Title of Invention


Abstract There is disclosed a method of forming a hardened surface on a substrate, comprising providing a substrate; and forming a molten alloy and cooling the alloy to form a metallic glass coating on the substrate, the forming comprising forming a successive buildup of metallic glass layers, the metallic glass coating having a hardness of 9.2 GPa or more, and comprising one or more materials selected from the group consisting of
This application claims benefit of U.S. Non-provisional application
10/841,873 filed on May 6, 2004, entitled METHOD FOR FORMING A HARDENED
SURFACE ON A SUBSTRATE which is incorporated herein by reference in its entirety.
The United States Government has certain rights in this invention pursuant to
Contract No. DE-AC07-99ID13727, and Contract No. DE-AC07-05ID14517 between the
United States Department of Energy and Battelle Energy Alliance, LLC.
The invention pertains to metallic coatings and methods of forrmng metallic coatings.
Steel is a metallic alloy which can have exceptional strength characteristics, and
which is accordingly commonly utilized in structures where strength is required or
advantageous. Steel can be utilized, for example, in the skeletal supports of building
structures, tools, engine components, and protective shielding of modern armaments.
The composition of steel varies depending on the application of the alloy. For
purposes of interpreting this disclosure and the claims that follow, "steel" is defined as any
iron-based alloy in which no other single element (besides iron) is present in excess of 30
weight percent, and for which the iron content amounts to at least 55 weight percent, and
carbon is limited to a maximum of 2 weight percent. In addition to iron, steel alloys can
incorporate, for example, manganese, nickel, chromium, molybdenum, and/or vanadium.
Steel alloys can also incorporate carbon, silicon, phosphorus and/or sulfur. However,
phosphorus, carbon, sulfur and silicon can be detrimental to overall steel quality if present in
quantities greater than a few percent. Accordingly, steel typically contains small amounts of
phosphorus, carbon, sulfur and silicon.
Steel comprises regular arrangements of atoms, with the periodic stacking
arrangements forming 3-dimensional lattices which define the internal structure of the steel.
The internal structure (sometimes called "microstructure") of conventional steel alloys is
always metallic and polycrystalline (consisting of many crystalline grains).
Steel is typically formed by cooling a molten alloy. The rate of cooling will determine
whether the alloy cools to form an internal structure that predominately comprises crystalline
grains, or, in rare cases, a structure which is predominately amorphous (a so-called metallic
glass). Generally, it is found that if the cooling proceeds slowly (i.e., at a rate less than about
104 K/s), large grain sizes occur, while if the cooling proceeds rapidly (i.e., at a rate greater
than or equal to about 104 K/s) macrocrystalline internal grain structures are formed, or, in
specific rare cases amorphous metallic glasses are formed. The particular composition of the
molten alloy generally determines whether the alloy solidifies to form microcrystalline grain
structures or an amorphous glass when the alloy is cooled rapidly. Also, it is noted that
particular alloy compositions (not iron based) have recently been discovered which can lead
to microscopic grain formation, or metallic glass formation, at relatively low cooling rates
(cooling rates on the order of 10 K/s).
Both microcrystalline grain internal structures and metallic glass internal structures
can have properties which are desirable in particular applications for steel. In some
applications, the amorphous character of metallic glass can provide desired properties. For
instance, some glasses can have exceptionally high strength and hardness. In other
applications, the particular properties of microcrystalline grain structures are preferred.
Frequently, if the properties of a grain structure are preferred, such properties will be
improved by decreasing the grain size. For instance, desired properties of microcrystalline
grains (i.e., grains having a size on the order of 10"6 meters) can frequently be improved by
reducing the grain size to that of nanocrystalline grains (i.e., grains having a size on the order
of 10-9 meters). It is generally more problematic to form grains of nanocrystalline grain size
than it is to form grains of microcrystalline grain size. Accordingly, it is desirable to develop
improved methods for forming nanocrystalline grain size steel materials. Further, as it is
frequently desired to have metallic glass structures, it is desirable to develop methods of
forming metallic glasses.
In one aspect, the invention encompasses a method of forming a metallic coating. A
metallic glass coating is formed over a metallic substrate. After formation of the coating, at
least a portion of the metallic glass can be converted into a crystalline material having a
nanocrystalline grain size.
In another aspect, the invention encompasses metallic coatings comprising metallic
In yet another aspect, the invention encompasses metallic coatings comprising
crystalline metallic material, with at least some of the crystalline metallic material having a
nanocrystalline grain size.
Accordingly, the present invention provides a method of forming a hardened surface on a
substrate, comprising providing a substrate; and forming a molten alloy and cooling the alloy to
form a metallic glass coating on the substrate, the forming comprising forming a successive
buildup of metallic glass layers, the metallic glass coating having a hardness of 9.2 GPa or more,
and comprising one or more materials selected from the group consisting of

Preferred embodiments of the invention are described below with reference to the
following accompanying drawings.
Fig. 1 is a block-diagram flowchart view of a method encompassed by the present
Fig. 2 is a diagrammatic perspective view of a barrel being treated according to a
method of the present invention.
Fig. 3 is a fragmentary, diagrammatic, cross-sectional view cf a metallic material
substrate at a preliminary step of a treatment process encompassed by the present invention.
Fig. 4 is a view of the Fig. 3 fragment shown at a processing step subsequent to that of
Fig. 5.
Fig. 5 is a view of the Fig. 3 fragment shown at a processing step subsequent to that of
Fig. 4.
Fig. 6 is a view of the Fig. 3 fragment shown at a processing step subsequent to that of
Fig. 5.
Fig. 7 is an optical micrograph of a metallic glass ribbon formed in accordance with
methodology of the present invention, and formed from a composition comprising
Fig. 8 is a scanning electron microscope micrograph of a cross section of a gas
atomized powder particle formed in accordance with the present invention, and formed from
a composition comprising Fe63Cr8Mo2B17C5Si1Al4.
Fig. 9 is a graph illustrating the results of a differential thermal analysis scan of a
ribbon produced in accordance with the present invention. The ribbon was produced from a
composition comprising Fe63Cr8Mo2B17C5Si1Al4. An exothermic glass to crystallization
transition occurs at 550°C, and an endothermic solid to liquid melting transition occurs at
Fig. 10 is a TEM micrograph of a steel alloy produced in accordance with the
methodology of the present invention, and comprising a composition Fe63Cr8Mo2B17C5Si1Al4,
which has been heat treated for 650°C for one hour. A nanoscale nanocomposite
rnicrostructure is visible, with phase sizes from 1 to 75 nanometers.
Fig. 11 illustrates Vickers hardness for different metallic alloys. Specifically, the
figure compares DAR1 (Fe63Cr8Mo2B17C5Si1Al4) with DAR20
(Fe64Ti3Cr5Mo2B l6C5Si1Al2La2). The hardness is compared as a function of heat treatment
Fig. 12 shows examples of Vickers hardness tests using a diamond pyramid indenter.
Specifically, a top portion of the figure shows the test relative to gas atomized powder
particles, and a lower portion shows the test utilized for a melt-spun ribbon. The tested
composition was Fe63Cr8Mo2B17C5Si1Al4.
Fig. 13 is an optical micrograph of a steel composition which has been plasma sprayed
onto a stainless steel substrate. The plasma-sprayed steel composition comprises
Fe63Cr8Mo2B17C5Si1Al4. The top portion of Fig. 9(a) is a cross-sectional view of the sprayed
material, and the lower portion (b) shows a top surface of the coated material.
Fig. 14 illustrates an x-ray diffraction scan of a plasma-sprayed deposit having a free
surface. The plasma-sprayed composition was Fe63Cr8Mo2B17C5Si1Al4.
Fig. 15 shows an x-ray diffraction scan of the plasma-sprayed composition of Fig. 14,
and illustrates the structure at the substrate surface.
Fig. 16 illustrates a graph showing coefficient of friction versus the number of turns
for Pin On Disk testing of a spray coating. The tested coating was Fe63Cr8Mo2B 17C5Si1Al4. It
is noted that while the initial friction was low, Si3N4 deposition and buildup caused the
friction to increase. (The sliding friction of Si3N4 on itself is 0.8).
Fig. 17 is a profile curve of a "wear-groove" on an as-sprayed steel substrate after
2,000 cycles of Pin On Disk testing. As shown, instead of a groove developing on the steel
substrate, the Si3N4 wore and deposited material onto the substrate. The tested composition
was Fe63Cr8Mo2BnC5Si1Al4.
Fig. 18 is an optical micrograph of an as-spun ribbon of (Fe0.8CR0.2)g1B17W2. The
alloy exhibits high ductility, and can be bent severely without fracture.
Fig. 19 illustrates data obtained from differential thermal analysis of
(Fe08Cr02)75B17Si4Al4 (top graph) and Fe63Cr8MO2B17C5Si1Al4 (lower graph). The graph
curves show glass to crystalline transitions and melting temperatures for the tested alloys.
Fig. 20 shows peak crystallization temperatures measured by differential thermal
analysis for a variety of alloys. Specifically, Fig. 20 shows the alloy Fe63Cr8Mo2B17CsSi1Al4
as 1, (Fe085Cr015)g3B17 as 2, (Fe08Cr02)83BI7 as 3, (Fe075Cr025)83B17 as 4, (Fe0-BMo02)83B17 as 5,
(Fe06Coa2Cr0.2)83B17 as 6, (FeoaCr015Moao5)83B17 as 7, (Fe08Cr0:z)79BnC4 as 8,
The invention encompasses methodology for forming steel materials having
nanocrystalline scale composite microstructures, methods of utilizing such steel materials,
and also encompasses the steel material compositions. A process encompassed by the present
invention is described generally with reference to the block diagram of Fig. I. At an initial
step (A) a molten alloy is formed. Such alloy comprises a steel composition. An exemplary
alloy comprises at least 50% Fe and at least one element selected from the group consisting of
Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
and Lu; and at least one element selected from the group consisting of B, C, N, O, P and S.
In particular aspects of the present invention, the alloy will be a magnetic alloy with ultrafine
crystal grains having a composition represented by the formula: Fe(100-x-y)M(x)B(y) (atomic
percent) wherein M represents at least one element selected from Ti, Zr, Hf, V, Nb, Mo, Ta,
Cr, W and Mn, wherein 15^x^4, wherein 25^y^2, and wherein 35^(x+y)27. Also, at least
50% of the alloy structure is preferably occupied by crystal grains having an average size of
1000A or less, with the crystal grains being based on a bcc structure. The alloy can further
contain X (Si, Ge, P, Ga, etc.) and/or T (Au, Co, Ni, etc.).
Alloys of the present invention preferably comprise fewer than 11 elements, and can
more preferably comprise fewer than seven elements. Additionally, the alloys can comprise
fewer than five elements. An advantage in having fewer elements in the compositions is that
it can be easier to reproduce a material if fewer components are utilized in forming the
material. Generally, alloys of the present invention have from four to six elements in their
compositions. Among such elements are iron; chromium, which can be included for
corrosion resistance; boron and/or phosphorus which can be included to generate a particular
glass transition temperature; and one or both of molybdenum and tungsten which can be
included for hardness.
Exemplary alloys which can be utilized in methodology of the present invention are:

The alloy of step (A) can be formed by, for example, melting a composition under an
argon atmosphere.
At step (B) of Fig. 1, the alloy is cooled to form a metallic glass. Such cooling
typically comprises a rate of at least about 104 K/s, with the rate varying depending on the
particular composition of the molten alloy. The cooling can be accomplished by a number of
different processes, including, for example, melt-spinning, gas atomization, centrifugal
atomization, water atomization and splat quenching. The powder can be consolidated by, for
example, hipping, hot pressing, hot extrusion, powder rolling, powder forging and dynamic
compaction. In an exemplary method, the cooling of step (B) is accomplished by centrifugal
atomization. Preferably, the melt stream leaves a centrifugal cup and is hit by high pressure
helium gas to facilitate fast cooling (greater than 105 K/s.) The helium gas can be collected,
purified and reused. The speed of the rotating centrifugal cup is preferably about 40,000
RPM, and such speed can be adjusted to produce a fine powder with about a 25 micrometer
mean size.
Referring to step (C) of Fig. 1, the metallic glass of step (B) is devitrified to form a
crystalline steel material having a nanocrystalline grain size. Such devitrification can be
accomplished by heating the metallic glass to a temperature of from about 600°C to less than
the melting temperature of the alloy. Such heating enables a solid state phase change wherein
the amorphous phase of the metallic glass is converted to one or more crystalline solid
phases. The solid state devitrification of the amorphous precursor from step (B) enables
uniform nucleation to occur throughout the metallic glass to form nanocrystalline grains
within the glass. The metal matrix microstructure formed via the devitrification can comprise
a steel matrix (iron with dissolved interstitials), with an intimate mixture of ceramic
precipitates (transition metal carbides, borides, silicides, etc.). The nanocrystalline scale
metal matrix composite grain structure can enable a combination of mechanical properties
which are improved compared to the properties which would exist with larger grain sizes or
with the metallic glass. Such improved mechanical properties can include, for example, high
strength, and high hardness coupled with significant ductility.
The particular temperature employed for devitrifying the metal glass can be varied
depending on the particular alloy utilized in the glass, and a particular time of application.
Post treatment of the devitrified metallic material from step (C) can include a surface
treatment utilized to transform only the surface of the material to a metallic glass. Exemplary
surface treatment techniques are high and low pressure plasma spraying, high velocity
oxyfuel spraying, and spray forming. The plasma spraying can be accomplished with a
plasma spray system. The post treatment can offer improvements in, for example, corrosion
resistance and lowering the coefficient of friction of a steel material. Accordingly, it can be
advantageous to treat at least the surface of a crystalline steel material to convert such surface
to a metallic glass. It is noted that a metallic glass coating can also offer advantages over
existing coatings such as, for example, chrome, nickel and tin plating in that the metallic
glass coating can be cheaper and can give a better metallurgical bond between the surface and
the base metal.
Referring to Fig. 2, a specific embodiment application of the present invention is
illustrated. Specifically, Fig. 2 illustrates a metallic barrel 50 being sprayed with a molten
metal material 52. Molten metal material 52 is sprayed from a spraying device 54, and can
comprise, for example, one or more of the above-described exemplary alloys of the present
invention. The molten metal can be formed by melting an alloy composition under an argon
atmosphere and subsequently centrifugally atomizing the alloy composition. As the melt
stream leaves a centrifugal cup, it can be hit by a high pressure helium gas to form a fine
powder of solidified metallic alloy material with such fine powder having about a 25
micrometer mean size. The fine powder can be fed into a plasma (high or low pressure)
system wherein it is converted to a liquid spray which is sprayed on the inside and outside of
metallic drum 50. In particular applications, drum 50 comprises a steel drum, such as, for
example, a 55 gallon steel drum. It is noted that the powder may or may not be fully melted
upon exposure to the plasma, and will be deposited into and onto the surface of barrel 50 as a
continuous coating. In either event, the metallic material 52 sprayed onto and within drum 50
cools rapidly to form a metallic glass. Drum 50 can be subsequently heat-treated at a
temperature of equal to or greater than 600°C to devitrify the metallic glass.
The metallic structure formed over and within barrel 50 from material 52 can have
greater corrosion resistance than stainless steel. Drum 50 be utilized, for example, for storing
corrosive and otherwise dangerous materials, such as, for example, spent nuclear fuel. If a
surface of material 52 is coated with a metallic glass, the anti-corrosive properties and low
coefficient of friction properties associated with metallic glass can be obtained.
Figs. 3-6 illustrate another embodiment application of the present invention.
Referring to Fig. 3, a metallic substrate 100 is provided. Such substrate can comprise, for
example, one or more of the above-described exemplary alloys of the present invention.
Referring to Fig. 4, a metallic melt 102 is sprayed onto substrate 100 utilizing a
sprayer 104. Melt 102 can comprise, for example, a molten alloy comprising one or more of

powder material heated to a sufficient temperature to bond with the metal of layer 100.
Material 102 deposits on substrate 100 to form a layer 106. Material 102 also heats an
exposed surface of material 100 to form a heat-treated portion 108 of material 100. If
material 100 comprises a metallic glass, heat-treated portion 108 can comprise a devitrified
material. Specifically, if layer 106 is formed at a temperature which heats a surface of layer
100 to greater than 600°C, such heating can devitrify a portion of material 100 exposed to
such temperatures. In particular applications, temperatures greater than 600oC can permeate
entirely through substrate 100 to heat-treat an entire thickness of material 100. Spray nozzle
104 is preferably resistant to the temperature and composition of material 102.
Referring to Fig. 5, substrate 100 is illustrated after layer 106 has been formed across
an entire surface of substrate 100. Heat-treated portion 108 also extends across an entire
surface of substrate 100. In particular embodiments, layer 106 can be formed as a metallic
Referring to Fig. 6, subsequent treatments of the type illustrated in Fig. 4 can be
utilized to form multiple heat-treated layers 120 and an exposed outer surface layer 124. Note
that one of the lower heat-treated layers 120 is previous layer 106. The subsequent formation
of another metallic glass layer over layer 106 has heat-treated the entire layer 106. In
particular embodiments wherein layer 106 comprises a metallic glass, such heat treatment can
devitrify layer 106. Accordingly, heat treated layers 120 can comprise devitrified metal
layers. In alternative methods of the present invention, each of the layers 106 and 120 can be
deposited as metallic glass and can remain in the metallic glass form during deposition of
remaining layers 120. Then, if desired, some or all of the deposited layers can be heat-treated
to at least partially devitrify the coating defined by layers 106 and 120.
Outermost layer 124 may or may not be heat-treated, and can comprise a metallic
glass. Accordingly, the method of the present invention has enabled an exterior coating to be
formed over layer 100, with said exterior coating comprising devitrified metal layers 120 and
an outermost surface of metallic glass 124.
The methodology described with reference to Figs. 3-6 can have application for a
number of uses, including military uses. Specifically, armor can be formed out of a material
100. If the armor becomes punctured or cracked, the methodology of Figs. 3-6 can be utilized
to repair the armor and effectively build a metallic shell over the weakened areas of the
armor. Spraying device 104 can be adapted to be utilizable in battlefield situations.
In addition to the utilizations described above for materials of the present invention,
the materials can also be utilized as powders for surface finishing (i.e., mechanical blasting)
and surface treatments such as, for example, shot peening.
The invention can be considered a method for forming a new class of steel called
devitrified nanocomposite (DNC) steel, with DNC steel being defined as having a primarily
nanoscale (less than 100 nanometer) microstructure grain size developed by processing the
steel through a solid-solid transformation (specifically, glass devitrification). Alloys are
developed having low cooling rates (less than 106 K/s) for metallic glass formation, and
accordingly the alloy compositions form metallic glasses when rapidly solidified by a chill
surface (such as, for example, melt-spinning, splat quenching, etc.) or atomization (gas,
water, centrifugal, etc.) methods. The glass is utilized as a precursor stage, and the alloy
subsequently processed through a glass devitrification transformation upon heating above a
crystallization temperature of the alloy. Due to uniform nucleation in the glass coupled with
a high nucleation frequency, there is little time for grain growth processes, and nanoscale
nanocomposite microstructures (i.e., grains) result. The nanocomposite microstructures can
lead to materials having significant increases in hardness and strength over conventional steel
Initial studies described herein show that DNC steel formed in accordance with
methodology of the present invention has exceptional hardness and wear resistance, and can
be used potentially for any application which involves sliding, rolling, or rotation.
Additionally, initial studies have shown that the unlubricated DNC steel surface has
exceptionally low coefficients of friction (in the range of lubricated steels) which can be a
beneficial property in reducing wear resistance, frictional energy losses, and heating between
moving surfaces. This can allow the use of DNC steel in unlubricated applications, and can
also be useful as a fail-safe mechanism allowing additional time before failure in some
applications, such as gasoline or diesel engines, where lubrication is unexpectedly lost. The
high wear resistance of DNC steel, coupled with low friction, can allow extension of the
lifetime of parts formed from DNC steel relative to parts formed from conventional steel
alloys. Such can enable large savings in both operating energy and cost associated with part
replacement, repair, maintenance and down-time. Exemplary applications for utilization of
DNC steels of the present invention include bearings, gun barrel surfaces, bearing journals,
hydraulic cylinder connecting rods, crankshafts, pistons, cylinder liners, gears, camshafts,
universal joints, valves, gun breach boxes, missile launcher tubes, and tank gear boxes.
Unlike conventional steel alloys which rely on manipulation of solid state eutectoid
transformation (Yso1=asol+Fe3C), DNC steel utilizes a different approach, and specifically
utilizes processing through a solid/solid state glass devitrification transformation. DNC steel
alloys have been developed which have exceptionally low cooling rates (103 K/s to 105 K/s)
for metallic glass formation. This can allow the production of metallic glass structures during
rapid solidification via chill surface or atomization methods.
Examples of DNC steel melt-spun ribbon and gas atomized powder are shown in Figs.
7 and 8, respectively. Metallic glass structures are produced by both of these rapid
solidification processing methods. The glass precursor can be devitrified into a nanoscale
composite microstructure by heating above the crystallization temperature.
A differential thermal analysis scan for as-spun DNC steel is shown in Fig. 9. The
glass crystallization temperature typically varies from 750K to 900K with enthalpies of
transformation from -75 Jig to -200 J/g, and melting temperatures from 1.375K to 1.500K for
alloys encompassed by the present invention (as described in the charts of Figs. 20-23).
Because there is uniform nucleation and extremely high nucleation frequency during
crystallization of alloys of the present invention, there can be little time for grain growth
before impingement between neighboring grains and accordingly nanoscale nanocomposite
microstrucrures are formed. The individual phase sizes can vary from 1 to 75 nanometers,
which is finer than conventional steels produced by conventional casting or even when
rapidly solidified. When the microstructure is. reduced to the nanoscale level, a high
percentage of the atoms of the material (about 30%) can be associated with grain boundaries,
and an extremely high density of two-dimensional defect interfaces (such as phase in grain
boundaries) reside in the microstructure. The microstructure of a devitrified ribbon showing
the nanoscale nanocomposite microstructure is shown in Fig. 10. The nanostructure results in
the development of extreme strength and hardness, which are significantly higher than found
in conventional steel or other metallic based alloys.
The hardness of glass and devitrified DNC steel has been measured using both
nanoindentor and Vickers microhardness testing, and excellent agreement is found between
the two methods. Specialized nanoindentor testing using a Berkovich indentor was
performed on the as-atomized and heat-treated sieved (10-20 micrometer and 75-100
micrometer) gas atomized particles from a Fe63Cr8Mo2B17C5Si1Al4 alloy as a function of depth
into the particle. The elastic modulus was found to be as high as 300 GPa, which is
approximately 50% higher than a conventional steel (which commonly exhibits elastic
moduli from 200 GPa to 220 GPa). This means that bonding strength is increased, which can
be of beneficial result since it allows close tolerances to be maintained during application of
high elastic loads, and can have additional benefits concerning wear resistance. The hardness
was also found to be extremely high at greater than 15 GPa, which is harder than
conventional metallic materials. Examples of various compositions which can be utilized in
methodology of the present invention for forming hard materials are shown in Table 1. In
referring to Table, the various compositions are given reference names (specifically, they are
referred to as alloys DARX) to simplify reference to the compositions herein. Table 2
contrasts hardness of various materials with the alloy DAR1.
From the hardness determined for DAR1, the yield strengths for the DNC steel can be
estimated to be 725 ksi, which is significantly higher than conventional (150 ksi) or ultra high
strength (220 ksi) steels. If the plasticity is fully developed, the yield strength can be
estimated to be 1/3 of the hardness. This gives the DNC steel a specific strength of 0.65 x
106M which makes this material an alternate for Al in lightweight applications. Little
hardness difference was found between the large and small heated powders indicating that
similar microstructures were obtained independent of powder size. It is noted that the
hardness tests described herein were relative to a material DAR1 (Fe63Cr8Mo2B17C5Si1Al4)
which is not a preferred material of the present invention. Rather, preferred materials of the
present invention would have fewer elements, and are listed as DAR2 through DAR 19 in
Table 1.
A preferred material of the present invention (specifically DAR20) is compared with
DAR1 in Fig. 11, Specifically, Vickers microhardness measurements with a 100 gram load
were performed on 75 micrometer to 100 micrometer powder size fractions for as-atomized
alloys, and also as a function of heat treatment temperature. The tested alloys exhibited
extreme hardness from 10.1 GPa to 16.0 GPa Vickers hardness. Examples of diamond
pyramid indentations on a melt-spun ribbon and gas-atomized powder particle are shown in
Fig. 12. While the Rockwell C is the most common hardness measurement for steels, it
cannot be used in the present case due to the extreme hardness of the alloys of the present
invention (which are off of the Rockwell C scale). Note that a Vickers Hardness number of
9.2 GPa corresponds to a Rockwell C of 68. Referring again to Fig. 11, it is noted that little
hardness change occurs in the as-atomized state of alloys of the present invention after
subsequent heat treating. This can be significant, as it means that optimum microstructures
are obtained directly during solidification and the optimum structures are stable to high
temperatures (at least to 850°C, as shown in Fig. 11).
DNC steels contain multiple combinations of elements which result in relatively low
melting points (typically around 1,150°C) and low melt viscosities, This can make the DNC
steels easy to process from the liquid state, and ideal feedstock materials for forming coatings
by thermal deposition methods. Initial low plasma spraying tests have been performed
utilizing the atomized 20 to 50 micrometer Fe63Cr8MO2B17C5Si1Al4 steel powder as feed stock.
Several uniform DNC steel coatings of 0.1 inch in thickness were deposited onto 4"x4" 301
stainless steel plates (shown in Fig. 13). While typical thermally deposited coatings are only
25 micrometers to 100 micrometers thick, much thicker coatings (up to 2,500 micrometers)
were sprayed to illustrate an extreme case (in other words, thinner coatings are easier to spray,
but thicker coatings were sprayed to illustrate operability of a method of the present
Metallographic examinations of the coatings indicate that the percent porosity of the
initial coatings was at least 3%. X-ray diffraction scans were performed both on the substrate
side and free surface side of the coatings, and show that an amorphous structure was obtained
through the cross-sectioning of the coatings (specifically, Fig. 14 shows an x-ray structure of
a free surface side of the coating, and Fig. 15 shows an x-ray structure of the substrate side of
the coating). Differential scanning calorimetry methods verified the formation of the glass
structure in the coating which exhibited a high crystallization enthalpy (-110 J/g). This result
is surprising due to the supreme thickness of the coating which resulted from successive
build-up of continuous layers of deposited powder, and the fact that the substrate was not
cooled. Thus, DNC steel coatings represent a class of materials called bulk glasses. Bulk
glasses are normally very difficult to produce, but readily form in the DNC alloys by thermal
processing methods.
The as-sprayed DNC metallic glass coatings can be devitrified into a nanoscale
structure by heating above the crystallization temperature. However, due to the unique
properties of the metallic glasses, the glass state itself may be useful as a coating. Metallic
glasses are essentially super-cooled liquids, and have structures which are very homogeneous.
Typically there are few defects, and there can be a complete absence of grains and phase
boundaries. Hardness testing was performed on both the as-sprayed (amorphous) and heat-
treated (800°C for one hour) nanocrystalline coatings. The Vickers hardness of these coatings
was found to be 10.9 GPa and 13.8 GPa for the as-sprayed and heat-treated coatings,
respectively. It is noted that while the amorphous sample is not as hard as the crystalline
sample, it is still harder than the hardest tool steel (about 9.3 GPa), or tungsten carbon (WC)
cemented carbide cutting tool (about 10.0 GPa).
Tribology testing experiments were done on the as-sprayed and heat-treated (100°C
for one hour) plasma sprayed coatings using ASTM G99 Pin-on-Disk tests. The "pin" was a
one-half inch diameter Si3N4 ball which was rotated at a test speed of 97 RPM, with a test
radius of 10.4 mm and with no lubrication. During the test, the coefficients of friction were
measured (shown in Fig. 16). The coefficient of static friction for the steel substrate in both"
the as-sprayed and heat-treated condition was 0.22, which represents a low value. For
example, the following coefficients of sliding friction were obtained for specimens sliding
over a normalized steel (0.13% C, 3.42% Ni): aluminum (0.6), cartridge brass (0.5), copper
(0.8), cast iron (0.4), and normalized steel (on itself 0.8). For conventional steels, the
coefficients of static friction for unlubricated surfaces generally vary from 0.8 to 1.0, while
lubricated steels have much lower values (typically from 0.1 to 0.25). Thus, the unlubricated
DNC steels have coefficients of static friction in the range of lubricated steel surfaces.
Accordingly, utilization of DNC steel coatings in place of conventional steel may allow the
elimination of lubrication in some applications. Note that the coefficient of sliding friction of
the steel substrate could not be measured due to Si3N4 deposition from the pin.
The profile of the wear surface of the steel showed that the steel experienced no wear
during the test (Fig. 17). Instead of the expected wear groove, a raised hill of deposited Si3N4
was found on the steel surface. Examination of the silicon nitride ball showed that it
experienced a large ball scar as a result of wear. This was surprising due to the hardness of
the ball material (15.4 GPa), which is used specifically for these type of tests due to its
excessive hardness and wear resistance. Note that Si3N4 is currently the hardest pin material
available to perform this ASTM test.
The Fe63Cr8Mo2B17C5Si1Al4 steel utilized in generating the data described above is an
exemplary DNC steel. However, it suffers from a disadvantage of having numerous elements
included therein, which can make it difficult to produce uniform batches of the material.
Accordingly, improved DNC alloys have been developed. Such improved alloys are listed in
Table 1 as DAR2 through DAR19. The alloys have been designed to form metallic glasses at
low cooling rates, and are further designed to reduce the number of elements utilized in the
Ingots of the 19 alloys listed in Table 1 were melt-spun at 15 m/s with the following
melt-spinning parameters: chamber 1/3 atmosphere helium, ejection pressure 150 Torr,
ejection temperature 1,400oC, crucible up to wheel distance 6 mm, and crucible orifice
diameter 0.81 mm to 0.84 mm.
All of the tested alloys were melt-spun with few problems. Interestingly, many of the
preferred alloys (i.e., DAR2 through DAR19) formed uniform continuous ribbons up to 10
meters in length. This may be due to increased glass forming ability and increased ductility
of the glass that is produced relative to the less preferred alloy DAR1. Qualitative inspections
of the ribbons by bending the ribbons back and forth until fracture indicated that all of the
alloys DAR2 through DAR19 have higher ductility than the DAR1 alloy. In fact, some of the
alloys DAR2 through DAR 19 in ribbon form cannot be broken by bending, and had to be
cut. An example of a melt-spun ribbon which exhibits high ductility is shown in Fig. 18, and
was formed from the material DAR18 (Fe0.8Cr0.2)81B17W2.
Differential thermal analysis (DTA) and differential thermal calorimetry (DSC)
studies were done on each melt-spun ribbon sample in ultra-high purity argon from 30°C to
1,375°C at a heating rate of 10°C/min. A typical DTA scan showing DAR14
((Fe0 8Cr02)75BnSi4Al4) compared with DAR1 (Fe63Cr8Mo2BnC5Si1Al4) is illustrated in Fig.
19. From the DTA/DSC studies, the glass to crystalline transformation temperatures,
enthalpy of transformation, transformation rate, and melting temperatures could be
determined. The results of these studies are shown in Figs. 20-23. As shown, all of the alloys
but one (specifically, DAR5 ((Fe0.8Mo0.2)83B17), formed a metallic glass structure when melt-
spun at reduced cooling rate. Thus, the alloys are expected to form metallic glass powders
when atomized.
Vickers hardness testing using a 100 gram load was done on the cross-sections of the
melt-spun ribbons of each alloy in the as-spun and heat-treated (700°C for one hour and
800°C for one hour) conditions. For each sample (60 samples total), 10 Vickers hardness
tests on five ribbons were done in order to get a reportable average value. In general, only
small variations were found to occur in hardness when the same sample was tested.
Summaries of the completed Vickers hardness measurements are shown in Table 4.
As indicated by the tables and Figures provided herein, materials of the present
invention having less than 11 elements, and more preferably less than seven elements, can
form glass compositions. It is not a trivial task to form materials having such limited number
of elements, which are also capable of forming metallic glasses. However, such has been
accomplished in the present invention. The present invention also has developed improved
ductility and toughness of DNC steel alloys, while maintaining or possibly even improving
hardness. The DNC alloys are believed to be useful for numerous services, including military
applications, due to their strength and wear resistance. The alloys can also be resistant to
electrochemical attack (i.e., corrosion). In general, as the scale of a microstructure decreases,
the electrochemical resistance of a particular material is expected to increase. Thus,
nanocrystalline scale DNC microstructures are expected to have good corrosion resistance.
Further, metallic glass DNC structures can have improved corrosion resistance due to high
homogeneity (short range order on a 2 nanometer length scale) and the absence of two-
dimensional defects (such as grain or phase boundaries). Specifically, a uniform single-phase
structure can make it difficult for sites to initiate for anodic attack and electron transfer since
there will not be distinct anodic and cathodic sites. While the metallic glass or nanostructure
of a certain composition can have a higher relative resistance to electrochemical attack than
the same material in bulk form, the material's nobility will be dependent on both the structure
and the composition. For instance, a high level of chromium can improve resistance to
electrochemical attack.
Among the advantages of the alloys described herein is that such alloys can have a
relatively simple composition (i.e., from four to six elements in the composition). Also, the
alloys can contain a relatively high percentage of transition metals (from 90% to 97%) which
can lead to improved industrial properties of the materials.
A distinction of the materials of the, present invention relative to conventional hard
materials is that the materials of the present invention can comprise no carbon. In
conventional steels, hardness is typically tied directly to carbon content in a martensite, In
contrast, the extreme hardness of DNC steels arises from development of nanoscale
nanocomposite microstructures, rather than from martensitic transformations. An advantage
of carbon-free compositions is that the extremely hard alloys can be developed to still be
reasonably ductile, which is typically not possible in conventional steel alloys (i.e.,
untempered martensite and transition metal carbides are typically hard, and also brittle).
Group VI transition metals (Cr, Mo, and W) can be particularly potent additions to
DNC steels. Chromium, consistent with data on conventional steel alloys, is expected to also
provide excellent corrosion resistance. Molybdenum and tungsten can be exceptionally
potent additions to promote hardness in DNC steels. Tungsten can also be potent at
increasing hardness while retaining or increasing ductility.
Because of its hardness and high strength (greater than 725 ksi), DNC steel can be
difficult to process into bulk parts starting from powder and using conventional powder
metallurgical consolidation processes. However, DNC steel can be easy to process from the •
liquid state. Alternatively, powder of DNC steel can be fed through a conventional plasma
gun and sprayed as a coating onto metal substrates with good adhesion and with absence of
cracking. Other methods for forming a coating of DNC steel include axial feed plasma
spray, conventional plasma spray, high velocity oxy-fuel spray, and a detonation gun.
When DNC steel is sprayed onto metallic substrates it can readily form a metallic
glass structure. If consecutive layers are continuously sprayed onto a bulk substrate
(thickness greater than 0.1 inches) metallic glasses can be formed. This may be the most
inexpensive and easiest way to form bulk metallic glass coatings or even bulk glass
monolithic parts.
DNC steels can be rapidly solidified into an amorphous glass precursor and then the
rapidly solidified powders can be consolidated into a useful form. Accordingly, the cost of
technology of the present invention can involve three items: the alloy cost, the powder
production cost, and the consolidation cost. All three items can be estimated. To produce
rapidly solidified powder, centrifugal atomization may be the best method, and even at
relatively low production rates. If it is feasible to produce DNC steel powder by water
atomization, processing cost to produce the powder could drop to a few pennies per pound.
The powder consolidation costs will vary depending on the specific application and the
thickness of the coating. Coatings from 5 micrometers to 2,500 micrometers in thickness can
be readily deposited using conventional commercially available thermal deposition methods,
such as plasma spraying or high velocity oxy-fuel spraying. The DNC steel's cost can
compare favorably to other hard materials such as, for example, diamond and cubic BN.
DNC steel coating may also be a direct competing technology to replace tungsten carbide
cemented carbide coatings, since the DNC steel exhibits higher hardness and greater tensile
Although the invention is described herein for coating steel alloy compositions of the
present invention on metallic substrates, it is to be understood that the alloys of the present
invention can also be coated on non-metallic substrates, such as, for example, ceramics, to
provide a hard and/or lubricating surface over the non-metallic substrates.
We Claim
1. A method of forming a hardened surface on a substrate, comprising:
providing a substrate;
and forming a molten alloy and cooling the alloy to form a metallic glass coating on the
substrate, the forming comprising forming a successive buildup of metallic glass layers, the
metallic glass coating having a first hardness of 9.2 GPa or more, and comprising one or
more materials selected from the group consisting of

2. The method as claimed in claim 1, wherein at least a portion of the metallic glass
coating is converted to a crystalline material having a nanocrystalline grain size and a second
hardness of 9.2 GPa or more.
3. The method as claimed in claim 1 wherein the substrate is a metallic material.
4. The method as claimed in claim 1 wherein the substrate is a ceramic material.
5. The method as claimed in claim 2 wherein the first hardness is 10.0 GPa or more.
6. The method as claimed in claim 1 wherein the metallic glass coating is applied to the
substrate as a plasma spray.
7. The method as claimed in claim 1 wherein the forming of the metallic glass coating
comprises an application of an atomized powder of a metallic glass material over the
8. The method as claimed in claim 2 wherein the forming of a metallic glass coating
comprises forming a successive buildup of continuous layers.
9. The method as claimed in claim 2 wherein the converting comprises heating the
metallic glass to above a crystallization temperature of the metallic glass.
10. The method as claimed in claim 9 wherein the heating comprises heating to a
temperature of 600°C or more and below a melting temperature of the metallic glass.
11. The method as claimed in claim 2 wherein the second hardness is 10.0 GPa or more.

There is disclosed a method of forming a hardened surface on a substrate, comprising
providing a substrate; and forming a molten alloy and cooling the alloy to form a metallic
glass coating on the substrate, the forming comprising forming a successive buildup of metallic
glass layers, the metallic glass coating having a hardness of 9.2 GPa or more, and comprising one
or more materials selected from the group consisting of




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Patent Number 250238
Indian Patent Application Number 3184/KOLNP/2006
PG Journal Number 51/2011
Publication Date 23-Dec-2011
Grant Date 19-Dec-2011
Date of Filing 01-Nov-2006
Applicant Address P.O. BOX 1625, IDAHO FALLS, ID 83415-3899
# Inventor's Name Inventor's Address
PCT International Classification Number C22C45/10
PCT International Application Number PCT/US2005/015365
PCT International Filing date 2005-05-02
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/841,873 2004-05-06 U.S.A.