U.S. patent number 3,865,572 [Application Number 05/327,323] was granted by the patent office on 1975-02-11 for mechanical alloying and interdispersion cold bonding agents therefor.
This patent grant is currently assigned to The International Nickel Company, Inc.. Invention is credited to Calvin Robert Cupp, Gordon Lloyd Fisher.
United States Patent |
3,865,572 |
Fisher , et al. |
February 11, 1975 |
MECHANICAL ALLOYING AND INTERDISPERSION COLD BONDING AGENTS
THEREFOR
Abstract
The invention involves mechanical alloying of powder wherein the
formation of composite powder particles characteristic of
mechanical alloying process is facilitated through the use of
special interdispersion cold bonding agents such as a halide, e.g.,
a metal halide.
Inventors: |
Fisher; Gordon Lloyd (Mahwah,
NJ), Cupp; Calvin Robert (Suffern, NY) |
Assignee: |
The International Nickel Company,
Inc. (New York, NY)
|
Family
ID: |
23276094 |
Appl.
No.: |
05/327,323 |
Filed: |
January 29, 1973 |
Current U.S.
Class: |
75/352; 419/32;
419/30 |
Current CPC
Class: |
B22F
9/04 (20130101); B22F 2009/041 (20130101); B22F
2009/043 (20130101) |
Current International
Class: |
B22F
9/04 (20060101); B22F 9/02 (20060101); B22f
009/00 () |
Field of
Search: |
;75/.5R,.5A,.5B,214,211
;264/111 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
"Feasibility of Producing Dispersion Strengthened Chromium by Ball
Milling in Hydrogen Halides": A. Arius NASA Note D-4912: 11/68, pp.
1-34..
|
Primary Examiner: Rutledge; L. Dewayne
Assistant Examiner: Steiner; Arthur J.
Attorney, Agent or Firm: MacQueen; Ewan C. Kenny; Raymond
J.
Claims
We claim:
1. In the process of producing mechanically alloyed composite
product powder particles, the improvement which comprises
conducting the mechanical alloying operation in the presence of an
inorganic interdispersion cold bonding agent (ICBCA) formed of a
halide, the halide being in contact with the powder particles to be
mechanically alloyed and being present in an amount effective to
provide the necessary control balance during the course of the
operation with the upper limit being about 3% by weight of the
powder charge, the control balance being such that an intimate
interdispersion of constituent powders is achieved without either
the formation of an appreciable amount of detrimentally large
composite particles or the deleterious adherence of powders to the
milling elements or mill interior surfaces and without incurring
serious impairment of the mechanical properties of the composition
to be produced.
2. A process as set forth in claim 1 in which the halide is from
the group consisting of HCl, HBr, HI and HF.
3. A process as set forth in claim 1 in which the halide is a gas
from the group consisting of chlorine, bromine, iodine and
fluorine.
4. In the process of producing mechanically alloyed composite
product powder particles, the improvement which comprises
conducting the mechanical alloying operation in the presence of an
inorganic interdispersion cold bonding agent (ICBCA) formed of a
metal halide, the metal halide being in contact with the powder
particles to be mechanically alloyed and being present in an amount
effective to provide the necessary control balance during the
course of the operation with the upper limit being about 3 percent
by weight of the powder charge, the control balance being such that
an intimate interdispersion of constituent powders is achieved
without either the formation of an appreciable amount of
detrimentally large composite particles or the deleterious
adherence of powders to the milling elements or mill interior
surfaces and without incurring serious impairment of the mechanical
properties of the composition to be produced.
5. A process as set forth in claim 4, in which the halide is a
nickel halide selected from the group consisting of nickelous
chloride, bromide and fluoride.
Description
The present invention relates to powder metallurgy, and is
particularly directed to the "mechanical alloying" of powder.
As is known, the recently introduced concept of "mechanical
alloying", described in U.S. Pat. No. 3,591,362 (incorporated
herein by reference), involves a dry, intensive milling of powders
in high energy machines, such as the Szegvari attritor. During this
unique process, initial constituent powders are repeatedly
fragmented and cold bonded by the continuous impacting action of
attriting elements, usually metal balls, for a period such that
composite product powder particles of substantial saturation
hardness are formed, the composition of which correspond to the
percentages of the respective constituents in the original charge.
The constituent powders become most intimately interdispersed at
close interparticle spacings, the composite particles being
exceptionally dense and homogeneous, and characterized by cohesive
internal structures.
For the most part "mechanical alloying" (often herein "MA") has
been conducted in the presence of an atmosphere comprised of an
oxygen-nitrogen mixture. However, such an environment can serve to
introduce various problems. If present to the excess, comminution
of the powders dominates to such an extent as to virtually preclude
the critically necessary cold bonding. Moreover, oxygen, for
example, is retained in the composite product particles formed. As
a consequence and depending upon the alloy composition to be
produced, this can subvert certain metallurgical properties,
tensile and creep ductility of nickel-base superalloys being
illustrative.
On the other hand, in the absence of such atmospheres the powders
either fixedly adhere to the attriting elements and interior
attritor surfaces (with subsequent buildup) or, depending upon the
composition of the attriting elements and powder charge, cold bond
in such manner as to form undesirably large particles. Whether by
reason of the thickness of the adherent powder or of the excessive
particle size, such powder cannot be satisfactorily deformed by the
energy available in subsequent collision events. Processing
therefore effectively ceases. Indeed, a point may be reached where
there is such an overload on the attritor as to bring about a self
induced shut-down. This, quite naturally, leads to considerable
loss occasioned by down-time. In any case, powder recovery is
extremely poor.
It is evident from the foregoing that an indispensibly necessary
mechanical alloying "control balance" must be achieved, this
"control balance" being defined as one in which the intimate
interdispersion of constituent powders continues by means of the
establishment of steady state processing (fragmentation and cold
bonding reaching a virtual equilibrium), but without (i) the
formation of appreciable quantities of detrimentally large
composite product particles, or (ii) the deleterious adherence of
powders to the attriting (milling) elements or other attritor
surfaces, and (iii) without incurring serious impairment of the
mechanical, physical or other properties of the alloy composition
being produced.
It has now been discovered that the above drawbacks can be
considerably minimized, if not virtually eliminated, that the
desired "control balance" can be attained, through incorporating an
effective percentage of at least one interdispersion, cold-bonding
control agent (ICBCA), as herein detailed.
Generally speaking, and in accordance herewith, it has been found
that an inorganic agent or gas capable of reacting with or of being
adsorbed on a plurality of the powder (particle) surfaces of an
initial powder charge and which is capable of residing thereon in
reacted or adsorbed form during at least a significant part of the
"mechanically alloying" process, is effective in achieving the
aforedescribed "control balance." It has been further found that
but a small quantity of such materials (ICBCAs) is required, though
this is somewhat dependent upon the given conditions used in
producing the desired mechanically alloyed composite product powder
particles. But it is worthy of note that as little as 0.05 percent
of certain ICBCAs (based upon the weight of the powder charge) has
been found satisfactory.
In carrying the invention into practice it is most advantageous
that the ICBCA be sublimable or decomposable, the sublimation or
decomposition temperature exceeding the operating temperature of
the attritor mill (or equivalent functioning high energy machine
such as the planetary or vibratory ball mills) but preferably not
exceeding about 2,000.degree. F. Halides, including the metal
halides, are deemed quite advantageous, small amounts of, for
example, nickelous chloride and bromide having given excellent
results.
By virtue of being sublimable or decomposable the interdispersion
cold bonding agent can be appreciably removed during subsequent
heat treatment of the mechanically alloyed composite product powder
particles. As is known, the composite product powder particles
produced by "MA" are hot consolidated, temperatures on the order of
1,600.degree. to 2,000.degree. F. being commonly used. Thus, an
ICBCA with a sublimation or decomposition temperature below about
2,000.degree. F., and advantageously below 1,600.degree. F., lends
itself to this treatment. This coupled with the fact that only a
small amount of an ICBCA is required as a matter of first instance
indicates that no particular problem need be experienced in
achieving the necessary "control balance."
It should be mentioned, however, that not all of the ICBCA can be
removed and this does focus attention on a major difference between
the subject invention and conventional ball milling in which
surfactants, lubricants and other grinding aids are used for
various purposes, mainly for powder comminution. Generally, the
latter are virtually completely removed from the powder by
expedients such as leaching or burning off. In contrast, due to the
necessary intimate interdispersion of constituent powders which
occurs by reason of "mechanical alloying," removal techniques
affecting only the composite particle powder surfaces are incapable
of extricating all the ICBCA since an amount of it is occluded in
interdispersed fashion.
In addition to the specific halides above mentioned, the following
sublimable, interdispersion, cold bonding control halides can be
used: aluminum chloride; nickelous iodide; cobaltous and cobaltic
chloride; vanadium trifluoride; chromic chloride, zirconium
tetrachloride, tetrabromide, tetraiodide and tetrafluoride;
titanium trichloride; hafnium tetrachloride; hafnium tetrabromide;
niobium oxychloride; cuprous fluoride; the trifluorides of
aluminum, chromium and rhodium; ammonium bromide and iodide;
rhodium trichloride; etc. Decomposable halide ICBCAs include
cuprous chloride; ferrous chloride; iridium di and trichloride;
palladium chloride; molybdenum di and trichloride; titanium
trichloride and titanium dibromide; zirconium di and tribromide;
iridium bromide and the iridium di and tribromides; ferric bromide;
palladium fluoride; manganese di-iodide; palladium fluoride;
palladium di-iodide; and the iodides of copper (cupric), rubidium,
strontium and samarium. This list of halides is not intended to be
exhaustive.
Apart from halides, appropriate nitrides, carbonates, nitrates,
nitrites, chlorates, sulfates and borates, etc., can be utilized,
including the nitrides of copper (Cu.sub.3 N), iron (Fe.sub.2 N)
and chromium (CrN); the carbonates of magnesium, calcium, cesium,
and nickel as well as cupric carbonate and ammonium carbonate;
ammonium nitrate and nitrite; etc. Gases such as chlorine, bromine,
iodine, fluorine and HC1, HBr, HI and HF also can be used.
The amount of an ICBCA employed will be largely influenced, inter
alia, by the alloy composition to be produced, milling time,
ball-to-powder ration, and the nature of the attriting elements,
particularly the latter. Hardened steels, stainless steels,
tungsten carbide, nickel and other metals as well as cermets may be
used as the attriting media; however, considerably less ICBCA will
usually be necessary in conjunction with the harder attriting
elements such as 52100 steel as opposed to, say, nickel, The longer
milling periods may require a slightly higher percentage of ICBCA
than otherwise. Generally, not more than 2 or 3 percent of an
effective ICBCA component need be employed, a range of 0.1 to 0.5
percent and up to 2 percent being deemed quite satisfactory.
Excessive amounts can be detrimental. In terms of a metal halide,
for example, a range of about 0.05 to 0.5 percent of halide as
metal halide is of advantage, the halide serving as the ICBCA.
Due to the high energy milling of mechanical alloying, a part of
the attriting composition may wear during processing and become a
part of the composite product particles. This can be beneficial but
if undesirable, recourse should be had to a more appropriate
attriting composition.
The following illustrative data are given.
EXAMPLE I
NiC1.sub.2 and NiBr.sub.2 were used as ICBCAs to determine particle
size results and ICBCA retention in processing commercial nickel
123 powder. 8 kg batches of the nickel powder were processed in a
4-gallon attritor for 5 hours at an impeller speed of 250 rpm using
3/8 inch diameter carbonyl nickel balls at a ball-to-powder ratio
of about 11.4 to 1. Oxygen, about 0.05 percent of the charge
weight, was added as air during processing. Nitrogen was also added
and served to maintain the oxygen partial pressure at about 1
percent of the weight of gas in the attritor.
The results of a sieve analysis to determine size distribution of
the processed powders are given in FIGS. 1 and 2. It is evident
that a very fine particle size distribution could be attained with
both halides, approximately 90 percent of the processed powder
being finer than about 105 microns in diameter at a halide content
of 0.5 percent. The curves reflect that a "control balance" could
be achieved.
The attrited powders were then placed in metal steel cans (31/2
inch diam.) and evacuated at 750.degree. F. to 20 hours. The cans
were sealed, heated for 1 hour at 1,800.degree. F. and extruded
thereat to 1 inch diameter rods.
Chemical analyses were made to determine retained chlorine and
bromine content of the extruded rods, the results appearing
below.
______________________________________ Chlorine Bromine Added
Retained Added Retained % % % %
______________________________________ 0.02 0.012 0.02 0.021 0.05
0.018 0.08 0.031 0.10 0.039 0.41 0.022 0.50 0.37
______________________________________
If the extrusion treatment had been carried out at a higher
temperature, say 2,00.degree. F., it is considered that a greater
amount of halide would have been removed. It is to advantage that
the sublimation (or decomposition) temperature be at least
200.degree. to 300.degree. F. below the temperature of hot
consolidation.
EXAMPLE II
The superalloy known as IN-792 (approximately 12.7% Cr, 9% Co,
2%Mo, 3.9%W 3.9%, Ta, 4.2%Ti, 3.2%A1, 0.21%C, balance Ni) was
mechanically alloyed in a 1-gallon attritor at 340 rpm for 20 hours
under argon, using 16 kg of +6.3 mm nickel pellets as the attriting
media, the ball-to-power ratio being 16:1. Several runs were made
using different percentages of Cl and NiCl.sub.2. The powder
recovery (draining was for 1 hour) was as follows: ICBCA Powder
Recovery ______________________________________ None 12.8% 0.05% Cl
25.6% 0.2% Cl 85.1% 0.5% Cl 102.0%
______________________________________
In this instance the 0.05 percent Cl addition was rather
inadequate. On the other hand, 0.5 percent was a little high, the
processed powders being too fine accompanied by excessive wear of
the processing media. The 0.2 percent chlorine batch gave an 85
percent recovery within the experimental draining period. From a
commercial production basis, if the recovery is virtually 100
percent for a practical draining period, this quantity, 0.2
percent, of Cl.sub.2 will be about optimum. Should the recovery be
below 100 percent for the same draining period, a slightly higher
amount of Cl.sub.2, e.g., 0.25 percent, would be in order. This is
not to suggest that the 0.2 percent chloride was insufficient
within the purview of the invention. Indeed, the recovery of the
0.05 percent Cl run would be markedly improved using steel
attriting elements and/or a higher rate of energy input. This is
reflected in Example III.
EXAMPLE III
Composite product powder particles of IN-792 were also produced
using various halide ICBCAs and either nickel or steel attriting
elements. Powder blends were used, each being comprised of carbonyl
nickel powder (99.1 percent nickel approximately 4 microns in
size), 0.15 percent Asbury flake graphite to raise the carbon
content to nominal and a low oxygen omnibus master alloy (-100 mesh
of 30 percent Ni, Cr, Mo, Co, A1, Ti, W, Ta, B, Zr and C) prepared
by vacuum induction melting and grinding in cold nitrogen. Each run
consisted of 5 grams of the blended powder plus the particular
ICBCA used as given in Table II.
A Spex mill was employed in each case, the respective runs being
conducted for 30 minutes under argon. The Spex mill jar was cooled
prior to opening, emptied and the balls replaced in the jar and
processed for an additional 30 seconds in air to remove any loosely
adherent powder. The total amount of drained powder was weighed to
ascertain the percentage of powder recovered. An oxygen analysis
was also made and retained ICBCA was determined. Runs Nos. 1 and 2
are included for purposes of comparison.
TABLE III
__________________________________________________________________________
Attriting Powder Oxygen Run ICBCA Element Recovery Analysis ICBCA
No. (%) (%) Retained
__________________________________________________________________________
1 None Nickel(100 gm) 32 0.30 -- 2 None Steel (100 gm) 57 0.27 -- 3
0.05% Cl Steel (100 gm) 83 0.20 0.023% Cl as NiCl.sub.2 4 0.1% Cl
Steel (100 gm) 86 0.33 0.072% Cl as NiCl.sub.2 5 0.25% Br Steel
(100 gm) 86 0.20 0.20% Br as NiBr.sub.2 6 0.1% F Steel (100 gm) 88
0.24 0.008% F as NaF
__________________________________________________________________________
The low recovery of Run No. 1 reflects the detrimental adherence of
the IN-792 powder to the milling elements and to the interior
surfaces of the mill. This was reduced somewhat by using the harder
steel impacting elements in Run No. 2.
In above describing the subject invention, reference has been made
to the well-known commercial alloy IN-792. However, the invention
is obviously not restricted to this particular composition, since
it can be utilized in mechanical alloying whatever be the desired
composition. It is particularly applicable to the production of
superalloys including those containing up to 65 percent, e.g., up
to 25 or 35 percent, chromium; up to 30 percent, e.g., 5 to 25
percent, cobalt; up to 10 percent, e.g., 1 to 9 percent, aluminum
and up to 8 percent, e.g., 1 to 7 percent, titanium; including
those alloys containing 4 or 5 percent or more of aluminum plus
titanium; up to 30 percent, e.g., 1 to 8 percent, molybdenum; up to
25 percent, e.g., 2 to 20 percent, tungsten; up to 10 percent
columbium; up to 10 percent tantalum; up to 7 percent zirconium, up
to 0.5 percent boron; up to 5 percent hafnium; up to 2 percent
vanadium; up to 6 percent copper; up to 5 percent manganese; up to
70 percent iron; up to 4 percent silicon, and the balance
essentially nickel. Cobalt-base alloys of similar composition can
be treated. Among the specific superalloys might be listed IN-738;
Rene alloys 41 and 95, Alloys 500, 700, 713 and 718, Waspaloy,
Astroloy, Mar-M alloys 200 and 246, A-286, B-1900, etc. The
superalloys and other contemplated alloys can also contain up to,
say, 10 percent by volume of a refractory dispersoid material
including the oxides, carbides, nitrides and borides. Such
refractory dispersoids can be of various elements including
yttrium, lanthanum, thorium, zirconium, hafnium, titanium, silicon,
aluminum, cerium, uranium, magnesium, calcium, beryllium and the
like. As a practical matter, only a very small amount of such
dispersoids need be employed, e.g., up to 2 percent by volume.
Other base alloys such as titanium and copper can be processed as
well as refractory alloys such as SU-16, TZM, Zircaloy, etc.
Finally, it will be understood that modifications and variations of
the invention may be resorted to without departing from the spirit
and scope thereof as those skilled in the art will readily
understand. Such are considered to be within the purview and scope
of the invention and appended claims.
* * * * *