, and was characterized
in that the carbon content of the steel is less than that of the powder used in Examples
1 and 2.
[0073] Decarburizing conditions are summarized in Table 9 and the chemical composition and
particle size distribution of the thus decarburized stainless steel powder are shown
in Table 10.
[0075] The principles, preferred embodiments and modes of operation of this invention have
been described in the foregoing specification. However, the invention which is intended
to be protected is not to be construed as limited to the particular embodiments disclosed.
The embodiments are illustrative, not restrictive.