Title of Invention

A METHOD FOR MILLING A PRODUCT IN A MEDIA MILL

Abstract The invention discloses a method for milling a product in a media mill, comprising the step of milling a product in a medial mill using grinding media, wherein the grinding media comprise-a multi-carbide material which includes-carbon and at least two carbide-forming metal.
Full Text MULTI-CARBIDE MATERIAL MANUFACTURE AND USE
A METHOD FOR MILLING A PRODUCT IN A MEDIA MILL
CROSS-REFERENCE TO RELATED APPLICATIONS

[01 ] This application claims priority from U.S. Provisional Application Serial No.
60/453,427 filed on March 11,2003 and entitled SPHERES IMPARTING HIGH WEAR
RATES, incorporated herein by reference.
FIELD OF THE INVENTION
£02] This invention relates generally to the field of grinding media composition, and
more specifically to multi-carbide materials for use as grinding media formed in the
shape of spheres or other shaped media.
BACKGROUND OF THE INVENTION
[03] Carbide materials are well known in the art of material science. They include a
range of compounds composed of carbon and one or more carbide-forming elements such
as chromium, hafnium, molybdenum, niobium, rhenium, tantalum, thallium, titanium,
tungsten, vanadium, zirconium, and others. Carbides are known for their extreme
hardness with high temperature tolerance, properties rendering them well-suited for
applications as cutting tools, drilling bits, and similar uses. Multi-element carbides are
known for their improved toughness and hardness relative to single element carbides.
Single element carbides are typically used with a metal binder to impart toughness.
[04] Multi-carbides are formed by combining two or more carbide-forming elements
with carbon. Some multi-carbides have other non-carbide forming elements in the
composition, such as nitrogen, but are here referred to simply as multi-carbides since the
dominant components are carbide-forming elements. For example, a combination of
tungsten and titanium with carbon and nitrogen would be such a multi-carbide material.
Some multi-carbide compositions are formed with a deficiency of carbon resulting in
some small percentage of carbide-forming element not being converted to a carbide and
instead remaining as uncombined elemental metal. These combinations can enhance
certain of the favorable qualities of carbides, with some combinations increasing
hardness, others increasing toughness, and so forth. Very small variations in composition
can greatly affect the material's properties. Many of these variations are well understood
by practitioners of the art and are amply published.
^J&SJ Spheres and solid bodies of other specific shapes, whether of carbide or multi-
carbide, are difficult to manufacture due to the very properties that make them useful.
Their high melting point necessitates a powerful energy source with difficulty in
temperature regulation and effect, and their hardness makes them costly to machine.
[06] For example, a primary manufacturing method used to manufacture carbides is to
place the elements to be fused on the recessed surface of a large electrode. A very high
current is passed from that electrode through the material and into another electrode in
proximity, subjecting the material to the heat of an electric arc. This process is effective
in fusing the materials, but causes inconsistent mixing of the elements in the compound
and some uncontrolled loss of material due to vaporization, phenomena that can greatly
compromise the properties of the resulting compound in uncontrolled and unpredictable
ways. Hardness is also a challenge, as the manufacturing process results in an
irregularly-shaped lump of resulting compound that is generally a few inches in diameter,
colorfully known as a "cow chip". The "chip" is very hard, and is worked into smaller
shapes only by percussive shocking or other crushing method that cleaves the chip into
useful sizes. These processes leave small cracks in the finished product that greatly
reduce both its hardness and its mechanical toughness. Re-melting of the material after
crushing imposes high cost, and cannot efficiently achieve regular particle sizes or
shapes. Consequently, although carbide is available in small spheres and other preferred
shapes, those spheres are not optimally composed, they are irregularly sized, they are
expensive, and they are lacking in effectiveness.
[07] The known art currently does not have a process whereby multi-carbide materials
can be formed into small and regular shapes without loss of optimized properties due to
process variation in manufacture or degradation of material during shaping.
[08] Reducing of particles, also known as comminution, is a very old art, practiced for
example by the ancients to produce flour from grain by stone wheel grinding. Later
practices required smaller and more regular powders for a variety of industrial
applications, and more refined techniques were developed to produce those products,
such as media milling. Modern technologies and practices now demand ever-finer
particles, measured in microns, thousandths of microns, and even angstroms; and with
greater regularity of particle size and purity at these reduced dimensions.
[09] Just as stone wheel grinding could not reliably provide the powders needed for
earlier industrial processes, current media mills and similar technologies cannot reliably
provide the ultra-fine and ultra-regular particles now required for certain applications.
[010] Various methods for reducing the size of particles have been employed. Many
use materials such as spheres, rods or more irregular objects ("grinding media") to crush
or beat the material to be reduced ("product material") to smaller dimensions by
processes known as grinding, milling, comminution, or dispersion. Grinding media range
greatly in size, from ore crushers that are several inches in diameter, down to micron-
sized particles that are themselves used to mill much smaller particles. Grinding media
also vary greatly in shape, including spherical, semi-spherical, oblate spherical,
cylindrical, diagonal, rods, and other shapes (hereinafter "shaped media"), and irregular
natural shapes such as grains of sand.
[011] Grinding media are used in various devices such ball mills, rod mills, attritor
mills, stirred media mills, pebble mills, etc. Regardless of their differences in design, all
mills operate by distributing product material around the grinding media and by causing
collisions to occur between grinding media units such that product material particles are
positioned between the colliding grinding media units. These collisions cause fracturing
of product material particles into to smaller dimensions, an effect known descriptively as
"size reduction" or "comminution."
[012] The materials used as grinding media also are frequently used as applied
abrasives. For example, such materials are aggregated in molds and held together by a
binder such as molten metal that is poured into the mold and cooled, rendering a "hard
body" that is impregnated by the binder material. Hard body materials (also known as
"hard bodies") of this kind are used in deep-well drilling and other applications. Similar
processes are used to impregnate the materials in grinding discs and wheels. Various
adhesives are used to bind the materials to textiles, papers and other strata for use as
sandpapers, sanding belts, and similar products.
[013] Different grinding and milling techniques produce different mean product
material particle sizes and uniformity. Gross differences in result are obtained primarily
as a function of the size and shape of the grinding media. Large grinding media produce
relatively large and irregular product material particles that are suitable for coarse
processes or for further refinement by finer processes. Small grinding media can be used
to produce finer and more regular materials as an end in itself, or to alter crystallite
aggregates, or to cause mechanochemical alloying, or some combination thereof. Small
grinding media are also used for polishing, burnishing, and deburring. Mills are
sometimes used in series, with progressively smaller grinding media employed to further
reduce product material particle size in stages. Variation of the shape of the grinding
media generally affects the regularity of particle size, the efficiency of the milling
process, the total cost to achieve a given size reduction, and other factors. These effects
generally are well known in the art.
[014] Extremely small particle sizes are proving to be useful for many new applications,
however, the size reduction and regularity necessary for standardized, acceptable results
cannot be achieved by any current milling methods. Production now requires alternate
particle fabrication methods such as chemical precipitation, either at a fast rate with
unacceptable process variation, or at very slow rates, with unacceptable time and
expense.
[015] Other important effects are obtained by varying the composition of the grinding
media itself. Three material properties dominantly affect grinding media performance:
hardness, mass density, and mechanical toughness. Hardness of the grinding medium
determines milling effectiveness, mass density determines milling efficiency, while
mechanical toughness determines product purity and overall process efficiency. Hard
materials transfer energy efficiently in collisions with product material for effective
milling, high-density materials increase the energy transfer per collision with product
material and thus increase milling efficiency, especially for small-dimension grinding
media, and tough materials can be used for longer periods before they fail and
contaminate the product material or otherwise require replacement. An ideal milling
material is thus very hard, of very high mass density, and very tough. Preferably, those
qualities will hold as the size of the grinding media is reduced, and regardless of the
chosen shape of the grinding media.
[016] The history of engineering materials for grinding media is a history of accepting
tradeoffs among these material properties, as improvement in one of these factors has
previously produced an offsetting reduction in one or more of the others. For example,
yttria-stabilized zirconia shows good mechanical toughness, but with low mass density.
Various metal media have relatively high mass density, but low mechanical toughness.
Carbides showed extreme hardness and mass density, even in small dimensions, but with
unavoidable media failures that cause unacceptable product contamination and more
general process failures that are incompatible with many applications.
[017] U.S. Patent No. 5,4_07,564 (Kaliski) is illustrative. Kaliski discloses a range of
high mass density, single-element carbides selected from tungsten, thallium, niobium,
and vanadium in sizes ranging between 10 and 100 microns with a requirement of high
theoretical density. As Kaliski explains, high theoretical density, nonporous materials are
needed. These materials showed impressive results in producing fine and regular product
material in small quantities under controlled laboratory conditions. Duplication of his
example showed his invention to cause contamination of the milled product, as longer-
term and higher-volume production attempts failed due to lack of mechanical toughness
that caused metallic and other contamination of product material. High density ceramics
without metal binders, such as tungsten carbide combined with tungsten di-carbide, also
are disclosed by Kaliski as a means to obtain high milling efficiency but with
contamination of product material from the grinding media. Kaliski specifically
recommends choosing among his claimed materials to select those whose contaminants
provide the most good, or at least do the least damage, to the milled product. These
materials changed the nature of but did not resolve the product material contaminant
issue, and did not solve the mechanical toughness problem. Rather, these materials
tended to fail by degradation into hard, fine and irregular shards that acted as abrasives in
the media mill, contaminating the product and on one occasion seriously damaging the
mill itself.
[018] U.S. Patent No. 5,704,556 (McLaughlin) discloses ceramic grinding media
without metal binders in dimensions of less than 100 microns diameter. While these
materials are acceptably hard, and show greater mechanical toughness than those
disclosed in Kaliski, they lack adequate density for many applications or for optimum
efficiency in others.
[019] The inventor of the present invention made an effort to make suitable grinding
media from available spherical carbides, of which only single element carbides are
known in the art. Tungsten carbide/tungsten di-carbide spheres were purchased in
conformance to Kaliski's specification and used in a shaker mill, but comminution to the
degree cited by Kaliski was not evident. Plasma-processed spherical tungsten
carbide/tungsten di-carbide was also purchased from another source, in conformance to
Kaliski's specification, in sufficient quantity to test on a production scale. This grinding
media fractured due to insufficient mechanical toughness, contaminating the product and
extensively damaging the media mill. Tungsten carbide failed due to the lack of
mechanical toughness despite experimental variation of media velocity, flow rate,
material volume, and other milling variables. Grinding media material in conformance to
Kaliski's specification was obtained from several difference sources worldwide, but
differences in sourcing produced no significant difference in results. In all attempts with
all materials supplied to the Kaliski specification, the level of product contamination was
a limitation on usefulness.
[020] U.S. Patent No. 2,581,414 (Hochberg), U.S. PatentNo.5,478,705(Czekai), and
U.S. Patent No. 5,518,187 (Bruno) disclose polymer grinding media which show high
mechanical toughness and cause relatively benign product material contamination upon
grinding media failure. However, they show low hardness and density relative to
ceramics. Polymer grinding media thus can be useful in milling relatively soft product
materials that are sensitive to product contamination, and in industries that are relatively
insensitive to processing cost, such as in drug processing or in dispersing biological cells
for analysis, but they are not appropriate for the majority of industrial applications.
[021] U.S. Patent Nos. 3,690,962, 3,737,289, 3,779,745, and 4,066,451 (all to Rudy)
disclose certain multi-carbides for use as cutting tools. Although the multi-carbides
disclosed showed a combination of hardness, density and mechanical toughness that
promised to be useful for milling, the known geometries for available multi-carbide
materials rendered them incompatible with such use. Difficulties included the large size
of multi-carbide material that is produced by current manufacturing methods, and
difficulty in machining or otherwise manipulating the material into sizes and shapes
useful for milling due in part to its hardness and mechanical toughness.
[022] V. N. Eremenko, et al, "Investigations of alloys or the ternary systems W-HfC-C
and W-ZrC-C at subsolidus temperatures," DokLAkad. Naulc. Ukr. SSSR, Ser. A No. 1,
83-88 (1976); L.V. Artyukh, et al, "Physicochemical reactions of tungsten carbide with
hafnium carbide," Izv. Akad. Nauk SSSR, Neorg. Mater., No. 4,634-637 (1976); and T.
Ya. Velikanova, et al, "Effect of alloying on the structure and properties of cast WCl-x
Materials," Poroshkovaya Metallurgiya, No. 2 (218), 53-58, (1981) teach how sensitive
the properties of single element carbides can be to small additions of other carbide
forming elements. This fact has greatly inhibited research into multi-carbide elements.
[023] As summarized above, the grinding media of the prior art all suffer some
technical disadvantage resulting in a proliferation of grinding media materials creating a
significant economic burden and also resulting in technically inferior milled products due
to contamination.
SUMMARY OF THE INVENTION
[024] Briefly stated, grinding media includes shaped media, such as spheres or rods,
ranging in size from 0.5 micron to 100 mm in diameter. The media are of a multi-carbide
material consisting essentially of two different carbide-forming elements and carbon,
either with or without an elemental form of a carbide-forming element. The media have
extremely high mass density, extreme hardness, and extreme mechanical toughness.
[025] According to an embodiment of the invention, grinding media include a multi-
carbide material consisting essentially of carbon and at least two different carbide-
forming elements wherein the multi-carbide material is formed into shaped grinding
media ranging in size from 0.5 micron to 100 mm in diameter.
[026] According to an embodiment of the invention, a method for making grinding
media includes the step of forming the media from a multi-carbide material consisting
essentially of carbon and at least two different carbide-forming elements wherein the
multi-carbide material is formed as grinding media for use in a media mill.
[027] According to an embodiment of the invention, a method for making spheres for
use in cladding materials includes the step of forming the spheres from a multi-carbide
material consisting essentially of carbon and at least two different carbide-forming
elements.
[028] According to an embodiment of the invention, a method for making spheres for
use in surfacing material includes the step of forming the spheres from a multi-carbide
material consisting essentially of carbon and at least two different carbide-forming
elements.
[029] According to an embodiment of the invention, a method for making spheres for
use in hard body materials includes the step of forming the spheres from a multi-carbide
material consisting essentially of carbon and at least two different carbide-forming
elements.
[030] According to an embodiment of the invention, a method for making grinding
media includes the step of forming the media from a multi-carbide material consisting
essentially of carbon and one element selected from the group consisting of chromium,
hafnium, niobium, tantalum, titanium, tungsten, molybdenum, vanadium, and zirconium,
along with the elemental metal of the carbide.
[031]- According to an embodiment of the invention, a method for making spheres for
use in cladding material includes the step of forming the spheres from a multi-carbide
material consisting essentially of carbon and one element selected from the group
consisting of chromium, hafnium, molybdenum, niobium, rhenium, tantalum, thallium,
titanium, tungsten, vanadium, and zirconium, along with the elemental metal of the
carbide.
[032] According to an embodiment of the invention, a method for making spheres for
use in surfacing material includes the step of forming the spheres from a multi-carbide
material consisting essentially of carbon and one element selected from the group
consisting of chromium, hafnium, molybdenum, niobium, rhenium, tantalum, thallium,
titanium, tungsten, vanadium, and zirconium, along with the elemental metal of the
carbide.
[033] According to an embodiment of the invention, a method for making spheres for
use in hard body material includes the step of forming the spheres from a multi-carbide
material consisting essentially of carbon and one element selected from the group
consisting of chromium, hafnium, molybdenum, niobium, rhenium, tantalum, thallium,
titanium, tungsten, vanadium, and zirconium, along with the elemental metal of the
carbide.
[054] According to an embodiment of the invention, a method for milling a product in a
media mill includes the step of using media consisting essentially of a multi-carbide
material which consists essentially of carbon and at least two carbide-forming elements
wherein the multi-carbide is formed as media for use in a media mill.
[055] According to an embodiment of the invention, a method for milling a product in a
media mill includes the step of using carbide media consisting essentially of carbon and
one element selected from the group consisting of chromium, hafnium, molybdenum,
niobium, rhenium, tantalum, thallium, titanium, tungsten, vanadium, and zirconium,
along with the elemental metal of the carbide.
[036] Fig. 1 shows particles produced according to the prior art.
[037] Fig. 2 shows particles produced according to an embodiment of the present
invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[058] According to the present invention, a compound is formed from a combination of
carbon and two or more different carbide-forming elements ("multi-carbide material",
defined more fully below). Multi-carbide materials have extreme hardness, extreme
density, and extreme mechanical toughness. In the present invention, the selection of
carbide-forming elements of the multi-carbide materials, and the precise proportional
composition for any combination of those elements, is modified to alter the properties of
the material. Multi-carbide material is combined with one or more elemental metals of
the chosen carbide to alter ductility and other properties of the material. Multi-carbide
material is formed effectively and efficiently into a variety of shaped media, preferably
into spheres, by the use of novel manufacturing methods.
[039] The manufacturing method of the present invention maintains proper element
composition to optimize desired material properties, produces useful shaped media,
avoids crushing or other degradation of the material to create said shaped media, and
greatly lowers manufacturing cost to produce shaped media formed from such material
while improving the quality of the material obtained. The manufacturing method
produces small and regular spheres of optimized multi-carbide material that is suitable for
use as grinding media in media mills ("multi-carbide grinding media"). The multi-
carbide grinding media of the present invention are used in shaped media ranging in size
from 100 mm or more down to 0.5 microns or less while maintaining their effective
material properties. The multi-carbide grinding media are used in media mills and other
extant milling processes of varying design and capacity. By such use of such multi-
carbide grinding media, greater product material size reduction, size regulation, and
purity can be achieved than by utilization of extant milling media materials.
[040] Such use improves the efficiency and outcome of current particle size reduction
methods. Less effective methods could be used as preliminary process steps to produce
particles of relatively great size and irregularity, with those particles being further refined
by the invention.
[041] The multi-carbide grinding media of the present invention are used effectively in
a variety of applications other than media mills, such as the manufacture of hard bodies,
grinding wheels, abrasive papers and textiles, cladding materials, and hard coating
materials.
[042] The invention permits the manufacture of materials in dimensions and purities
that previously were unattainable ("ultra-fine particles"). Ultra-fine particles will enable
the manufacture of products previously unattainable, or attainable only by less effective
or more expensive methods. Examples include sub-micron sized oxides, such as oxides
of titanium. Reduction of certain oxides of titania with sufficiently low impurities causes
that compound to exhibit special properties including high transparency. Fine size
reduction of pigments improve the efficiency of color distribution in dyes and paints.
Similar results are obtained by high refinement of varnishes and other finishes. Ultra-fine
particles of certain metals and other materials, such as cobalt, hydrides, molybdenum,
nitrides, titanium, tungsten, and various alloys and other compounds of the same, will
permit the manufacture of those materials at previously-unachieved economic or
performance properties and in superalloy and other combinations not previously
obtainable. Diamond particles can be reduced to dimensions not previously obtainable
due to their hardness relative to known grinding media, permitting more efficient use of
diamond particles at reduced cost. Ultra-fine particles will become available that can be
formed by molding, electrostatic deposition and other known methods into
microelectromechanical products and other micron-scale devices that previously were
obtainable only by etching of glass or silicon or other semiconductors. Ultra-fine
particles can be introduced to certain liquids to form fluids that exhibit special properties
of heat transmission, solubility and other qualities.
[043] Through use of the invention, samples produced either by more coarse milling or
by high-rate precipitation are further refined through milling process with multi-carbide
grinding media to preferred specifications at high speed and relatively low cost. Other
valuable materials are made uniquely possible by the claimed methods of the invention.
[044] The invention also permits the manufacture of ultra-fine particles with geometries
superior to those achieved by known manufacturing methods. Por example, chemical
precipitation can create particles of certain materials in extremely small dimensions.
Those particles, however, generally exhibit smooth and rounded shapes. Fig. 1 shows
particles that were assembled atomistically by precipitation. Such particles are also
typical of those particles produced by known means such as sol gel, vapor phase
condensation, etc. The science dealing with the surface topography of particles speaks in
terms of a fractured surface which has discernible cleavage facets and cleavage steps.
These two features are specifically absent from the particles produced by the known
processing methods for producing very small particles. Another missing feature in
particles produced according to prior art methods is concavity. Concavity is defined as
that condition where some portion of the surface lies beneath the surrounding surface. In
precipitated particles, the surface is bulbulous, meaning that a portion of the surface
protrudes above the surrounding surface such as is always true in the case of a sphere.
[045] As shown in Fig. 2, ultra-fine particles produced by milling according to the
present invention exhibit more angular geometries with cleaved surfaces and angular
intersecting surfaces that exhibit higher activity relative to the materials formed by other
means, causing ultra-fine milled particles to tend to exhibit superior chemical and
mechanical properties over particles of similar size and dimension that are manufactured
by precipitation and similar methods. Note the corners, flat edges, etc. of the very small
particles produced by the milling method of the present invention.
[046] A catalyst produced according to the present invention is less than 30 x 10"9
meters in all dimensions and possesses cleaved surfaces, the catalyst being uniquely
distinguishable by its particle surface features having a preponderance of cleavage facets
and/or cleavage steps, the catalyst alternatively being uniquely distinguishable by the
acutance of a preponderance of intersecting surfaces in which the arc length of the edge is
less than the radius of the edge, the catalyst alternatively being uniquely distinguishable
by surface concavities greater than 5% of the particle diameter, the catalyst alternatively
being uniquely distinguishable by the acutance of a preponderance of intersecting
surfaces in which the included angle of the edge radius is about, or less than, the included
angle of the intersecting surfaces.
[047] Intermetallic particles produced according to the present invention have less than
30 x 10" meters in all dimensions and possess cleaved surfaces. The product is uniquely
distinguishable by its particle surface features having a preponderance of cleavage facets
and/or cleavage steps, the product alternatively being uniquely distinguishable by the
acutance of a preponderance of intersecting surfaces in which the arc length of the edge is
less than the radius of the edge, the catalyst alternatively being uniquely distinguishable
by surface concavities greater than 5% of the particle diameter, the product alternatively
being uniquely distinguishable by the acutance of a preponderance of intersecting
surfaces in which the included angle of the edge radius is about, or less than, the included
angle of the intersecting surfaces.
[048] The grinding media of the present invention are also useful in other fields.
Examples include the manufacture of "hard bodies" for drilling or grinding, laser
cladding and other cladding processes, use as surface materials, and other applications.
For instance, grinding media are used without media mills as a component of alloys to be
applied to surfaces for improved wear resistance. Two common methods of applying
such protective coatings are known as cladding and surfacing. Each of these have many
methods employed, the choice of which depending on the object and alloy to be treated.
Generically, binder materials such as polymers or metals are used to hold grinding media
onto the surface of the object being treated by cladding or surfacing. The binder
materials are melted or cast into place along with the grinding media material which itself
is not melted during the cladding or surfacing operation. Typical melting methods
include laser, furnace melting, welding tubes and plasma heat sources. When in use, the
binder material itself often cannot withstand the wear imposed on the surface by the
operating environment such as in oil well drilling. This binder wear exposes the grinding
media to the surface, thereby providing a wear resisting surface protection. These same
surfaces are often exposed to very high shock impacts which the grinding media is able to
withstand.
[049] To create multi-carbide grinding media, a compound ("multi-carbide material") is
formed from carbon and at least two carbide-forming elements. U.S. Patent Nos.
3,690,962, 3,737,289, 3,779,745, and 4,066,451 (all to Rudy), incorporated herein by
reference, disclose how to make such multi-carbide materials for use as cutting tools.
[050] In an embodiment of the invention, the multi-carbide material is formed from
carbon and carbide-forming elements selected from the group consisting of chromium,
hafnium, molybdenum, niobium, rhenium, tantalum, thallium, titanium, tungsten,
vanadium, zirconium, and any other carbide forming element. Multi-carbide material can
be formed either with or without some of the carbide-forming elements not being fully
carburized and thus remaining in the material in its elemental state. The multi-carbide
material can contain a certain amount of impurities and other extraneous elements
without significantly affecting its material properties.
[051] The production of spheres from irregular shaped particles can be achieved by
various means. One common method of processing ultrahigh melting point materials into
spheres is with the use of a thermal plasma torch. Such a torch can operate at
temperatures well beyond the melting point of all multi-carbide materials. Other
methods, such as melt atomization or arc melting, are known to those familiar with the art
and there is no intention to limit the practice to just the use of these named methods. In
short, any known technique for applying heat which brings the material to its melting
point will work. How to form other shaped media is also known in the art.
[052] The known methods of forming spheres from carbides also form spheres when the
known methods are applied to multi-carbide materials, but the acceptable spheres amount
to approximately 40 % of the total produced. A new method for producing spheres from
multi-carbide materials was therefore developed. According to an embodiment of the
invention, the method for producing spheres from multi-carbide materials is as follows.
The multi-carbide material is formed into spheres preferably by admixing fine particles of
the elements intended to comprise fee multi-carbide material in appropriate ratios, by
adequately mixing the components, by maintaining the stability of the mixture by
introduction of an inert binding agent, by subdividing the mixture into aggregates each
having a mass approximately equal to that of the desired sphere to be formed, by
applying heat to the subdivided aggregate sufficient to cause its elements to fuse, and by
cooling the fused sphere in a manner that preserves its spherical shape. This
manufacturing process is used to make small and regular spheres that are composed of
multi-carbide material. Spheres of very small diameters, i.e., less man 500 microns
diameter and down to 0.5 microns diameter, with regular geometries and predictable,
optimized compositions can be produced.
[053] Spheres of multi-carbide material can be formed in this manner by the use of a
thermal plasma torch or vertical thermal tube to raise the temperature of the multi-carbide
particles above their melting point as they pass through the plasma or down the tube.
Other methods that can so raise the temperature of the multi-carbides, such as melt
atomization or arc melting, also should be effective.
[054] Such spheres can be utilized as grinding media in media mills ("multi-carbide
grinding media"), as the grinding medium in a hard body drill bit or grinding wheel, as
the abrasive medium for "sand blasting" shaping techniques^ and in other applications.
[055] Shapes other than spheres can be formed. For example, a variety of shapes can be
formed by molding and sintering sufficiently small particles of the multi-carbide material.
The geometry of such shapes can be varied nearly arbitrarily to achieve different grinding
properties. The manufacturing process is an improvement over the current art in that it
forms multi-carbides by processes that better mix and do not vaporize elements during
manufacture, improving predictability and performance characteristics of the produced
material; and that do not crack or otherwise degrade the material as it is formed into
useful shapes, to improve the mechanical toughness of the produced material.
[056] The multi-carbide grinding media, of whatever shape, can be used in media mills
to achieve efficient and thorough comminution of materials with high purity due to the
extreme hardness, extreme density, and extreme mechanical toughness of the material,
independent of size or shape. In such applications, particles of product material to be
reduced in size are admixed with the colliding grinding media. The product material
particles, interspersed between the grinding media units, are rapidly reduced in size.
Reductions to controlled dimensions as small as 10"9 meters can be achieved and readily
reproduced with the right combination of initial source material, grinding media and
media mill or other reduction process. Due to the engineered material properties of the
multi-carbide grinding media, the wear rates of the grinding media units are extremely
low and their grinding effectiveness is very high, enabling the efficient conversion of
coarse particles into extremely small product size while maintaining high purity. That is,
the multi-carbide grinding media deliver virtually no contamination to the product
material.
[057] Separation of product from the multi-carbide grinding media is accomplished by
various means known in the art, such as washing and filtering or gravity separation. The
product particles are much smaller than the grinding media, so separation can be
accomplished efficiently and effectively.
[058] Selection of appropriate grinding media material is critical to outcome. Very
small variations in the chemical composition of a material can have a great effect upon its
performance as a grinding or milling medium. Changes of in a carbide have been shown to cause changes of 40% or more in hardness, mechanical
toughness, or other important property of the compound.
[059] All of the above compositional and processing considerations for producing
microspheres of superior performance for milling also apply for producing spheres of the
present invention for laser cladding, other surfacing techniques, and hard bodies.
[060] For example, the media of the present invention include mill media of any
geometry composed of multiple carbide-forming elements, with carbon, having a density
greater than 8 gm/cc and a combination of hardness and toughness sufficient to permit
use in a media mill without contamination of the milled product to an amount greater
than 800 ppm.
[061] According to the present invention, a method for making spheres, composed of
multiple carbide-forming elements, with carbon, for use as mill media, or in cladding
material, as surfacing material, or in hard body materials containing these spheres,
includes the steps of:
(a) obtaining fine particles of appropriate compositions to form the desired
composition;
(b) admixing the particles in appropriate ratios to form the desired composition
and for adequate mixing of components;
(c) subdividing the mixture into aggregates each having a weight about that of the
desired sphere size range; and
(d) fusing the aggregates to at least 90% theoretical density by any means
providing temperature, and time at temperature, appropriate for fusion of the components.
[062] According to the present invention, a method for producing fine oxides of any
metal but in particular titanium, being of a size less than 3 microns and including down to
1 x 10"9 using larger particles of oxides of titanium, includes the steps of:
(a) obtaining large particles of oxides, especially of titanium, because such oxide
particles are typically much cheaper to procure than fine particles of oxides of titanium,
hereinafter such particles being termed feed oxides;
(b) processing the feed oxides in a media mill using spheres of multi-carbide
materials with a mass density greater than 8 gm/cc and a hardness and toughness
sufficient so as not to contaminate the milled oxides of titanium to a degree greater than
200 ppm; and
(c) processing the feed oxides at an energy intensity to cause size reduction of the
feed oxide, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to the preferred size. Such oxides are useful for applications such as
pigments, fillers, gas sensors, optronic devices, catalyst, and the manufacture of ceramics,
manufacture of components, while being more economic to produce than those obtained
by other methods.
[063] According to the present invention, a method for producing highly transparent
oxides of titanium includes the steps of:
(a) obtaining a slurry of not adequately transparent titania;
(b) processing the titania slurry in a media mill using spheres of multi-carbide
material with a mass density greater than 8 gm/cc and a hardness and toughness sufficient
to not contaminate the milled oxides of titanium to a degree greater than 100 ppm; and
(c) processing the slurry until the size distribution of the particles has a D100 of
90 xlO"9 meters or less.
[064] According to the present invention, a method for producing titanium metal
includes the steps of:
(a) obtaining titania feed material, where the feed material is from a high purity
source such as readily available chloride processed titania;
(b) processing the titania in a media mill using spheres of multi-carbide material
with a mass density greater than 8 gm/cc and a hardness and toughness sufficient not to
contaminate the milled oxides of titanium to a degree greater than 800 ppm;
(c) processing the titania at an energy intensity to cause size reduction of the feed
oxide, in a dry or wet media mill, for a period of time sufficient to reduce the particle size
to about 200 x 10'9 meters or less;
(d) chemically reducing the titania to titanium metal using a reducing agent such
as hydrogen in combination with another reducing agent, if needed, such as a
carbothermic reduction agent such as CO or carbon under conditions suitable for oxide
reduction without the formation of titanium carbide;
(e) either removing the titanium metal from the reduction equipment without
exposure to oxygen or nitrogen under conditions causing oxidation or nitridation of the
ultrafine titanium metal or raising the temperature of the ultraflne titanium metal to cause
fusion of the particles before removal from the reduction equipment. Other reducing
agents are known in the art.
[065] The present invention can be used for producing diamond particles of less than
about 100 x 10"9 meters in all dimensions and, if desired, of a tight particle size
distribution, with the diamond particles being usable for CMP (chemical mechanical
polishing) and other polishing applications. According to the present invention, a method
for producing such diamond includes the steps of:
(a) obtaining industrial diamonds of suitable feed material size;
(b) processing the diamonds in a media mill using spheres of multi-carbide
material with a mass density greater than 8 gm/cc and a hardness and toughness sufficient
cause size reduction of the diamond material;
(c) processing the diamonds at an energy intensity to cause size reduction of the
diamond particles, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to between about 100 x 10'9 meters and about 2 x 10"9 meters;
(d) purifying the processed diamonds, if necessary to remove contaminants, by
chemical dissolution of impurities or by other methods known in the art.
[066] According to the present invention, a method for producing devices of silicon or
other semiconductors or other materials, of micro ornanoscale dimensions, typically
called MEMS, by building the device with ultrafine particles rather than substractively
forming the device from solid semiconductor material with etching or other methods,
includes the steps of:
(a) obtaining particulate feed material of the desired composition or combinations
of particulate materials to be composed into a target composition; t
(b) processing the feed material in a media mill using spheres of multi-carbide
material with a mass density greater than 8 gm/cc and a hardness and toughness sufficient
not to contaminate the milled feed material to a degree greater than 200 ppm;
(c) processing the feed material at an energy intensity to cause size reduction, in a
dry or wet media mill, for a period of time sufficient to reduce the particle size to about
200 x 10"9 meters or less and more preferably to 50 x 10"9 meters or less;
(d) forming the processed particulates into a molded article, by means known in
the art such as pressure molding, injection molding, freeze molding, electrophoretic
shaping, electrostatic deposition and other known methods; whereby the forming method
allows for creation of unique MEMS devices whereby different parts of the structure can
have different materials of construction; and
(e) fusing the molded article to sufficient density to have properties adequate for
the intended performance of the device, where such properties are determined specifically
by the design application.
[067] According to the present invention, a method for producing fine SiC of a size less
than 1 micron and including down to 0.001 microns vising larger particles of SiC includes
the steps of:
(a) obtaining large particles of SiC because such large particles are typically much
cheaper to procure than fine particles of SiC, these particles being termed feed particles;
(b) processing the feed particles in a media mill using spheres of multi-carbide
material with a mass density greater than 8 gm/cc and a hardness and toughness sufficient
not to contaminate the milled particles to a degree greater than 600 ppm; and
(c) processing the feed particles at an energy intensity to cause size reduction of
the feed particles, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to the preferred size; with such particles being useful for the manufacture of
silicon carbide ceramic bodies, ceramic bodies containing silicon carbide in the
composition, applications such as pigments, polishing compounds, polymer fillers,
sensors, catalyst, and the manufacture of ceramics, manufacture of components and also
being more economic than that obtained by other methods.
[068] According to the present invention, a method for producing fine A12O3 being of a
size less than 1 micron and including down to 0.001 microns using larger particles of
A12O3 includes the steps of:
(a) obtaining large particles of A12O3. Such large particles are typically much
cheaper to procure than fine particles of A12O3. These particles are termed "feed
particles."
(b) processing the feed particles in a media mill using spheres of multi-carbide
materials with a mass density greater than 8 gm/cc and a hardness and toughness
sufficient not to contaminate the milled particles to a degree greater than 600 ppm; and
(c) processing the feed particles at an energy intensity to cause size reduction of
the feed particles, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to the preferred size. Such particles are useful for the manufacture of
alumina ceramic bodies, ceramic bodies containing alumina in the composition,
applications such as pigments, polishing compounds, polymer fillers, sensors, catalyst,
and the manufacture of ceramics, manufacture of components and also are more
economic than that obtained by other methods.
[069] According to the present invention, a method for producing nanofhiids having
suspended particles with a size distribution of D50=30 x 10~9 or less includes the steps of:
(a) obtaining particulate feed material of the desired composition;
(b) processing the feed material in a media mill using spheres of multi-carbide
material with a mass density greater than 8 gm/cc and a hardness and toughness sufficient
to not contaminate the milled feed material to a degree greater than 400 ppm;
(c) processing the feed material at an energy intensity to cause size reduction, in a
dry or wet media mill, for a period of time sufficient to reduce the particle size to a milled
product of about 200 x 10"9 meters or less and more preferably to 50 x 10"9 meters or less
and most preferably to 10 x 10'9 meters or less;
(d) concentrating the milled product in suitable carrier fluid, such carrier fluids
being specified by the application and including water, oil, and organics, with the degree
of concentration of particulate material in the fluid being specified by the application.
[070] According to the present invention, a method for producing fine tungsten particles
of a size less than 400 x 10"9 meters and including down to 1 x 10"9 meters using larger
particles of tungsten, including the steps of:
(a) obtaining large particles of tungsten because large particles are typically much
cheaper to procure than fine particles of tungsten, with the particles being termed feed
particles;
(b) nitriding the feed material, such nitride being known to be brittle, by known
methods of nitriding such as heating tungsten in dissociated ammonia at 500 degrees C
for a length of time proportionate to the feed material size but sufficient to cause
nitridation;
(c) processing the nitrided feed particles in a media mill using spheres of multi-
carbide material with a mass density greater than 8 gm/cc and a hardness and toughness
sufficient not to contaminate the milled particles to a degree greater than 900 ppm;
(d) processing the feed particles at an energy intensity to cause size reduction of
the feed particles, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to the preferred size; and
(e) if desired, denitriding the tungsten nitride particulates by heating to about 600
degrees C or higher by methods now known in the art. Such particles are useful for the
manufacture of tungsten bodies, tungsten alloy bodies, ceramic bodies containing
tungsten in the composition, applications such as pigments, polishing compounds,
electronic inks, metallo-organic compounds, polymer fillers, sensors, catalyst, and the
manufacture of metal-ceramics, manufacture of components and are also more economic
than that obtained by other methods.
[070] According to the present invention, a method for producing tungsten components,
or tungsten alloy components, from the fine tungsten particles produced by the method
detailed in the preceding paragraph, includes the steps of:
(a) obtaining nitrided tungsten milled product of a size less than 400 x 10-9 meters
and more preferably less than 100 x 10"9 meters and most preferably of less than 50 x 10"9
meters;
(b) producing tungsten metal components by powder metallurgy processing by
consolidation and forming the tungsten nitride prior to denitridation;
(c) denitriding the tungsten nitride component during heating to sintering
temperatures with the release of nitrogen contributing to flushing residual gases from
between the particles; and
(d) sintering the formed component at temperatures proportionate to the particle
size, with these temperatures being substantially less than now required in the art for
commercially available tungsten powders.
[072] According to the present invention, a method for producing fine molybdenum
particles of a size less than 400 x 10-9 meters and including down to 1 x 10-9 meters using
larger particles of molybdenum includes the steps of:
(a) obtaining large particles of molybdenum, such large particles typically being
much cheaper to procure than fine particles of molybdenum, said particles being termed
feed particles;
(b) nitriding the feed material, such nitride being known to be brittle, by known
methods of nitriding such as heating molybdenum in dissociated ammonia at about 500
degrees C for a length of time proportionate to the feed material size but sufficient to
cause nitridation;
(c) processing the nitrided feed particles in a media mill using spheres of multi-
carbide material with a mass density greater than 8 gm/cc and a hardness and toughness
sufficient to not contaminate the milled particles to a degree greater than 900 ppm;
(d) processing the feed particles at an energy intensity to cause size reduction of
the feed particles, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to the preferred size; and
(e) if desired, denitriding the molybdenum nitride particulates by heating to about
600 degrees C or higher by methods now known in the art. Such particles are useful for
the manufacture of molybdenum bodies, molybdenum alloy bodies, ceramic bodies
containing molybdenum in the composition, electronic inks, metallo-organic compounds,
applications such as pigments, polishing compounds, polymer fillers, sensors, catalyst,
and the manufacture of metal-ceramics, manufacture of components and also are more
economic than particles obtained by other methods.
[073] According to the present invention, a method for producing molybdenum or
molybdenum alloy components from particles produced according to the method of the
preceding paragraph include the steps of:
(a) obtaining nitrided molybdenum milled product of a size less than 400 x 10'9
meters and more preferably less than 100 x 10"9 meters and most preferably of less than
50 x 10'9 meters;
(b) producing molybdenum metal or alloy components by powder metallurgy
processing by consolidation and forming the molybdenum nitride prior to denitridation;
(c) denitriding the molybdenum nitride during heating to sintering temperatures
with the release of nitrogen contributing to flushing residual gases from between the
particles; and
(d) sintering the formed component at temperatures proportionate to the particle
size, where these temperatures are substantially less than now required in the art for
commercially available molybdenum powders.
[074] According to the present invention, a method for producing fine cobalt particles
or cobalt nitride particles being of a size less than 5 microns and including down to 1 x
10"9 meters using larger particles of cobalt includes the steps of:
(a) obtaining large particles of cobalt or cobalt nitride, such large particles
typically being gas atomized and therefore much cheaper to procure than fine particles of
cobalt or cobalt nitride, with such particles being termed feed particles;
(b) nitriding the feed material, if not already nitrided, such nitride being known to
be brittle, by known methods of nitriding such as heating cobalt in dissociated ammonia
at about 600 degrees C for a length of time proportionate to the feed material size but
1 sufficient to cause nitridation;
(c) processing the nitrided feed particles in a media mill using spheres of multi-
carbide material with a mass density greater than 8 gm/cc and a hardness and toughness
sufficient not to contaminate the milled particles to a degree greater than 500 ppm;
(d) processing the feed particles at an energy intensity to cause size reduction of
the feed particles, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to the preferred size; and
(e) if desired, denitriding the cobalt nitride particulates by heating to about 600
degrees C or higher by methods now known in the art. Such particles are useful for the
manufacture of catalyst, alloy bodies containing cobalt, ceramic bodies containing cobalt
in the composition, electronic inks, metallo-organic compounds, applications such as
pigments, polishing compounds, polymer fillers, sensors, catalyst, promoters, the
manufacture of superalloy components containing cobalt, for use in the hard metals
industries where cobalt is a binder metal and also are more economic to produce than
those obtained by other methods.
[075] According to the present invention, a method for producing fine metal particles
from metal nitrides, being of a size less than 20 microns and including down to 1 x 10"9
meters using larger particles of metals includes the steps of:
(a) obtaining large particles of metal or metals nitride from that group of metals
having nitrides that dissociate when heated from 300 degrees C to about 900 degrees C,
such large particles typically being gas atomized and therefore much cheaper to procure
than fine particles of metals or metals nitride, such particles being termed feed particles;
(b) nitriding the feed material, if not already nitrided, such nitride being known to
be more brittle than metal which is ductile, by known methods of nitriding such as
heating metals particles in dissociated ammonia at a temperature sufficient to cause
nitridation for a length of time proportionate to the feed material size but sufficient to
cause nitridation;
(c) processing the nitrided feed particles in a media mill using spheres of multi-
carbide material with a mass density greater than 8 gm/cc and a hardness and toughness
sufficient not to contaminate the milled particles to a degree greater than 900 ppm;
(d) processing the feed particles at an energy intensity to cause size reduction of
the feed particles, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to the preferred size; and
(e) if desired, denitriding the metals nitride particulates by heating to about 600
degrees C or higher by methods now known in the art. Such particles are useful for the
manufacture of catalyst, alloy bodies containing metals, ceramic bodies containing metals
in the composition, electronic inks, metallo-organic compounds, applications such as
pigments, polishing compounds, polymer fillers, sensors, catalyst, promoters, the
manufacture of superalloy components, the manufacture of metal components combining
various metals processed by this claim, for use in the hard metals industries where metals
is a binder metal and also are more economical to produce than those obtained by other
methods.
[076] According to the present invention, a method for producing fine metal particles or
metal hydride particles from metal hydrides such as titanium and tantalum, being of a
size less than 300 x 10"9 meters and including down to 1 x 10"9 meters using larger
particles of metals includes the steps of:
(a) obtaining large particles of metal hydrides from that group of metals forming
hydrides that dissociate when heated, such large particles typically being pressure
hydrided and therefore much cheaper to procure than fine particles of metals or metal
hydrides, with such particles being termed feed particles;
(b) processing the hydrided feed particles in a media mill using spheres of multi-
carbide material with a mass density greater than 8 gm/cc and a hardness and toughness
sufficient not to contaminate the milled particles to a degree greater than 900 ppm;
(c) processing the feed particles at an energy intensity to cause size reduction of
the feed particles, in a dry or wet media mill, for a period of time sufficient to reduce the
particle size to the preferred size; and
(d) if desired, dehydriding the ultrafine metals hydride particulates by heating to
the dehydration temperature by methods now known in the art. Such particles are useful
for the manufacture of catalyst, alloy bodies containing metals, ceramic bodies containing
metals in the composition, electronic inks, metallo-organic compounds, applications such
as pigments, polishing compounds, polymer fillers, sensors, catalyst, promoters, the
manufacture of superalloy components, the manufacture of metal components combining
various metals processed by this claim, for use in the hard metals industries where metals
is a binder metal and also being more economic than that obtained by other means
[077] As discussed in the Background section, the search for an optimal material to be
used as mill media has been ongoing. After much experimentation and testing, multi-
carbides were identified by the inventor as a possible material. Although the multi-
carbides disclosed by the Rudy patents showed a combination of hardness, density and
mechanical toughness that promised to be useful for milling, the known geometries for
available multi-carbide materials rendered them incompatible with such use. Difficulties
included the large size of multi-carbide material that is produced by current
manufacturing methods, and difficulty in machining or otherwise manipulating the
material into sizes and shapes useful for milling due in part to its hardness and
mechanical toughness.
[078] After extensive analysis and experimentation, the effectiveness of using multi-
carbide grinding media was shown empirically in the following experiment. Spheres
according to the present invention were formed by taking material composed of Ti, W,
and C and preparing spheres 150 microns in diameter. The test composition in this
example was 86.7 wt% tungsten, 4.5 wt% carbon, and the balance titanium.
Agglomerates of particulates of this test composition were spheridized in an RF Plasma
spray unit. The density of the material was confirmed as being the same as the multi-
carbide material that was sought to be made.
[079] The multi-carbide spheres of the present invention were then subjected to
hardness testing. A compression test was employed in which a single small sphere was
isolated between two pieces of ground tungsten plate and a force was applied to one of
the plates. The intention was to increase the applied pressure until the sphere fragmented
due to the extreme load at the point contact between the plate and the sphere.
Unexpectedly, spheres of the test composition did not fracture, but instead embedded into
the tungsten plate, demonstrating hardness of the test material well above that of pure
tungsten. In a second test, several spheres were positioned between two tungsten plates
and the top plate was struck with a weight so as to induce high transitory g-forces on the
spheres. None of the spheres fractured, with many of the spheres embedded into the
tungsten plate. In two instances of the experiment, the tungsten plate fractured and
cleaved, but with no apparent damage to the spheres. In another experiment, spheres of
the test composition were placed between two ground glass plates. Upon applying
pressure, the glass micro-fragmented around its points of contact with the spheres, but no
damage to the spheres was observed.
[080] The multi-carbide spheres were subjected to mechanical toughness testing.
Spheres of the test composition were placed in a vibratory mill with calcium carbide and
agitated for a period of time sufficient to cause significant grinding media degradation by
all known grinding media. No evidence of contamination by grinding media degradation
was observed from such use of the resultant spheres, and very fine, regular and pure
calcium carbide was obtained.
[081] The multi-carbide spheres were also subjected to testing by use in standard
industry processes. The spheres were used in a high-volume media mill and operated
under nominal industrial production conditions used to mill titania. Titania is particularly
sensitive to discoloration from contamination and was chosen to be a sensitive indicator
to see if the microspheres were able to impart wear without themselves wearing
significantly. Billions of particles of titania were processed to a final particle size of
approximately 7 x 10"8 meters without perceptible evidence of grinding media
degradation.
[082] While testing and. processing various materials, impurities were occasionally
measured to see how the process was working. Tests were conducted with calcium
carbonate processed to less than 100 nm using standard media mill operating conditions
and the grinding media of the invention of 120 microns diameter. The contamination
level in the milled product was measured to be less than 100 ppm, and in some instances,
less than 10 ppm. It is expected that the contamination level should always be below 300
ppm. The contamination level is dependent on the substance being milled, with calcium
carbonate being relatively soft. It is expected that the contamination level should always
be below 300 ppm even when milling alumina.
[083] While the present invention has been described with reference to a particular
preferred embodiment, it will be understood by those skilled in the art that the invention
is not limited to the preferred embodiment and that various modifications and the like
could be made thereto without departing from the scope of the invention as defined in the
following claims.
We Claim:
1. A method for milling a product in a media mill, comprising the step of milling a product
in a medial mill using grinding media, wherein the grinding media comprise-a multi-carbide
material which includes-carbon and at least two carbide-forming metal.
2. A method as claimed in claim 1, wherein said carbide-forming metal elements are
selected from the group consisting of chromium, hafnium, molybdenum, niobium, rhenium,
tantalum, thallium, titanium, tungsten, vanadium, and zirconium.
3. A method as claimed in claims 1 or 2 wherein said multi-carbide material further includes
a carbide-forming element in its elemental state.
4. A method as claimed in claim 1, wherein said multi-carbide materialconsists essentially
of titanium, tungsten, and carbon, in the ratios of from about 10 to 90 at% tungsten, from about 2
to 97 at% titanium, and the balance carbon.
5. A method as claimed in any preceding_claims, wherein the grinding media comprise
spheres ranging in size from 0.5 micron to 100 mm in diameter.
6. A method as claimed in any preceding claim, wherein the grinding media have a size of
less than 500 micron.
7. A method as claimed in 1, comprising milling the product to a size of less than 100
nanometers.
8. A method as claimed in 1, comprising milling the product to a size of less than 30
nanometers.
9. A method as claimed in claim 1, comprising milling the product to a size of less than 100
nanometers and a contamination level of less than 800 ppm.
10. A method as claimed in claim 1, comprising milling the product to a size of less than 100
nanometers and a contamination level of less than 300 ppm.
11. A method as claimed in claim 1, comprising milling the product to a size of less than 100
nanometers in at least one dimension.
12. A method as claimed in claim 1, comprising milling catalytic particles to a size of less
than 30 nanometers.
13. A method as claimed in claim 1, comprising milling intermetallic particles to a size of
less than 30 nanometers.
14. A method as claimed in claim 1, comprising milling titania particles to a size of less than
90 nanometers and a contamination level of less than 100 ppm.
15. A method as claimed in claim 1, comprising milling diamond particles to a size of less
than 100 nanometers.
16. A method as claimed in claim 1, comprising milling semiconductor particles to a size of
less than 50 nanometers and a contamination level of less than 200 ppm.
17. A method as claimed in claim 1, comprising milling silicon carbide particles to a size of
less than 1 micron and a contamination level of less than 600 ppm.
18. A method as claimed in claim 1, comprising milling alumina particles to a size of less
than 30 nanometers and a contamination level of less than 600 ppm.
19. A method as claimed in claim 1, comprising milling tungsten particles to a size of less
than 400 nm and a contamination level of less than 900 ppm.
20 A method as claimed in claim 1, comprising milling molybdenum particles to a size of
less than 400 nm and a contamination level of less than 900 ppm.
21. A method as claimed in claim 1, comprising milling cobalt or cobalt nitride particles to a
size of less than 5 microns and a contamination level of less than 500 ppm.
22. A method as claimed in claim 1, comprising milling metal nitride particles to a size of
less than 20 microns and a contamination level of less than 900 ppm.
23. A method as claimed in claim 1, comprising milling metal hydride particles to a size of
less than 300 nm and a contamination level of less than 900 ppm.
24. A method as claimed in claim 1, wherein the multi-carbide material comprises at least
tungsten and titanium as the multi-carbide forming elements.
25. A method as claimed in claim 1, wherein the multi-carbide material comprises titanium
and/or alloying substituents for titanium, tungsten and/or alloying substituents for tungsten, and
carbon.
26. A method as claimed in claim 1, comprising milling the product to a size of less than 100
nanometers and a contamination level less than 10 ppm.
The invention discloses a method for milling a product in a media mill, comprising the step of
milling a product in a medial mill using grinding media, wherein the grinding media comprise-a
multi-carbide material which includes-carbon and at least two carbide-forming metal.

Documents:

1992-KOLNP-2005-CORRESPONDENCE.pdf

1992-KOLNP-2005-FORM 27-1.1.pdf

1992-KOLNP-2005-FORM 27.pdf

1992-KOLNP-2005-FORM-27.pdf

1992-kolnp-2005-granted-abstract.pdf

1992-kolnp-2005-granted-assignment.pdf

1992-kolnp-2005-granted-claims.pdf

1992-kolnp-2005-granted-correspondence.pdf

1992-kolnp-2005-granted-description (complete).pdf

1992-kolnp-2005-granted-drawings.pdf

1992-kolnp-2005-granted-examination report.pdf

1992-kolnp-2005-granted-form 1.pdf

1992-kolnp-2005-granted-form 18.pdf

1992-kolnp-2005-granted-form 3.pdf

1992-kolnp-2005-granted-form 5.pdf

1992-kolnp-2005-granted-gpa.pdf

1992-kolnp-2005-granted-reply to examination report.pdf

1992-kolnp-2005-granted-specification.pdf


Patent Number 223850
Indian Patent Application Number 1992/KOLNP/2005
PG Journal Number 39/2008
Publication Date 26-Sep-2008
Grant Date 23-Sep-2008
Date of Filing 07-Oct-2005
Name of Patentee PRIMET PRECISION MATERIALS, INC.
Applicant Address 1005 HUDSON STREET EXT., ITHACA, NY
Inventors:
# Inventor's Name Inventor's Address
1 ROBERT, DOBBS 67 BANK STREET, NEWFIELD, NY 14867
PCT International Classification Number B24B
PCT International Application Number PCT/US2004/007290
PCT International Filing date 2004-03-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/453,427 2003-03-11 U.S.A.