U.S. patent application number 13/118035 was filed with the patent office on 2011-12-01 for alloys exhibiting spinodal glass matrix microconstituents structure and deformation mechanisms.
Invention is credited to Daniel James BRANAGAN, Brian E. MEACHAM, Alla V. SERGUEEVA, Jason K. WALLESER, Jikou ZHOU.
Application Number | 20110293463 13/118035 |
Document ID | / |
Family ID | 45004881 |
Filed Date | 2011-12-01 |
United States Patent
Application |
20110293463 |
Kind Code |
A1 |
BRANAGAN; Daniel James ; et
al. |
December 1, 2011 |
ALLOYS EXHIBITING SPINODAL GLASS MATRIX MICROCONSTITUENTS STRUCTURE
AND DEFORMATION MECHANISMS
Abstract
An alloy composition comprising iron present in the range of 49
atomic percent (at %) to 65 at %, nickel present in the range of
10.0 at % to 16.5 at %, cobalt optionally present in the range of
0.1 at % to 12 at %, boron present in the range of 12.5 at % to
16.5 at %, silicon optionally present in the range of 0.1 at % to
8.0 at %, carbon optionally present in the range of 2 at % to 5 at
%, chromium optionally present in the range of 2.5 at % to 13.35 at
%, and niobium optionally present in the range of 1.5 at % to 2.5
at %, wherein the alloy composition exhibits spinodal glass matrix
microconstituents when cooled at a rate in the range of 10.sup.3K/s
to 10.sup.4K/s and develops a number of shear bands per linear
meter in the range of greater than 1.1.times.10.sup.2 m.sup.-1 to
10.sup.7 m.sup.-1 upon application of a tensile force applied at a
rate of 0.001 s.sup.-1.
Inventors: |
BRANAGAN; Daniel James;
(Idaho Falls, ID) ; MEACHAM; Brian E.; (Idaho
Falls, ID) ; WALLESER; Jason K.; (Idaho Falls,
ID) ; ZHOU; Jikou; (Pleasanton, CA) ;
SERGUEEVA; Alla V.; (Idaho Falls, ID) |
Family ID: |
45004881 |
Appl. No.: |
13/118035 |
Filed: |
May 27, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61348823 |
May 27, 2010 |
|
|
|
Current U.S.
Class: |
420/14 ; 420/43;
420/581; 420/585; 420/9; 420/95; 420/97 |
Current CPC
Class: |
C22C 38/02 20130101;
C22C 38/54 20130101; C22C 38/56 20130101; C22C 38/34 20130101; C22C
38/48 20130101; C22C 38/08 20130101; C22C 38/002 20130101; C22C
45/02 20130101; C22C 38/52 20130101; C21D 9/525 20130101; C22C
37/10 20130101; C22C 38/105 20130101 |
Class at
Publication: |
420/14 ; 420/95;
420/9; 420/97; 420/43; 420/585; 420/581 |
International
Class: |
C22C 37/10 20060101
C22C037/10; C22C 30/00 20060101 C22C030/00; C22C 38/00 20060101
C22C038/00; C22C 38/54 20060101 C22C038/54; C22C 38/10 20060101
C22C038/10; C22C 38/08 20060101 C22C038/08 |
Claims
1. An alloy composition comprising: iron present in the range of 49
atomic percent (at %) to 65 at %, nickel present in the range of 10
at % to 16.5 at %, cobalt optionally present in the range of 0.1 at
% to 12 at %, boron present in the range of 12.5 at % to 16.5 at %,
silicon optionally present in the range of 0.1 at % to 8.0 at %,
carbon optionally present in the range of 2 at % to 5 at %,
chromium optionally present in the range of 2.5 at % to 13.35 at %,
and niobium optionally present in the range of 1.5 at % to 2.5 at
%, wherein said alloy composition exhibits spinodal glass matrix
microconstituents when cooled at a rate in the range of 10.sup.3K/s
to 10.sup.4K/s and develops a number of shear bands per linear
meter in the range of greater than 1.1.times.10.sup.2 m.sup.-1 to
10.sup.7 m.sup.-1 upon application of a tensile force applied at a
rate of 0.001 s.sup.-1.
2. The alloy composition of claim 1, wherein said composition
consists essentially of iron, nickel, boron, silicon and one or
more of the following cobalt, chromium, carbon and niobium.
3. The alloy composition of claim 1, wherein said composition
consists essentially of iron, nickel, boron, silicon and
chromium.
4. The alloy composition of claim 1, further comprising: iron
present in the range of 49 at % to 65 at %, nickel present in the
range of 14.5 at % to 16.5 at %, cobalt present in the range of 2.5
at % to 12 at %, boron present in the range of 12.5 at % to 16.5 at
%, silicon present in the range of 0.5 at % to 8.0 at %, carbon
optionally present in the range of 2 at % to 5 at %, chromium
optionally present in the range of 2.5 at % to 13.35 at %, and
niobium optionally present in the range of 1.5 at % to 2.5 at
%.
5. The alloy composition of claim 1, further comprising: iron
present in the range of 53 at % to 62 at %, nickel present in the
range of 15.5 at % to 16.5 at %, cobalt present in the range of 4.0
at % to 10 at %, boron present in the range of 12 at % to 16 at %,
carbon present in the range of 4.5 at % to 4.6 at %, and silicon
present in the range of 0.4 at % to 0.5 at %.
6. The alloy composition of claim 1, further comprising: iron
present in the range of 51 at % to 65 at %, nickel present in the
range of 16.5 at %, cobalt present in the range of 3 at % to 12 at
%, boron present in the range of 15 at % to 16.5 at %, and silicon
present in the range of 0.4 at % to 4 at %.
7. The alloy composition of claim 1, further comprising: iron
present in the range of 49 at % to 61 at %, nickel present in the
range of 14.5 at % to 16 at %, cobalt present in the range of 2.5
at % to 12 at %, boron present in the range of 13 at % to 16 at %,
silicon present in the range of 3 at % to 8 at %, and chromium
present in the range of 2.5 at % to 3 at %.
8. The alloy composition of claim 1, further comprising: iron
present in the range of 57 at % to 60 at %, nickel present in the
range of 14.5 at % to 15.5 at %, cobalt present in the range of 2.5
at % to 3 at %, boron present in the range of 13 at % to 14 at %,
silicon present in the range of 3.5 at % to 8 at %, chromium
present in the range of 2.5 at % to 3 at %, and niobium optionally
present at 2 at %.
9. The alloy composition of claim 1, further comprising: iron
present in the range of 52 at % to 65 at %, nickel present in the
range of 10 at % to 16.5 at %, boron present in the range of 13 at
% to 15 at %, silicon present in the range of 0.4 at % to 0.5 at %,
and chromium present in the range of 3 at % to 13.35 at %.
10. The alloy composition of claim 1, wherein said spinodal glass
matrix microconstituents include crystalline or semi-crystalline
clusters having a size in the range of 1 nm to 15 nm in thickness
and 2 nm to 60 nm in length.
11. The alloy composition of claim 1, wherein said alloy
composition exhibits a glass to crystalline onset to peak in the
range of 395.degree. C. to 576.degree. C., when measured at a rate
of 10.degree. C./min.
12. The alloy composition of claim 1, wherein said alloy
composition exhibits a primary onset glass transition temperature
in the range of 395.degree. C. to 505.degree. C. and a primary peak
glass transition temperature in the range of 419.degree. C. to
521.degree. C., when measured at a rate of 10.degree. C./min.
13. The alloy composition of claim 1, wherein said alloy
composition exhibits an ultimate tensile strength in the range of
0.62 GPa to 5.8 GPa, when measured at a strain rate of 0.001
s.sup.-1.
14. The alloy composition of claim 1, wherein said alloy
composition exhibits a total elongation in the range of 0.67% to
12.8%, when measured at a strain rate of 0.001 s.sup.-1.
15. The alloy composition of claim 1, wherein said alloy
composition is in the form of one or more of the following: ribbon,
fiber, foil, sheet and microwire.
16. The alloy composition of claim 15, wherein said alloy
composition has a thickness in the range of 0.001 mm to 3 mm.
17. The alloy composition of claim 1, wherein said alloy
composition exhibits an average microhardness in the range of 9.10
GPa to 9.21 GPa when tested under a 50 gram load.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit of the filing
date of U.S. Provisional Application Ser. No. 61/348,823, filed on
May 27, 2010, the teachings of which are incorporated herein by
reference.
FIELD OF INVENTION
[0002] The present application relates to metallic compositions
that are capable of developing plasticity at room temperature by
triggering the formation of spinodal glass matrix microconstituent
structures and an associated number of shear bands per linear
unit.
BACKGROUND
[0003] Despite promising property combinations such as high
hardness, tensile stress and fracture strength, practical
applications of metallic glasses and nanomaterials have been
relatively limited. One issue that has arisen in both material
classes is that the materials may exhibit relatively brittle
response. Commercial exploitation of these material classes has
been facilitated by utilizing their soft and hard magnetic
properties for applications including transformers and high energy
density permanent magnets and, more recently, for surface
technology applications whereby coatings including these materials
may be applied to a surface to solve corrosion, erosion, and/or
wear issues.
[0004] Although both metallic glasses and nanomaterials can show
ductility when tested in compression, the same materials when
tested in tension, may generally exhibit a tensile ductility which
may be close to zero and fracture in a brittle manner. Due to the
extremely fine length scale of the structural order (i.e. molecular
associations) and near defect free nature of these materials (i.e.
no 1-d dislocation or 2-d grain/phase boundary defects), relatively
high strength may be obtained. However, due to the lack of
crystallinity, dislocations may not be found and so far there does
not appear to be a mechanism for significant (i.e. >2%) tensile
elongation. Metallic glasses may exhibit relatively limited
fracture toughness associated with the rapid propagation of shear
bands and/or cracks which may be a concern for the technological
utilization of these materials.
[0005] In metallic glasses deformed at room temperature, plastic
deformation may be inhomogeneous with cooperative atomic
reorganization in shear transformation zones, which may take place
in thin bands of shear bands. In unconstrained loading such as
under tension, shear bands may propagate in a runaway fashion
followed by the commensurate nucleation of cracks, which may result
in catastrophic failure. For nanocrystalline materials, as the
grain size is progressively decreased, the formation of dislocation
pile-ups may become more difficult and their movement may be
limited by the large amount of 2-d defect phases and grain
boundaries. Reductions in grain/phase size may render otherwise
mobile dislocations immobile due to the effective disruption of
slip systems in the grain/phase boundary area. As a result, the
ability of nanoscale materials to exhibit significant levels of
plastic deformation may be suppressed even in very ductile
nanoscale FCC metals such as copper and nickel. Thus, the
achievement of adequate ductility (>1%) in nanocrystalline
materials has been a challenge. The inherent inability of these
classes of material to be able to deform in tension at room
temperature may be a relatively limiting factor for potential
structural applications where intrinsic ductility may be needed to
avoid catastrophic failure.
SUMMARY
[0006] An aspect of the present disclosure relates to an alloy
composition. The alloy composition may include iron present in the
range of 49 atomic percent (at %) to 65 at %, nickel present in the
range of 10.0 at % to 16.5 at %, cobalt optionally present in the
range of 0.1 at % to 12 at %, boron present in the range of 12.5 at
% to 16.5 at %, silicon optionally present in the range of 0.1 at %
to 8.0 at %, carbon optionally present in the range of 2 at % to 5
at %, chromium optionally present in the range of 2.5 at % to 13.35
at %, and niobium optionally present in the range of 1.5 at % to
2.5 at %, wherein the alloy composition exhibits spinodal glass
matrix microconstituents when cooled at a rate in the range of
10.sup.3K/s to 10.sup.4K/s and develops a number of shear bands per
linear meter in the range of greater than 1.1.times.10.sup.2
m.sup.-1 to 10.sup.7 m.sup.-1 upon application of a tensile force
applied at a rate of 0.001 s.sup.-1.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The above-mentioned and other features of this disclosure,
and the manner of attaining them, will become more apparent and
better understood by reference to the following description of
embodiments described herein taken in conjunction with the
accompanying drawings, wherein:
[0008] FIG. 1 illustrates an example of foil produced from Alloy 1
by the Planar Flow Casting process.
[0009] FIGS. 2a and 2b illustrate an example of microwire produced
from Alloy 2 by the Taylor-Ulitovsky process.
[0010] FIG. 3 illustrates microwire produced from Alloy 3 by the
Taylor-Ulitovsky process.
[0011] FIG. 4 illustrates foils produced from Alloy 4 by the Planar
Flow Casting process.
[0012] FIG. 5 illustrates microwires produced from Alloy 4 by the
Taylor-Ulitovsky process.
[0013] FIG. 6 illustrates microwire produced from Alloy 5 by the
Taylor-Ulitovsky process.
[0014] FIG. 7 illustrates foils produced from Alloy 6 by the Planar
Flow Casting process.
[0015] FIGS. 8a and 8b illustrate microwire produced from Alloy 7
by the Taylor-Ulitovsky process.
[0016] FIG. 9 illustrates foils produced from Alloy 8 produced by
the Planar Flow Casting process.
[0017] FIG. 10 illustrates microwire produced from Alloy 8 by the
Taylor-Ulitovsky process.
[0018] FIG. 11 illustrates fibers produced from Alloy 8 by the
Hyperquenching process.
[0019] FIG. 12 illustrates a foil produced from Alloy 9 by the
Planar Flow Casting process.
[0020] FIG. 13 illustrates an image of a corrugated foil from Alloy
6.
[0021] FIG. 14 illustrates bendability of fibers produced from
Alloy 8 by the hyperquenching process as a function of wheel speed
optimization.
[0022] FIGS. 15a and 15b illustrates macrodefects in fibers
produced from Alloy 8 by the hyperquenching process; wherein FIG.
15a illustrates the left side external surface and FIG. 15b
illustrates a cross-section.
[0023] FIGS. 16a, 16b and 16c illustrate TEM micrographs of the
SGMM structure in melt-spun ribbons; wherein FIG. 16a illustrates a
TEM micrograph of Alloy 1; FIG. 16b illustrates a TEM micrograph of
Alloy 4, and FIG. 16c illustrates a TEM micrograph of Alloy 8.
[0024] FIGS. 17ai, 17aii, 17bi, 17bii, 17ci, and 17cii illustrate
TEM micrographs and SAED patterns of SGMM structure in microwires
produced by the Taylor-Ulitovsky process; FIG. 17ai) illustrates
TEM micrographs for Alloy 1 and FIG. 17aii illustrates SAED
patterns for Alloy 1; FIG. 17bi illustrates TEM micrographs for
Alloy 4 and FIG. 17bii illustrates SAED patterns for Alloy 4; and
FIG. 17ci illustrates TEM micrographs for Alloy 8 and FIG. 17cii
illustrates SAED patterns for Alloy 8.
[0025] FIGS. 18a and 18b illustrate a TEM micrograph (18a) and the
corresponding SAED (18b) pattern of SGMM structure in a foil from
Alloy 8 produced by the Planar Flow Casting process.
[0026] FIGS. 19a and 19b illustrate a TEM micrograph (19a) and SAED
pattern (19b) of the SGMM structure in a fiber from Alloy 8
produced through the Hyperquenching process.
[0027] FIGS. 20a and 20b illustrate an SEM image of multiple shear
bands on a surface of melt-spun ribbon from Alloy 1 after tensile
testing; FIG. 20a illustrates the wheel side ribbon surface (i.e.,
the surface of the ribbon which contacts the wheel during casting)
and FIG. 20b illustrates the free side ribbon surface (i.e., the
surface of the ribbon opposite the wheel during casting).
[0028] FIGS. 21a and 21b illustrate multiple shear bands on the
surface of the microwire from Alloy 2 after tensile testing (FIG.
21a) and necking prior to failure (FIG. 21b).
[0029] FIG. 22 illustrates multiple shear bands on the surface of
the foil from Alloy 1 (tension side) after bend testing.
[0030] FIG. 23 illustrates multiple shear bands on the surface of
the fiber from Alloy 8 after bend testing.
[0031] FIG. 24 illustrates localized deformation induced changes
(LDIC) occurring ahead of the moving shear band are shown near the
middle of the TEM micrograph in front of a shear band which is
moving from left to right.
[0032] FIGS. 25a and 25b illustrate a TEM micrograph of the
localized deformation induced changes (LDIC) around a shear band
(FIG. 25a) and corresponding selected area electron diffraction
(SAED) patterns showing phase transformation induced by propagating
shear band (FIG. 25b).
[0033] FIGS. 26a and 26b illustrate Induced Shear Band Blunting
(ISBB) in deformed melt-spun ribbon from Alloy 1 caused by
interaction of propagating shear band with SGMM structure (FIG.
26a) and an enlarged image of the area marked D in (a) showing LDIC
ahead of propagating shear band (FIG. 26b).
[0034] FIGS. 27a and 27b illustrate a TEM image of Shear Band
Arresting Interactions (SBAI) in deformed melt-spun ribbon from
Alloy 4 (FIG. 27a) and an Enlarged TEM image of the shear band
interaction area showing shear band branching and arresting (FIG.
27b).
[0035] FIG. 28 illustrates a stress-strain curves for various
commercial product forms including a melt-spun ribbon from Alloy 1,
a microwire from Alloy 2 produced by the Taylor-Ulitovsky process,
a foil from Alloy 9 produced by the Planar Flow Casting process,
and a fiber from Alloy 8 produced by the hyperquenching
process.
[0036] FIG. 29 is an SEM micrograph showing multiple levels of
shear bands in a surface of an Alloy 3 microwire sample that was
tested under unconstrained tension-torsion loading.
DETAILED DESCRIPTION
[0037] The present application relates to metallic glass forming
chemistries which may be triggered to form spinodal glass matrix
microconstituent (SGMM) structures that exhibit relatively
significant ductility (elongations of greater than or equal to
.about.1.0%) and high tensile strength (greater than or equal to
2.35 GPa for wire and greater than or equal to 0.62 GPa for
fibers). In addition, the alloys herein may be configured to
provide shear band per linear meter of greater than
1.1.times.10.sup.2 m.sup.-1 to 10.sup.7 m.sup.-1.
[0038] Spinodal microconstituents may be understood as
microconstituents formed by a transformation mechanism which is not
nucleation controlled. More basically, spinodal decomposition may
be understood as a mechanism by which a solution of two or more
components (e.g. metal compositions) of the alloy can separate into
distinct regions (or phases) with distinctly different chemical
compositions and physical properties. This mechanism differs from
classical nucleation in that phase separation may occur uniformly
throughout the material and not just at discrete nucleation sites.
One or more semicrystalline clusters or crystalline phases may
therefore form through a successive diffusion of atoms on a local
level until the chemistry fluctuations lead to at least one
distinct crystalline phase. Semi-crystalline clusters may be
understood herein as exhibiting a largest linear dimension of 2 nm
or less, whereas crystalline clusters may exhibit a largest linear
dimension of greater than 2 nm. Note that during the early stages
of the spinodal decomposition, the clusters which are formed may be
relatively small and while their chemistry differs from the glass
matrix, they are not yet fully crystalline and have not yet
achieved well ordered crystalline periodicity. Additional
crystalline phases may exhibit the same crystal structure or
distinct structures. Furthermore the glass matrix may be understood
to include microstructures that may exhibit associations of
structural units in the solid phase that may be randomly packed
together. The level of refinement, or the size, of the structural
units may be in the angstrom scale range (i.e. 5 .ANG. to 100
.ANG.) and additionally may range up in size up to the nm range (10
to 100 nm). Examples of the SGMM structure are included in the Case
Examples in this application.
[0039] In addition, the alloys may be triggered to provide
deformation responses including Induced Shear Band Blunting (ISBB)
and Shear Band Arresting Interactions (SBAI) which are associated
with the spinodal glass matrix microconstituent (SGMM). ISBB
involves the ability to blunt and stop propagating shear bands
through interactions with the SGMM structure. SBAI involves
arresting of shear bands through shear band/shear band interactions
and occur after the initial or primary shear bands are blunted
through ISBB.
[0040] While conventional materials deform through dislocations
moving on specific slip systems in crystalline metals, the alloys
herein are configured to involve moving shear bands (i.e.,
discontinuities where localized deformation occurs) in a spinodal
glass matrix microconstituent which are blunted by localized
deformation induced changes (LDIC). LDIC is described further
herein. With increasing levels of stress, once a shear band is
blunted, new shear bands may be nucleated and then interact with
existing shear bands creating relatively high shear band densities
in tension and the development of relatively significant levels of
plasticity. Thus, the alloys herein with the triggered SGMM
structures are capable of preventing or mitigating shear band
propagation in tension, which results in relatively significant
tensile ductility (.gtoreq.1% elongation) and leads to strain
hardening during tensile testing. Specific examples of the alloys
and their properties are included in the Case Examples reported
below.
[0041] Glass forming chemistries that may be used to form
compositions including the spinodal glass matrix microconstituent
structures may include certain iron based glass forming alloys
which are then processed to provide the SGMM structures noted
herein.
[0042] The operable system size may be defined as the volume of
material containing the SGMM structure. Additionally, for a liquid
melt cooling on a chill surface such as a wheel or roller (which
can be as wide as engineering will allow) 2-dimensional cooling
dominates so the thickness will be the limiting factor on structure
formation and resulting operable system size. At thicknesses above
a reasonable system size compared to the mechanism size, the
ductility mechanism will be unaffected. For example, the shear band
widths are relatively small (10 to 100 nm) and even with the LDIC
interactions with the structure the interaction size is from 20 to
200 nm. Thus, for example, achievement of significant ductility
(.gtoreq.1%) at a 100 micron thickness means that the system
thickness is already 500 to 10,000 times greater than ductility
mechanism sizes. The operable system size which when exceeded would
allow for ISBB and SBAI interactions would be .about.1 micron in
thickness or 1 .mu.m.sup.3 in volume. Achieving thicknesses greater
.about.1 micron or operable volumes greater 1 .mu.m.sup.3 would not
be expected to significantly affect the operable mechanisms or
achievement of significant levels of plasticity. Thus, greater
thickness or greater volume samples or products would be
contemplated to achieve an operable ductility with ISBB and SBAI
mechanisms in a similar fashion as identified as long as the SGMM
structure is formed.
[0043] In one embodiment, the glass forming alloys may include iron
present at atomic ratios of 44 to 59, including all values and
increments therein, nickel may be present at atomic ratios of 13 to
15, including all values and increments therein, cobalt may be
present at atomic ratios of 2 to 11, including all values and
increments therein, boron may be present at atomic ratios of 11 to
15, including all values and increments therein, silicon may be
present at atomic ratios of 0.4 to 8, including all values and
increments therein, carbon may optionally be present at atomic
ratios of 1.5 to 4.5, including all values and increments therein,
chromium may optionally be present at atomic ratios of 2 to 3,
including all values and increments therein, and niobium may
optionally be present at atomic ratios of 1.5 to 2.0, including all
values and increments therein. The above atomic ratios may be
understood as the ratio of the given element to the remainder of
the elements present in the base alloys composition. It may be
appreciated that the base alloy composition may be present in the
range of 70 to 100 percent of a given glass forming chemistry,
including all values and ranges therein, such as one or more values
or ranges selected from the following: 70, 71, 72, 73, 74, 75, 76,
77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93,
94, 95, 96, 97, 98, 99, 100.
[0044] Accordingly, it may be appreciated that iron may be present
at one or more atomic ratios selected from the following 44.0,
44.1, 44.2, 44.3, 44.4, 44.5, 44.6, 44.7, 44.8, 44.9, 45.0, 45.1,
45.2, 45.3, 45.4, 45.5, 45.6, 45.7, 45.8, 45.9, 46.0, 46.1, 46.2,
46.3, 46.4, 46.5, 46.6, 46.7, 46.8, 46.9, 47.0, 47.1, 47.2, 47.3,
47.4, 47.5, 47.6, 47.7, 47.8, 47.9, 48.0, 48.1, 48.2, 48.3, 48.4,
48.5, 48.6, 48.7, 48.8, 48.9, 49.0, 49.1, 49.2, 49.3, 49.4, 49.5,
49.6, 49.7, 49.8, 49.9, 50.0, 50.1, 50.2, 50.3, 50.4, 50.5, 50.6,
50.7, 50.8, 50.9, 51.0, 51.1, 51.2, 51.3, 51.4, 51.5, 51.6, 51.7,
51.8, 51.9, 52.0, 52.1, 52.2, 52.3, 52.4, 52.5, 52.6, 52.7, 52.8,
52.9, 53.0, 53.1, 53.2, 53.3, 53.4, 53.5, 53.6, 53.7, 53.8, 53.9,
54.0, 54.1, 54.2, 54.3, 54.4, 54.5, 54.6, 54.7, 54.8, 54.9, 55.0,
55.1, 55.2, 55.3, 55.4, 55.5, 55.6, 55.7, 55.8, 55.9, 56.0, 56.1,
56.2, 56.3, 56.4, 56.5, 56.6, 56.7, 56.8, 56.9, 57.0, 57.1, 57.2,
57.3, 57.4, 57.5, 57.6, 57.7, 57.8, 57.9, 58.0, 58.1, 58.2, 58.3,
58.4, 58.5, 58.6, 58.7, 58.8, 58.9, or 59.0, nickel may be present
at one or more atomic ratios selected from the following: of 10.0,
10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11.0, 11.1,
11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1, 12.2,
12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2, 13.3,
13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, 14.1, 14.2, 14.3, 14.4,
14.5, 14.6, 14.7, 14.8, 14.9, or 15.0, cobalt may optionally be
present at one or more atomic ratios selected from the following:
0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3,
1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,
2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9,
4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2,
5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5,
6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8,
7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1,
9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2, 10.3,
10.4, 10.5, 10.6, 10.7, 10.8, 10.9, or 11.0, boron may be present
at one or more atomic ratios selected from the following: 11.0,
11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0, 12.1,
12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1, 13.2,
13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, 14.0, 14.1, 14.2, 14.3,
14.4, 14.5, 14.6, 14.7, 14.8, 14.9, or 15.0, silicon optionally may
be present at one or more atomic ratios selected from the
following: 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4,
1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7,
2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0,
4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3,
5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6,
6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, or
8.0, carbon may be present at one or more atomic ratios selected
from the following: 0, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3,
2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7,
3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, or 4.5, chromium may be present at
one or more atomic ratios selected from the following: 0, 2.0, 2.1,
2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4,
3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7,
4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0,
6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3,
7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6,
8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9,
10.0, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, or
11.0, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12.0,
12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13.0, 13.1,
13.2, 13.3, 13.4, 13.5, 13.6, 13.7, 13.8, 13.9, or 14.0 and niobium
may be present at one or more atomic ratios selected from the
following: 0, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. The atomic ratios
being that of the base alloy composition.
[0045] In another embodiment, the glass forming chemistries which
may form the SGMM may include, consist of or consist essentially of
iron present in the range of 49 atomic percent (at %) to 65 at %,
nickel present in the range of 10.0 at % to 16.5 at %, cobalt
optionally present in the range of 0.1 at % to 12 at %, boron
present in the range of 12.5 at % to 16.5 at %, silicon optionally
present in the range of 0.1 at % to 8.0 at %, carbon optionally
present in the range of 2 at % to 5 at %, chromium optionally
present in the range of 2.5 at % to 13.35 at %, and niobium
optionally present in the range of 1.5 at % to 2.5 at %. It may be
appreciated that up to 10 at % of the composition may include
impurities. Again the atomic percents may be that of a base alloy
composition, which may be present in the glass forming chemistry in
the range of 70 at % to 100 at %, including all values and
increments therein, such as 70 at %, 71 at %, 72 at %, 73 at %, 74
at %, 75 at %, 76 at %, 77 at %, 78 at %, 79 at %, 80 at %, 81 at
%, 82 at %, 83 at %, 84 at %, 85 at %, 86 at %, 87 at %, 88 at %,
89 at %, 90 at %, 91 at %, 92 at %, 93 at %, 94 at %, 95 at %, 96
at %, 97 at %, 98 at %, 99 at %, 100 at %. For example, it may be
appreciated that up to 10 at % of the composition may include
impurities.
[0046] It may be appreciated that iron may be present at one or
more of the following atomic percentages: 49.0 at %, 49.1 at %,
49.2 at %, 49.3 at %, 49.4 at %, 49.5 at %, 49.6 at %, 49.7 at %,
49.8 at %, 49.9 at %, 50.0 at %, 50.1 at %, 50.2 at %, 50.3 at %,
50.4 at %, 50.5 at %, 50.6 at %, 50.7 at %, 50.8 at %, 50.9 at %,
51.0 at %, 51.1 at %, 51.2 at %, 51.3 at %, 51.4 at %, 51.5 at %,
51.6 at %, 51.7 at %, 51.8 at %, 51.9 at %, 52.0 at %, 52.1 at %,
52.2 at %, 52.3 at %, 52.4 at %, 52.5 at %, 52.6 at %, 52.7 at %,
52.8 at %, 52.9 at %, 53.0 at %, 53.1 at %, 53.2 at %, 53.3 at %,
53.4 at %, 53.5 at %, 53.6 at %, 53.7 at %, 53.8 at %, 53.9 at %,
54.0 at %, 54.1 at %, 54.2 at %, 54.3 at %, 54.4 at %, 54.5 at %,
54.6 at %, 54.7 at %, 54.8 at %, 54.9 at %, 55.0 at %, 55.1 at %,
55.2 at %, 55.3 at %, 55.4 at %, 55.5 at %, 55.6 at %, 55.7 at %,
55.8 at %, 55.9 at %, 56.0 at %, 56.1 at %, 56.2 at %, 56.3 at %,
56.4 at %, 56.5 at %, 56.6 at %, 56.7 at %, 56.8 at %, 56.9 at %,
57.0 at %, 57.1 at %, 57.2 at %, 57.3 at %, 57.4 at %, 57.5 at %,
57.6 at %, 57.7 at %, 57.8 at %, 57.9 at %, 58.0 at %, 58.1 at %,
58.2 at %, 58.3 at %, 58.4 at %, 58.5 at %, 58.6 at %, 58.7 at %,
58.8 at %, 58.9 at %, 59.0 at %, 59.1 at %, 59.2 at %, 59.3 at %,
59.4 at %, 59.5 at %, 59.6 at %, 59.7 at %, 59.8 at %, 59.9 at %,
60.0 at %, 60.1 at %, 60.2 at %, 60.3 at %, 60.4 at %, 60.5 at %,
60.6 at %, 60.7 at %, 60.8 at %, 60.9 at %, 61.0 at %, 61.1 at %,
61.2 at %, 61.3 at %, 61.4 at %, 61.5 at %, 61.6 at %, 61.7 at %,
61.8 at %, 61.9 at %, 62.0 at %, 62.1 at %, 62.2 at %, 62.3 at %,
62.4 at %, 62.5 at %, 62.6 at %, 62.7 at %, 62.8 at %, 62.9 at %,
63.0 at %, 63.1 at %, 63.2 at %, 63.3 at %, 63.4 at %, 63.5 at %,
63.6 at %, 63.7 at %, 63.8 at %, 63.9 at %, 64.0 at %, 64.1 at %,
64.2 at %, 64.3 at %, 64.4 at %, 64.5 at %, 64.6 at %, 64.7 at %,
64.8 at %, 64.9 at %, or 65.0 at %, nickel may be present at one or
more of the following atomic percentages: 10.0 at %, 10.1 at %,
10.2 at %, 10.3 at %, 10.4 at %, 10.5 at %, 10.6 at %, 10.7 at %,
10.8 at %, 10.9 at %, 11.0 at %, 11.1 at %, 11.2 at %, 11.3 at %,
11.4 at %, 11.5 at %, 11.6 at %, 11.7 at %, 11.8 at %, 11.9 at %,
or 12.0 at %, 12.5 at %, 12.6 at %, 12.7 at %, 12.8 at %, 12.9 at
%, 13.0 at %, 13.1 at %, 13.2 at %, 13.3 at %, 13.4 at %, 13.5 at
%, 13.6 at %, 13.7 at %, 13.8 at %, 13.9 at %, 14.0 at %, 14.1 at
%, 14.2 at %, 14.3 at %, 14.4 at %, 14.5 at %, 14.6 at %, 14.7 at
%, 14.8 at %, 14.9 at %, 15.0 at %, 15.1 at %, 15.2 at %, 15.3 at
%, 15.4 at %, 15.5 at %, 15.6 at %, 15.7 at %, 15.8 at %, 15.9 at
%, 16.0 at %, 16.1 at %, 16.2 at %, 16.3 at %, 16.4 at %, or 16.5
at %, cobalt may be present at one or more of the following atomic
percentages: 0.0 at %, 0.1 at %, 0.2 at %, 0.3 at %, 0.4 at %, 0.5
at %, 0.6 at %, 0.7 at %, 0.8 at %, 0.9 at %, 1.0 at %, 1.1 at %,
1.2 at %, 1.3 at %, 1.4 at %, 1.5 at %, 1.6 at %, 1.7 at %, 1.8 at
%, 1.9 at %, 2.0 at %, 2.1 at %, 2.2 at %, 2.3 at %, 2.4 at %, 2.5
at %, 2.6 at %, 2.7 at %, 2.8 at %, 2.9 at %, 3.0 at %, 3.1 at %,
3.2 at %, 3.3 at %, 3.4 at %, 3.5 at %, 3.6 at %, 3.7 at %, 3.8 at
%, 3.9 at %, 4.0 at %, 4.1 at %, 4.2 at %, 4.3 at %, 4.4 at %, 4.5
at %, 4.6 at %, 4.7 at %, 4.8 at %, 4.9 at %, 5.0 at %, 5.1 at %,
5.2 at %, 5.3 at %, 5.4 at %, 5.5 at %, 5.6 at %, 5.7 at %, 5.8 at
%, 5.9 at %, 6.0 at %, 6.1 at %, 6.2 at %, 6.3 at %, 6.4 at %, 6.5
at %, 6.6 at %, 6.7 at %, 6.8 at %, 6.9 at %, 7.0 at %, 7.1 at %,
7.2 at %, 7.3 at %, 7.4 at %, 7.5 at %, 7.6 at %, 7.7 at %, 7.8 at
%, 7.9 at %, 8.0 at %, 8.1 at %, 8.2 at %, 8.3 at %, 8.4 at %, 8.5
at %, 8.6 at %, 8.7 at %, 8.8 at %, 8.9 at %, 9.0 at %, 9.1 at %,
9.2 at %, 9.3 at %, 9.4 at %, 9.5 at %, 9.6 at %, 9.7 at %, 9.8 at
%, 9.9 at %, 10.0 at %, 10.1 at %, 10.2 at %, 10.3 at %, 10.4 at %,
10.5 at %, 10.6 at %, 10.7 at %, 10.8 at %, 10.9 at %, 11.0 at %,
11.1 at %, 11.2 at %, 11.3 at %, 11.4 at %, 11.5 at %, 11.6 at %,
11.7 at %, 11.8 at %, 11.9 at %, or 12.0 at %, boron may be present
at one or more of the following atomic percentages: 12.5 at %, 12.6
at %, 12.7 at %, 12.8 at %, 12.9 at %, 13.0 at %, 13.1 at %, 13.2
at %, 13.3 at %, 13.4 at %, 13.5 at %, 13.6 at %, 13.7 at %, 13.8
at %, 13.9 at %, 14.0 at %, 14.1 at %, 14.2 at %, 14.3 at %, 14.4
at %, 14.5 at %, 14.6 at %, 14.7 at %, 14.8 at %, 14.9 at %, 15.0
at %, 15.1 at %, 15.2 at %, 15.3 at %, 15.4 at %, 15.5 at %, 15.6
at %, 15.7 at %, 15.8 at %, 15.9 at %, 16.0 at %, 16.1 at %, 16.2
at %, 16.3 at %, 16.4 at %, or 16.5 at %, silicon may be present at
one or more of the following atomic percentages: 0.0 at %, 0.1 at
%, 0.2 at %, 0.3 at %, 0.4 at %, 0.5 at %, 0.6 at %, 0.7 at %, 0.8
at %, 0.9 at %, 1.0 at %, 1.1 at %, 1.2 at %, 1.3 at %, 1.4 at %,
1.5 at %, 1.6 at %, 1.7 at %, 1.8 at %, 1.9 at %, 2.0 at %, 2.1 at
%, 2.2 at %, 2.3 at %, 2.4 at %, 2.5 at %, 2.6 at %, 2.7 at %, 2.8
at %, 2.9 at %, 3.0 at %, 3.1 at %, 3.2 at %, 3.3 at %, 3.4 at %,
3.5 at %, 3.6 at %, 3.7 at %, 3.8 at %, 3.9 at %, 4.0 at %, 4.1 at
%, 4.2 at %, 4.3 at %, 4.4 at %, 4.5 at %, 4.6 at %, 4.7 at %, 4.8
at %, 4.9 at %, 5.0 at %, 5.1 at %, 5.2 at %, 5.3 at %, 5.4 at %,
5.5 at %, 5.6 at %, 5.7 at %, 5.8 at %, 5.9 at %, 6.0 at %, 6.1 at
%, 6.2 at %, 6.3 at %, 6.4 at %, 6.5 at %, 6.6 at %, 6.7 at %, 6.8
at %, 6.9 at %, 7.0 at %, 7.1 at %, 7.2 at %, 7.3 at %, 7.4 at %,
7.5 at %, 7.6 at %, 7.7 at %, 7.8 at %, 7.9 at %, or 8.0 at %,
carbon may be present at one or more of the following atomic
percentages: 0 at %, 2.0 at %, 2.1 at %, 2.2 at %, 2.3 at %, 2.4 at
%, 2.5 at %, 2.6 at %, 2.7 at %, 2.8 at %, 2.9 at %, 3.0 at %, 3.1
at %, 3.2 at %, 3.3 at %, 3.4 at %, 3.5 at %, 3.6 at %, 3.7 at %,
3.8 at %, 3.9 at %, 4.0 at %, 4.1 at %, 4.2 at %, 4.3 at %, 4.4 at
%, 4.5 at %, 4.6 at %, 4.7 at %, 4.8 at %, 4.9 at %, or 5.0 at %,
chromium may be present at one or more of the following atomic
percentages: 0 at %, 2.5 at %, 2.6 at %, 2.7 at %, 2.8 at %, 2.9 at
%, or 3.0 at %, 3.1 at %, 3.2 at %, 3.3 at %, 3.4 at %, 3.5 at %,
3.6 at %, 3.7 at %, 3.8 at %, 3.9 at %, 4.0 at %, 4.1 at %, 4.2 at
%, 4.3 at %, 4.4 at %, 4.5 at %, 4.6 at %, 4.7 at %, 4.8 at %, 4.9
at %, 5.0 at %, 5.1 at %, 5.2 at %, 5.3 at %, 5.4 at %, 5.5 at %,
5.6 at %, 5.7 at %, 5.8 at %, 5.9 at %, 6.0 at %, 6.1 at %, 6.2 at
%, 6.3 at %, 6.4 at %, 6.5 at %, 6.6 at %, 6.7 at %, 6.8 at %, 6.9
at %, 7.0 at %, 7.1 at %, 7.2 at %, 7.3 at %, 7.4 at %, 7.5 at %,
7.6 at %, 7.7 at %, 7.8 at %, 7.9 at %, 8.0 at %, 8.1 at %, 8.2 at
%, 8.3 at %, 8.4 at %, 8.5 at %, 8.6 at %, 8.7 at %, 8.8 at %, 8.9
at %, 9.0 at %, 9.1 at %, 9.2 at %, 9.3 at %, 9.4 at %, 9.5 at %,
9.6 at %, 9.7 at %, 9.8 at %, 9.9 at %, 10.0 at %, 10.1 at %, 10.2
at %, 10.3 at %, 10.4 at %, 10.5 at %, 10.6 at %, 10.7 at %, 10.8
at %, 10.9 at %, 11.0 at %, 11.1 at %, 11.2 at %, 11.3 at %, 11.4
at %, 11.5 at %, 11.6 at %, 11.7 at %, 11.8 at %, 11.9 at %, or
12.0 at %, 12.5 at %, 12.6 at %, 12.7 at %, 12.8 at %, 12.9 at %,
13.0 at %, 13.1 at %, 13.2 at %, 13.3 at %, 13.4 at %, 13.5 at %,
13.6 at %, 13.7 at %, 13.8 at %, 13.9 at %, 14.0 at %, and niobium
may be present at one or more of the following atomic percentages:
0 at %, 1.5 at %, 1.6 at %, 1.7 at %, 1.8 at %, 1.9 at %, 2.0 at %,
2.1 at %, 2.2 at %, 2.3 at %, 2.4 at %, or 2.5 at %.
[0047] In one embodiment, the alloy composition may consist
essentially of a minimum of five of the above listed elements. In
another embodiment, the alloy composition may consist essentially
of five to seven of the above listed elements. In a further
embodiment, the alloy composition may consist essentially of iron,
nickel, boron, silicon and one or more of the following: cobalt,
chromium, carbon and niobium. In another embodiment, the alloy may
composition consist essentially of iron, nickel, boron, silicon and
chromium.
[0048] For example, the glass forming chemistries which may form
the SGMM may include, consist of or consist essentially of iron
present in the range of 49 at % to 65 at %, nickel present in the
range of 14.5 at % to 16.5 at %, cobalt present in the range of 2.5
at % to 12 at %, boron present in the range of 12.5 at % to 16.5 at
%, silicon present in the range of 0.4 at % to 8.0 at %, carbon
optionally present in the range of 2 at % to 5 at %, chromium
optionally present in the range of 2.5 at % to 13.35 at %, and
niobium optionally present in the range of 1.5 at % to 2.5 at
%.
[0049] For example, in one embodiment, the alloy may include 53 at
% to 62 at % iron, 15.5 at % to 16.5 at % nickel, optionally 4 at %
to 10 at % cobalt, 12 at % to 16 at % boron, 4.5 at % to 4.6 at %
carbon, and 0.4 at % to 0.5 at % silicon. In another embodiment,
the alloy may include 51 at % to 65 at % iron, 16.5 at % nickel,
optionally 3 at % to 12 at % cobalt, 15 at % to 16.5 at % boron,
and 0.4 at % to 4 at % silicon. In a further embodiment, the alloy
may include 49 at % to 61 at % iron, 14.5 at % to 16 at % nickel,
2.5 at % to 12 at % cobalt, 13 at % to 16 at % boron, 3 at % to 8
at % silicon, and 2.5 at % to 3 at % chromium. In yet a further
embodiment, the alloy may include 57 at % to 60 at % iron, 14.5 at
% to 15.5 at % nickel, 2.5 at % to 3 at % cobalt, 13 at % to 14 at
% boron, 3.5 at % to 8 at % silicon, 2.5 at % to 3 at % chromium
and optionally 2 at % niobium.
[0050] The alloys in ingot form may exhibit a density in the range
of 7.5 grams per cubic centimeter (g/cm.sup.3) to 7.8 g/cm.sup.3,
including all values and increments therein, such as 7.50, 7.51,
7.52, 7.53, 7.54, 7.55, 7.56, 7.57, 7.58, 7.59, 7.60, 7.61, 7.62,
7.63, 7.64, 7.65, 7.66, 7.67, 7.68, 7.69, 7.70, 7.71, 7.72, 7.73,
7.74, 7.75, 7.76, 7.77, 7.78, 7.79, 7.80.
[0051] The alloys may be processed by a number of processing
techniques to yield thin product forms including ribbons, fibers,
foils (relatively thin sheet), relatively thick sheet and
microwires. Examples of processing techniques that may be
configured to provide the SGMM structures herein and associated
plasticity include but are not limited to melt-spinning/jet
Casting, hyperquenching, Taylor-Ulitovsky wire casting, planar flow
casting, and twin roll casting. Additional details of these
manufacturing techniques, operating in a manner to provide the SGMM
structures herein, are included below. Cooling rates may be in the
range of 10.sup.3K/s to 10.sup.6 K/s, including all values and
ranges therein, such as 10.sup.4K/s-10.sup.6K/s, etc. In addition,
the products may exhibit a thickness in the range of 0.001 mm to 3
mm, including all values and ranges therein. For example, the
products may have a thickness in the range of 0.001 mm to 0.15 mm,
0.001 mm to 0.12 mm, 0.016 mm to 0.075 mm, etc.
[0052] In the melt-spinning process, a liquid melt may be ejected
using gas pressure onto a rapidly moving copper wheel. Continuous
or broken up lengths of ribbon may be produced. In some
embodiments, the ribbon may be in the range of 1 to 2 mm wide and
0.015 to 0.15 mm thick, including all values and increments
therein. The width and thickness may depend on the melt spun
materials viscosity and surface tension and the wheel tangential
velocity. Typical cooling rates in the melt-spinning process may be
from .about.10.sup.4 to .about.10.sup.6 K/s, including all values
and increments therein. Ribbons may generally be produced in a
continuous fashion up to 25 m long using a laboratory scale system.
Existing commercial systems used for magnetic materials may also be
called jet casters.
[0053] Process parameters in one embodiment of melt spinning may
include providing the liquid melt in a chamber, which is in an
environment including air or an inert gas, such as helium, carbon
dioxide, carbon dioxide and carbon monoxide mixtures, or carbon
dioxide and argon mixtures. The chamber pressure may be in the
range of 0.25 atm to 1 atm, including all values and increments
therein. Further, the casting wheel tangential velocity may be in
the range of 15 meters per second (m/s) to 30 m/s, including all
values and increments therein. Resulting ejection pressures may be
in the range of 100 to 300 mbar and resulting ejection temperatures
may be in the range of 1000.degree. C. to 1300.degree. C.,
including all values and increments therein.
[0054] Hyperquenching may be understood as a relatively large scale
commercial process that may be based on relatively continuous rapid
solidification molten metal and used for fiber production. Molten
metal may be consistently poured onto the moving surface of a
rotating chill roll with a specifically designed groove pattern.
Fibers may be solidified on the chill roll at lengths which can
vary from a few mm's to a 100 mm, including all values and
increments therein and thickness from 0.015 to 0.15 mm, including
all values and increments therein. Typical cooling rates in the
melt-spinning process may be from .about.10.sup.4 to
.about.10.sup.6 K/s, including all values and increments
therein.
[0055] An example of a process for producing relatively small
diameter wire with a circular cross section is the Taylor-Ulitovsky
process. In this wire making process, metal feedstock in the form
of a powder, ingot, or wire/ribbon may be held in a glass tube,
typically a borosilicate composition, which is closed at one end.
This end of the tube may then be heated in order to soften the
glass to a temperature at which the metal part is in liquid state
while the glass may be softened yet not melted. The glass
containing the liquid melt may then be drawn down to produce a fine
glass capillary containing a metal core. At suitable drawing
conditions, the molten metal fills the glass capillary and a
microwire may be produced where the metal core is completely coated
by a glass shell. The process may be continuous by continuously
feeding the metal drop using powder or wire/ribbon with new alloy
material. The method has been touted as a relatively low cost
production method. The amount of glass used in the process may be
balanced by the continuous feeding of the glass tube through the
inductor zone, whereas the formation of the metallic core is
restricted by the initial quantity of the master alloy droplet. The
microstructure of a microwire (and hence, its properties) may
depend mainly on the cooling rate, which can be controlled by a
cooling mechanism when the metal-filled capillary enters into a
stream of cooling liquid (water or oil) on its way to the receiving
coil. Metal cores in the range of 1 to 120 .mu.m with a glass
coating which may be in the range of 2 to 20 .mu.m in thickness,
including all values and increments therein, may be produced by
this method. Cooling rates may vary from 10.sup.3 to 10.sup.6 K/s,
including all values and increments therein, in the process.
[0056] Planar flow casting may be understood as a relatively low
cost and relatively high volume technique to produce wide ribbon in
the form of continuous sheet and involves flowing a liquid melt at
a close distance over a chill surface. Widths of thin foil/sheet up
to 18.4'' (215 mm), including all values and increments in the
range of 10 mm to 215 mm, may be produced on a commercial scale
with thickness in the range of 0.016 to 0.075 mm, including all
values and increments therein, with cooling rates which may be in
the range of .about.10.sup.4 to .about.10.sup.6 K/s, including all
values and increments therein. After production of sheets, the
individual sheets (from 5 to 50) can be warm pressed to roll bond
the compacts into sheets. Sheets may also be cut, chopped, slit,
and corrugated into other product and product forms.
[0057] In the twin roll casting process, a liquid melt is quenched
between two rollers rotating in opposite directions. Solidification
begins at first contact between the upper part of each of the rolls
and the liquid melt. Two individual shells begin to form on each
chill surface and, as the process continues, are subsequently
brought together at the roll nip by the chill rolls to form one
continuous sheet. By this approach, solidification occurs rapidly
and direct melt thicknesses can be achieved much thinner than
conventional melt processes and typically into the 1.5 to 3.0 mm
range prior to any post processing steps such as hot rolling. The
process is similar in many ways to planar flow casting with one of
the main differences is that two chill rollers are used to produce
sheet in twin roll casting rather than a single chill roller in
planar flow casting. However, in the context of the sheet that may
be produced herein, having the indicated SGMM structure, the
thickness may be in the range of 0.5 to 5.0 mm.
[0058] In some embodiments, the glass forming alloys, upon
formation, may exhibit glass to crystalline temperature ranges,
which may exhibit one or more transition peaks. For example, the
glass to crystalline onset to peak range may be 395.degree. C. to
576.degree. C., including all values and increments therein, when
measured at 10.degree. C./min. Primary onset glass transition
temperatures may be in the range of 395.degree. C. to 505.degree.
C. and secondary onset glass transition temperatures, when present,
may be in the range of 460.degree. C. to 541.degree. C. Primary
peak glass transition temperatures may be in the range of
419.degree. C. to 521.degree. C. and secondary onset glass
transition temperatures, when present, may be in the range of
465.degree. C. to 576.degree. C. Further, the enthalpies of
transformation may be in the range of -21.4 J/g to -115.3 J/g,
including all values and increments therein. The properties may be
obtained either by DSC or DTA when measure at a heating/cooling
rate of 10.degree. C./min.
[0059] The formed alloys may also exhibit complete bending on one
or both sides of the formed alloys, when tested under the
180.degree. bend test. That is, a ribbon or foil of the alloys
described herein, having a thickness in the range of 20 .mu.m to 85
.mu.m, may be folded completely over in either direction. In
addition, the formed alloys in ribbon form (as formed by melt
spinning), may exhibit the following mechanical properties when
tested at a strain rate of 0.001 s.sup.-1. The ultimate tensile
strength may be in the range of 2.30 GPa to 3.27 GPa, including all
values and increments therein. The total elongation may be in the
range of 2.27% to 4.78%, including all values and increments
therein. When formed into a foil (as formed by planar flow casting)
the alloys may exhibit an ultimate tensile strength in the range of
1.77 GPa to 3.13 GPa and a total elongation of 2.6% to 3.6%. In
addition, the foils may exhibit an average microhardness in the
range of 9.10 GPa to 9.21 GPa when tested under a 50 gram load.
[0060] The formed alloys in wire form (as formed by the
Taylor-Ulitovsky Process), may exhibit the following mechanical
properties when tested at a strain rate of 0.001 s.sup.-1. The
ultimate tensile strength may be in the range of 2.3 GPa to 5.8
GPa, including all values and increments therein. The total
elongation may be in the range of 1.9% to 12.8%, including all
values and increments therein. When formed into fibers (as formed
by hyperquenching) the alloys may exhibit an ultimate tensile
strength in the range of 0.62 GPa to 1.47 GPa and a total
elongation of 0.67% to 2.56%.
[0061] Thus, in general, the alloy compositions may exhibit an
ultimate tensile strength in the range of 0.62 GPa to 5.8 GPa,
including all values and ranges therein, when measured at a strain
rate of 0.001 s.sup.-1. Furthermore, the alloy compositions may
exhibit a total elongation in the range of 0.67% to 12.8%,
including all values and ranges therein, when measured at a strain
rate of 0.001 s.sup.-1. The alloys may also exhibit a microhardness
in the range of 9.10 GPa to 9.21 GPa, including all values and
ranges therein when tested under a 50 gram load. In addition, the
formed alloys as noted when produced as noted indicate a number of
nanoscale features and exhibit the formation of the indicated SGMM
structures and shear band densities or number per unit of
measurement, such as linear meter. In some embodiments a metallic
glass matrix may be present wherein the matrix may include
semi-crystalline or crystalline clusters. The clusters may exhibit
a size in the range of 1 to 15 nm in thickness and 2 to 60 nm in
length. In other embodiments, the metallic glass matrix may include
interconnected nanoscale phases range from several nm in length to
125 nanometers in length.
EXAMPLES
Sample Preparation
[0062] Using high purity and commercial purity elements, 15 g alloy
feedstocks of the targeted alloys were weighed out according to the
atomic ratios provided in Tables 1. The feedstock material was then
placed into the copper hearth of an arc-melting system. The
feedstock was arc-melted into an ingot using high purity argon as a
shielding gas. The ingots were flipped several times and re-melted
to ensure homogeneity. After mixing, the ingots were then cast in
the form of a finger approximately 12 mm wide by 30 mm long and 8
mm thick. The resulting fingers were then placed in a melt-spinning
chamber in a quartz crucible with a hole diameter of .about.0.81
mm. The ingots were then processed by melting in different
atmospheres and temperatures using RF induction and then ejected
onto a 245 mm diameter copper wheel which was rotating at
tangential velocities varying from 10.5 to 39 m/s.
TABLE-US-00001 TABLE 1 Chemical Composition of Alloys Alloy Fe Ni
Co B C Si Cr Nb 1 48.15 13.95 9.00 14.40 4.05 0.45 -- -- 2 55.80
14.50 3.95 11.24 4.09 0.42 -- -- 3 58.53 14.85 2.70 13.50 -- 0.42
-- -- 4 45.91 14.85 10.80 14.84 -- 3.60 -- -- 5 44.53 14.41 10.48
14.40 -- 3.48 2.70 -- 6 54.76 13.90 2.53 12.62 -- 3.60 2.60 -- 7
52.46 13.32 2.42 12.11 -- 7.20 2.49 -- 8 51.46 13.07 2.38 11.87
1.80 6.98 2.44 -- 9 44.84 13.07 10.80 11.87 -- 6.98 2.44 -- 10
53.65 13.62 2.48 12.38 -- 3.53 2.56 1.80 11 64.97 16.49 -- 14.99 --
0.46 3.09 -- 12 62.83 10.00 -- 13.40 -- 0.42 13.35 --
[0063] The alloys of Table 1 were melt-spun under various
conditions. Representative melt-spinning parameters for each alloy
are listed in Table 2, which resulted in the achievement of
relatively significant levels of tensile ductility.
TABLE-US-00002 TABLE 2 Melt-Spinning Parameters of Alloys Pressure
in Wheel Ejection Ejection Chamber chamber Speed Pressure
Temperature Alloy Purity gas [atm] [m/s] [mbar] [.degree. C.] 1 HP
He 1/3 16 280 1200 2 HP Air 1/3 30 280 1250 3 HP He 1/3 10.5 280
1200 4 CP Norco 9 1/3 15 280 1225 (CO.sub.2/Ar) 5 HP He 1/3 16 280
1250 6 CP Air 1 25 280 1200 7 CP Air 1/3 25 280 1300 8 CP CO.sub.2
1/3 25 140 1300 9 CP CO.sub.2 + CO 1/3 25 280 1250 10 CP Air 1/3 25
140 1200 11 CP CO2 1/3 25 280 1208 12 CP CO2 1/3 25 280 1276
[0064] The density of the alloys in ingot form was measured using
the Archimedes method in a specifically constructed balance
allowing for weighing in both air and distilled water. The density
of the arc-melted 15 gram ingots for each alloy is tabulated in
Table 3 and was found to vary from 7.56 g/cm.sup.3 to 7.75
g/cm.sup.3. Experimental results have revealed that the accuracy of
this technique is +/-0.01 g/cm.sup.3.
TABLE-US-00003 TABLE 3 Density of Alloys Density Alloy (g/cm.sup.3)
1 7.73 2 7.75 3 7.75 4 7.70 5 7.71 6 7.70 7 7.56 8 7.58 9 7.64 10
7.71 11 7.73 12 7.66
[0065] Thermal analysis was performed on the as-solidified ribbon
structure on a Perkin Elmer DTA-7 system with the DSC-7 option or a
NETZSCH DSC404 F3 DSC. Differential thermal analysis (DTA) and
differential scanning calorimetry (DSC) was performed at a heating
rate of 10.degree. C./minute with samples protected from oxidation
through the use of flowing ultrahigh purity argon. In Table 4, the
DSC data related to the glass to crystalline transformation is
shown for each alloy listed in Table 1 and melt-spun at parameters
specified in Table 2. As can be seen, all alloys exhibit glass to
crystalline transformations verifying that the as-spun state
contains relatively significant fractions of metallic glass, e.g.
at a volume percent level of greater than or equal to 10%. The
glass to crystalline transformation occurs in either one stage or
two stages in the range of temperature from 395.degree. C. to
576.degree. C. and with enthalpies of transformation from -21.4 J/g
to -115.3 J/g.
TABLE-US-00004 TABLE 4 DSC Data for Glass to Crystalline
Transformations in Melt-Spun Ribbons Peak #1 Peak #1 Peak #2 Peak
#2 Onset Peak .DELTA.H Onset Peak .DELTA.H Alloy Glass (.degree.
C.) (.degree. C.) (-J/g) (.degree. C.) (.degree. C.) (-J/g) 1 Yes
466 469 115.3 -- -- -- 2 Yes 439 450 30.2 477 483 65.3 3 Yes 395
419 21.4 460 465 55.1 4 Yes 485 492 43.2* -- -- -- 5 Yes 484 492
51.1 -- -- -- 6 Yes 457 463 23.0 501 509 33.8 7 Yes 505 520 114.0
-- -- -- 8 Yes 499 521 102.4 -- -- -- 9 Yes 486 496 35.1 517 531
49.4 10 Yes 469 480 40.7 541 576 53.3 11 Yes 402 417 52 451 472 69
12 Yes 433 448 53 481 501 76 at %,*Two overlapping peaks
[0066] The ability of the ribbons to bend completely flat indicates
a ductile condition whereby relatively high strain can be obtained
but not measured by traditional bend testing. When the ribbons are
folded completely around themselves, they experience high strain
which can be as high as 119.8% as derived from complex mechanics.
During 180.degree. bending (i.e. flat), four types of behavior can
be observed; Type 1 Behavior--not bendable without breaking, Type 2
Behavior--bendable on one side with the side contacting the casting
wheel facing outward (wheel side), Type 3 Behavior--bendable on one
side with the side away from the casting wheel facing outward (free
side), and Type 4 Behavior--bendable on both sides, either the side
contacting the casting wheel or the side not contacting the casting
wheel. In Table 5, a summary of the 180.degree. bending results
including the specific behavior type are shown for each alloy
listed in Table 1 and melt-spun at parameters specified in Table 2.
The thickness of melt-spun ribbons varies from 20 to 85 .mu.m.
TABLE-US-00005 TABLE 5 Summary on Ribbon Thickness and Bending
Behavior Thickness Behavior Alloy (.mu.m) Bending Response Alloy
Type 1 35-42 Bendable on free side 3 2 20-25 Bendable on both side
along entire length 4 3 80-85 Bendable on both side along entire
length 4 4 50-67 Bendable on both side along entire length 4 5
27-31 Bendable on both side along entire length 4 6 36-42 Bendable
on both side along entire length 4 7 47-49 Bendable on both side
along entire length 4 8 35-42 Bendable on both side along entire
length 4 9 41-44 Bendable on both side along entire length 4 10
27-37 Bendable on both side along entire length 4 11 39-55 Bendable
on both side along entire length 4 12 40-60 Bendable on both side
along entire length 4
[0067] The mechanical properties of metallic ribbons were obtained
at room temperature using microscale tensile testing. The testing
was carried out in a commercial tensile stage made by Ernest Fullam
Inc., which was monitored and controlled by a MTEST Windows
software program. The deformation was applied by a stepping motor
through the gripping system while the load was measured by a load
cell that was connected to the end of one gripping jaw.
Displacement was obtained using a Linear Variable Differential
Transformer (LVDT) which was attached to the two gripping jaws to
measure the change of gauge length. Before testing, the thickness
and width of a ribbon tensile specimen was carefully measured at
least three times at different locations in the gauge length. The
average values were then recorded as gauge thickness and width, and
used as input parameters for subsequent stress and strain
calculation. The initial gauge length for tensile testing was set
at .about.7 to .about.9 mm with the exact value determined after
the ribbon was fixed, by accurately measuring the ribbon span
between the front faces of the two gripping jaws. All tests were
performed under displacement control, with a strain rate of
.about.0.001 s.sup.-1. A summary of the tensile test results
including total elongation, yield strength, ultimate tensile
strength, and Young's Modulus are shown in Table 6 for each alloy
listed in Table 1 and melt-spun at parameters specified in Table 2.
Note that the results shown in Table 6 have been adjusted for
machine compliance and have been measured at a gauge length of 9
mm. Also, note that each distinct alloy was measured in triplicate
since occasional macrodefects arising from the melt-spinning
process can lead to localized areas with reduced properties. As can
be seen, the tensile strength values vary from 2.30 GPa to 3.27 GPa
while the total elongation values vary from 2.27% to 4.78%. Young's
Modulus value for the alloys was measured in a range from 66.4 to
188.5 GPa. Additionally, all alloys have demonstrated the ability
to exhibit strain hardening like a crystalline metal.
TABLE-US-00006 TABLE 6 Summary on Tensile Properties of Melt-Spun
Ribbons Yield Young's Total Strength UTS Modulus Alloy Elongation
(%) (GPa) (GPa) (GPa) 1 2.27 1.97 2.90 160.2 3.11 2.08 3.24 113.4
2.87 1.78 2.92 122.0 2 4.70 1.91 3.18 127.8 2.57 1.56 2.56 133.0
3.00 1.78 2.77 125.5 3 3.88 1.83 3.04 123.9 3.70 1.80 2.92 125.1
3.99 1.67 3.14 116.8 4 2.78 1.66 2.92 151.0 3.00 1.67 2.57 156.2
2.89 1.70 2.93 152.2 5 3.88 1.44 2.97 115.9 4.62 1.44 3.16 114.9
3.73 1.69 3.27 140.1 6 2.78 1.83 2.63 144.3 2.78 1.81 2.67 140.0
2.44 1.73 2.56 146.5 7 3.56 1.13 2.35 142.9 2.78 1.58 2.38 150.2
2.67 1.79 2.62 160.6 8 4.33 1.06 2.68 125.9 3.56 1.18 2.68 162.0
4.78 0.82 2.65 137.1 9 3.20 1.05 2.71 167.2 3.20 1.04 2.59 159.8
2.80 1.40 2.59 183.4 10 3.44 1.23 2.89 161.8 3.00 1.55 2.95 188.5
2.78 1.60 3.11 163.7 11 3.50 1.85 2.52 83.2 3.06 2.06 2.56 92.4
4.59 1.76 2.59 66.4 12 3.38 1.40 2.37 91.9 3.24 1.45 2.30 88.8 3.22
1.68 2.42 92.8
Case Examples
Case Example 1
[0068] For commercial processing studies, the alloys listed in
Table 1 were made up in commercial purity (up to 10 at % impurity)
using various ferroadditive and other readily commercially
available constituents chosen to minimize alloy cost. In Table 7, a
summary of the alloys utilized for commercial production trials is
presented. A description of the resulting commercial product forms
including the physical dimensions and the total length produced is
provided in Table 8. Further examples of the products for each
alloy type are provided in FIGS. 1 through 12.
TABLE-US-00007 TABLE 7 Summary on Alloys Used For Commercial
Production Trials Alloy Number Demonstrated Production Approaches
Alloy 1 Planar Flow Casting Alloy 2 Taylor-Ulitovsky Process Alloy
3 Taylor-Ulitovsky Process Alloy 4 Taylor-Ulitovsky, Planar Flow
Casting Alloy 5 Taylor-Ulitovsky Process Alloy 6 Planar Flow
Casting, Taylor-Ulitovsky Process Alloy 7 Taylor-Ulitovsky Process
Alloy 8 Taylor-Ulitovsky Process, Planar Flow Casting,
Hyperquenching Process Alloy 9 Planar Flow Casting Alloy 11 Planar
Flow Casting Alloy 12 Planar Flow Casting
TABLE-US-00008 TABLE 8 Summary on Commercial Products Alloy
Demonstrated Produc- Number tion Approaches Product Form Alloy 1
Planar Flow Casting Foil thickness: 25-28 .mu.m Foil width: 7.5 mm
Foil length: 100 m Alloy 2 Taylor-Ulitovsky Total wire diameters:
34-61 .mu.m Process Metal core diameters: 21-35 .mu.m Glass
thickness: 6-13 .mu.m Total Length: 0.4 km Alloy 3 Taylor-Ulitovsky
Total wire diameters: 22-74 .mu.m Process Metal core diameters:
11.2-45 .mu.m Glass thickness: 2.5-18 .mu.m Total Length: 4.6 km
Alloy 4 Taylor-Ulitovsky Total wire diameters: 5.5-181.8 .mu.m
Process Metal core diameters: 3-161.6 .mu.m Glass thickness: 2.5-18
.mu.m Total Length: 219 km Alloy 4 Planar Flow Casting Foil
thickness: 20-22 .mu.m Foil width: 6.5 mm Foil length: 100 m Alloy
5 Taylor-Ulitovsky Total wire diameters: 31.6-141.1 .mu.m Process
Metal core diameters: 15.1-74.2 .mu.m Glass thickness: 7.7-34.2
.mu.m Total Length: 1.4 km Alloy 6 Planar Flow Casting Foil
thickness: 24-30 .mu.m Foil width: 7.4-7.6 mm Foil length: 300 m
Alloy 7 Taylor-Ulitovsky Total wire diameters: 24-110.2 .mu.m Metal
core diameters: 13.2-67.0 .mu.m Glass thickness: 4.3-27.3 .mu.m
Total Length: 10.4 km Alloy 8 Taylor-Ulitovksy Total wire
diameters: 32.4-43 .mu.m Metal core diameters: 14-30 .mu.m Glass
thickness: 3.6-11 .mu.m Total Length: 12.4 km Alloy 8 Planar Flow
Casting Foil thickness: 22-24 .mu.m Foil width: 7.5 mm Foil length:
100m Alloy 8 Hyperquenching Fiber width: 1.4-2.3 mm Process Fiber
length:: 25-30 mm Fiber thickness: 37-53 .mu.m Total amount: 280 kg
Alloy 9 Planar Flow Casting Foil thickness: 24-32 .mu.m Foil width:
7.5-8.0 mm Foil length: 300 m Alloy 11 Planar Flow Casting Foil
thickness: 24-49 .mu.m Foil width: 17-50 mm Foil length: >300 m
Foil mass: >100 kg Alloy 12 Planar Flow Casting Foil thickness:
32-36 .mu.m Foil width: 50 mm Foil length: >300 m Foil mass:
>9 kg
Case Example #2
[0069] Using the Taylor-Ulitovsky process, a range of wire was
produced using a wide variety of parameter variations including
variations in the liquid metal droplet position inside the
inductor, melt temperature superheat, glass feed velocity, vacuum
pressure force, spool winding velocity, glass feedstock type etc. A
summary of parameters of produced microwires is given in Table 8.
The metal core diameter varied from 3 to 162 .mu.m while the total
wire diameter (i.e. with glass coating) varied from 5 to 182 .mu.m.
The length of the wire produced varied from 28 to 9000 m depending
on the stability of the process conditions.
[0070] The mechanical properties of microwires were measured at
room temperature using microscale tensile testing. The testing was
carried out in a commercial tensile stage made by Ernest Fullam,
Inc., which was monitored and controlled by a MTEST Windows
software program. The deformation was applied by a stepping motor
through the gripping system while the load was measured by a load
cell that was connected to the end of one gripping jaw.
Displacement was obtained using a Linear Variable Differential
Transformer (LVDT) which was attached to the two gripping jaws to
measure the change of gauge length. Before testing, the diameter of
each wire was carefully measured at least three times at different
locations in the gauge length. The average value was then recorded
as gauge diameter and used as input for subsequent stress and
strain calculation. All tests were performed under displacement
control, with a strain rate of .about.0.001 s.sup.-1. A summary of
the tensile test results including the wire diameter (metal core
and total), measured gauge length, total elongation, applied load
(preloading and peak loading) and measure strength (yield stress
and ultimate tensile strength) are given in Tables 9 through 13. As
can be seen, the tensile strength values vary from 2.3 GPa to 5.8
GPa while the total elongation values vary from 1.9% to 12.8%.
TABLE-US-00009 TABLE 9 Tensile Properties of Alloy 2 Microwires
Diameters Gauge Strength (mm) Length Elongation Load (N) (GPa)
Outside Core (mm) (mm) (%) Pre Peak Yield UTS 0.051 0.03 26.0 1.31
5.07 N/A 2.919 1.36 4.13 0.051 0.027 28.0 1.75 6.25 N/A 2.293 1.39
4.01 0.048 0.025 31.0 1.79 5.77 N/A 2.006 N/A 4.09 0.048 0.022 11.8
0.66 5.77 0.145 1.315 N/A 3.84 0.048 0.022 12.1 1.00 8.28 0.107
1.344 N/A 3.82 0.048 0.022 19.8 0.75 3.79 0.088 0.940 N/A 2.71
0.051 0.031 14.5 1.29 8.90 0.107 2.872 N/A 3.95 0.048 0.028 14.2
1.20 8.43 0.443 2.210 N/A 4.31 0.048 0.028 16.1 1.71 10.62 0.254
2.267 N/A 4.10 0.061 0.035 40.0 0.77 1.93 0.039 3.214 1.24 3.38
0.053 0.035 40.0 1.27 3.18 0.046 3.246 1.46 3.42 0.034 0.022 26.0
1.46 5.62 0.063 1.769 N/A 4.82 0.034 0.022 24.4 2.16 8.85 0.041
1.719 N/A 4.63 0.038 0.021 14.0 0.49 3.50 0.023 1.079 N/A 3.18
0.038 0.021 12.1 0.71 5.87 0.069 1.025 N/A 3.16 0.038 0.021 10.0
0.63 6.30 0.092 0.965 N/A 3.05 0.038 0.021 16.8 0.57 3.39 0.061
1.162 N/A 3.53 0.038 0.021 10.9 1.00 9.17 0.129 0.966 N/A 3.16
0.038 0.021 12.0 0.74 6.17 0.03 1.166 N/A 3.45
TABLE-US-00010 TABLE 10 Tensile Properties of Alloy 3 Microwires
Gauge Diameters (mm) Length Elongation Load (N) Strength (GPa)
Outside Core (mm) (mm) (%) Pre Peak Yield UTS 0.051 0.021 20.00 N/A
N/A N/A 1.456 N/A 4.21 0.051 0.021 20.00 0.67 3.45 N/A 0.992 1.28
2.87 0.054 0.033 25.00 2.50 10.05 N/A 4.538 2.14 4.54 0.053 0.033
30.00 1.81 6.04 N/A 4.389 N/A 5.82 0.043 0.013 11.41 0.95 8.33
0.080 0.5 1.59 4.37 0.043 0.013 15.71 0.84 5.35 0.031 0.457 1.82
3.68 0.043 0.013 11.47 0.74 6.45 0.035 0.526 N/A 4.23 0.057 0.037
12.11 1.55 12.80 0.205 4.454 1.67 4.34 0.057 0.037 11.22 1.38 12.30
0.546 4.287 1.26 4.50 0.057 0.037 12.93 1.00 7.73 1.341 3.282 1.95
4.30 0.054 0.032 10.33 0.80 7.74 0.176 3.56 1.96 4.65 0.054 0.032
11.53 0.57 4.94 0.817 3.623 2.69 5.52 0.054 0.032 10.31 0.82 7.95
0.101 4.212 2.35 5.37 0.044 0.025 11.53 0.55 4.77 0.031 1.418 1.96
2.95
TABLE-US-00011 TABLE 11 Tensile Properties of Alloy 4 Microwires
Gauge Diameters (mm) Length Elongation Load (N) Strength (GPa)
Outside Core (mm) (mm) (%) Pre Peak Yield UTS 0.056 0.031 22.00
0.63 2.86 N/A 2.978 1.61 3.95 0.078 0.033 26.00 0.77 2.96 N/A 3.344
1.19 3.91 0.061 0.038 32.00 1.42 4.44 N/A 4.760 N/A 4.20 0.061
0.038 28.00 1.06 3.79 N/A 5.050 N/A 4.45 0.066 0.042 11.34 0.56
4.94 0.154 4.769 0.89 3.56 0.066 0.042 11.43 0.74 6.47 0.198 4.490
1.20 3.39 0.066 0.042 12.60 0.59 4.68 0.241 4.577 1.31 3.48 0.066
0.042 18.10 0.70 3.87 0.224 4.429 1.03 3.36 0.057 0.033 11.46 0.61
5.32 0.855 2.702 1.71 4.16 0.057 0.033 12.38 1.05 8.48 0.268 3.417
1.20 4.31 0.057 0.033 12.45 0.95 7.63 0.153 3.338 1.48 4.08 0.057
0.033 20.31 0.90 4.43 0.198 3.192 2.24 3.97 0.033 0.014 11.32 0.74
6.54 0.042 0.597 2.54 4.15 0.033 0.014 12.11 0.66 5.45 0.000 0.466
2.23 3.03 0.033 0.014 12.62 0.52 4.12 0.023 0.711 2.23 4.77 0.033
0.014 13.14 0.61 4.64 0.025 0.710 2.45 4.78 0.042 0.026 13.35 0.74
5.54 0.161 1.808 1.90 3.71 0.042 0.026 11.54 0.83 7.19 0.117 1.957
1.57 3.91 0.042 0.026 12.42 0.77 6.20 0.185 1.863 2.46 3.86 0.069
0.044 12.08 0.55 4.55 0.201 4.771 2.46 3.27 0.069 0.044 12.34 0.48
3.89 0.158 4.738 1.56 3.22 0.069 0.044 19.31 0.74 3.83 0.657 4.428
1.99 3.35 0.069 0.044 20.99 0.47 2.24 0.241 3.279 0.71 2.32
TABLE-US-00012 TABLE 12 Tensile Properties of Alloy 5 Microwires
Gauge Failure Diameters (mm) Length Elongation Load Strength (GPa)
Outside Core (mm) (mm) (%) (N) Yield UTS 0.125 0.069 24.99 0.62
2.48 9.89 1.47 2.65 0.115 0.069 12.04 0.52 4.32 10.91 1.41 2.92
0.118 0.068 12.13 0.61 5.03 9.35 1.73 2.58 0.127 0.068 12.71 0.46
3.62 11.63 1.69 3.20 0.124 0.067 15.17 0.51 3.36 11.37 1.23 3.23
0.113 0.065 12.27 0.47 3.83 10.39 0.88 3.13 0.125 0.063 17.73 0.58
3.27 9.66 2.22 3.10 0.117 0.068 12.40 0.36 2.90 10.92 2.89 3.01
0.129 0.066 11.48 0.36 3.14 11.95 3.38 3.50 0.123 0.064 11.42 0.36
3.15 10.33 2.30 3.21 0.119 0.063 21.54 1.26 5.85 9.08 0.82 2.92
0.105 0.063 35.39 2.01 5.68 9.69 1.95 3.11 0.125 0.044 18.35 0.41
2.23 4.86 1.36 3.20 0.115 0.044 17.34 0.49 2.83 5.09 1.24 3.35
0.115 0.043 12.77 0.40 3.13 4.91 1.38 3.38 0.115 0.043 13.10 0.40
3.05 5.10 1.25 3.51 0.076 0.027 10.23 0.26 2.54 2.31 1.58 4.04
0.073 0.029 9.83 0.39 3.97 2.65 2.12 4.02 0.073 0.029 13.50 0.44
3.26 2.23 1.90 3.38 0.036 0.013 14.20 0.70 4.93 0.49 2.15 3.69
0.036 0.013 11.56 0.80 6.92 0.50 2.68 3.75 0.036 0.013 12.36 0.73
5.91 0.54 1.81 4.08 0.036 0.013 10.12 0.94 9.29 0.52 1.91 3.93
0.036 0.013 11.02 0.41 3.72 0.59 3.28 4.47
TABLE-US-00013 TABLE 13 Tensile Properties of Alloy 7 Microwires
Gauge Failure Diameters (mm) Length Elongation Load Strength (GPa)
Outside Core (mm) (mm) (%) (N) Yield UTS 0.081 0.053 9.00 0.45 5.0
8.6 2.13 3.88 0.075 0.054 9.00 0.41 4.6 8.6 1.52 3.75 0.076 0.053
9.00 0.34 3.8 7.8 1.51 3.53 0.081 0.057 13.25 0.36 2.7 7.4 1.21
2.89 0.077 0.057 12.57 0.35 2.8 7.6 1.33 2.98 0.069 0.056 12.21
0.38 3.1 7.3 1.79 2.95 0.075 0.037 13.88 0.33 2.4 5.9 2.57 3.47
0.075 0.038 12.42 0.36 2.9 6.5 2.40 3.76 0.075 0.037 11.14 0.37 3.3
7.1 3.83 4.59
Case Example #3
[0071] Using the Planar Flow Casting process, foils from Alloy 6,
Alloy 8, Alloy 9, Alloy 11, and Alloy 12 were produced. The foil
thickness varied from 22 to 49 .mu.m, foil width varied from 6.5 to
50 mm and the length of the foil produced was .about.100 m to
greater than 1 km per run. Bend ability of foils was estimated by
corrugation method on 1 m long continuous foil using a custom-built
corrugation machine. An image of the foil after corrugation is
presented in FIG. 13. All five alloys have demonstrated Type 4
bending behavior with 0 breaks during corrugation deformation
(Table 14).
TABLE-US-00014 TABLE 14 Results on Bend Ability Testing of Foils
Alloy Bend ability Breaks per 1 m 6 Type 4 0 8 Type 4 0 9 Type 4 0
11 Type 4 0 12 Type 4 0
[0072] The mechanical properties of foils were estimated by
microhardness measurement and tensile testing. Microhardness
testing was performed under a load of 50 g using a M400H1
microhardness tester manufactured by Leco Corporation. Summary of
microhardness data is presented in Table 15. As it can be seen, all
three alloys have shown average microhardness values in a range
from 9.10 to 9.21 GPa. Using a well established relationship where
the tensile strength of a material is .about.1/3 of its hardness,
the strength level of foil material can be estimated. Expected
strength value for all three alloys in foil form is at least 3
GPa.
TABLE-US-00015 TABLE 15 Microhardness of Foil Products (GPa) #
Alloy 6 Alloy 8 Alloy 9 1 9.12 9.02 9.20 2 9.14 9.31 9.03 3 9.21
9.09 9.12 4 8.97 9.32 9.20 5 9.05 9.33 9.10 Average 9.10 9.21
9.13
[0073] Tensile properties of the foils were measured at room
temperature using microscale tensile testing. The testing was
carried out in a commercial tensile stage made by Ernest Fullam,
Inc., which was monitored and controlled by a MTEST Windows
software program. The deformation was applied by a stepping motor
through the gripping system while the load was measured by a load
cell that was connected to the end of one gripping jaw.
Displacement was obtained using a Linear Variable Differential
Transformer (LVDT) which was attached to the two gripping jaws to
measure the change of gauge length. Dogbone specimens with gauge
length of 9 mm and gauge width of 2 mm were cut by EDM. Before
testing, the geometrical parameters of each specimen were carefully
measured at least three times at different locations in the gauge
length. The average values were then recorded including gauge
length, thickness and width and used as input for subsequent stress
and strain calculation. All tests were performed under displacement
control with a strain rate of .about.0.001 s.sup.-1. A summary of
the tensile test results including values of the foil thickness,
width, gauge length, total elongation, breaking load and measure
strength (yield stress and ultimate tensile strength) are given in
Table 16. As can be seen, the tensile strength values vary from
1.77 GPa to 3.13 GPa, the total elongation values vary from 2.6% to
3.6%. The scattering in measured strength values found is believed
to be a result of the macroscale defects in commercially produced
foils as a result of non-optimized process parameters.
TABLE-US-00016 TABLE 16 Tensile Properties of Foil Products
Specimen Size Gauge Elongation Breaking Strength [GPa] Alloy
Thickness Width length [mm] [%] Load [N] Yield UTS Alloy 6 0.024
2.58 10.00 0.27 2.70 124.4 1.73 2.01 0.024 2.58 10.00 0.28 2.80
122.3 1.02 1.98 0.024 2.58 10.00 0.30 3.00 131.9 1.36 2.13 0.024
2.58 10.00 0.36 3.60 141.1 1.30 2.28 Alloy 8 0.023 2.58 10.00 0.26
2.60 105.0 1.07 1.77 0.023 2.58 10.00 0.28 2.80 113.3 1.37 1.91
0.023 2.58 10.00 0.27 2.70 107.2 1.06 1.81 0.023 2.58 10.00 0.26
2.60 107.0 1.11 1.80 Alloy 9 0.250 2.58 10.00 0.30 2.98 89.1 1.14
1.84 0.026 2.61 10.00 0.35 3.50 99.5 1.47 2.87 0.028 2.58 10.00
0.33 3.30 121.5 1.68 3.13 Alloy 11 1.14 0.041 9 0.308 3.42 136.02
1.999 2.91 1.35 0.04 9 0.323 3.59 154.21 1.714 2.86 1.42 0.041 9
0.322 3.58 164.02 1.761 2.82 Alloy 12 1.6 0.036 9 0.247 2.74 127.85
1.432 2.24 1.57 0.036 9 0.262 2.91 130.47 1.609 2.33 1.44 0.036 9
0.253 2.81 119.89 1.595 2.33
Case Example #4
[0074] Using the hyperquenching process, fibers from Alloy 8 were
produced. The fiber thickness varied from 37 to 53 .mu.m, with a
fiber width from 1.4 to 2.3 mm and lengths from 25 to 30 mm. The
ability of the fibers to bend completely flat indicates a ductile
condition whereby high strain can be obtained but not measured by
traditional bend testing. When the fibers are folded completely
around themselves, they experience high strain which can be as high
as 119.8% as derived from complex mechanics. During 180.degree.
bending (i.e. flat) of fibers produced at different conditions,
four types of behavior were observed; Type 1 Behavior--not bendable
without breaking, Type 2 Behavior--bendable on one side with wheel
side out (wheel side), Type 3 Behavior--bendable on one side with
free side out (free side), and Type 4 Behavior--bendable on both
sides. In FIG. 14 a summary of the 180.degree. bending results as a
function of wheel speed during the hyperquenching process is
presented.
[0075] Tensile properties of the fibers that exhibited 100%
bendability were measured at room temperature using microscale
tensile testing. The testing was carried out in a commercial
tensile stage made by Ernest Fullam, Inc., which was monitored and
controlled by a MTEST Windows software program. The deformation was
applied by a stepping motor through the gripping system while the
load was measured by a load cell that was connected to the end of
one gripping jaw. Displacement was obtained using a Linear Variable
Differential Transformer (LVDT) which was attached to the two
gripping jaws to measure the change of gauge length. Before
testing, the geometrical parameters of each specimen were carefully
measured at least three times at different locations in the gauge
length. The average values were then recorded as gauge length,
thickness, and width and used as input for subsequent stress and
strain calculation. All tests were performed under displacement
control, with a strain rate of .about.0.001 s.sup.-1. A summary of
the tensile test results including values of the fiber thickness,
width, gauge length, total elongation, breaking load and measure
strength (yield stress and ultimate tensile strength) is given in
Table 17. The tensile strength values of commercially produced
fibers vary from 0.62 GPa to 1.47 GPa and the total elongation
values vary from 0.67% to 2.56%.
TABLE-US-00017 TABLE 17 Tensile Property of Alloy 8 Fiber Products
Gauge Break Strength Dimensions (mm) Elongation (%) Load (GPa) W t
l Tot Elastic Plastic (N) Yield UTS 2.01 0.042 9.00 0.67 0.67 0.00
61.4 0.73 0.73 2.11 0.043 9.00 1.56 1.11 0.44 69.3 0.52 0.76 1.85
0.039 9.00 1.89 1.11 0.78 105.9 0.82 1.47 1.81 0.041 9.00 1.89 1.89
0.00 73.1 0.83 0.99 2.01 0.039 9.00 2.56 1.11 1.44 102.5 0.69 1.31
1.9 0.041 9.00 1.89 1.11 0.78 90.6 0.87 1.16 2.01 0.039 9.00 1.22
1.11 0.11 70.3 0.89 0.90 2.21 0.037 9.00 1.11 0.56 0.56 62.8 0.46
0.77 1.84 0.043 9.00 2.00 1.22 0.78 77.8 0.64 0.98 1.97 0.04 9.00
2.33 1.22 1.11 103.2 0.74 1.31 1.61 0.037 9.00 2.00 1.11 0.89 77.7
0.83 1.30 2.25 0.044 9.00 1.00 0.89 0.11 67.2 0.54 0.68 1.86 0.039
9.00 2.22 1.56 0.67 85.0 0.77 1.17 2.08 0.046 9.00 1.33 1.33 0.00
75.6 0.69 0.79 2.04 0.044 9.00 2.00 1.33 0.67 82.98 0.68 0.92 1.53
0.039 9.00 0.78 0.56 0.22 40.7 0.54 0.68 2.15 0.053 9.00 1.22 1.11
0.11 78.6 0.56 0.69 1.97 0.042 9.00 1.44 1.22 0.22 68.6 0.60 0.83
1.66 0.045 9.00 1.44 1.33 0.11 46.5 0.61 0.62 1.41 0.038 9.00 1.89
1.56 0.33 45.5 0.75 0.85 1.95 0.049 9.00 1.33 1.11 0.22 72.5 0.55
0.76 1.67 0.041 9.00 1.56 1.11 0.44 73.9 0.75 1.08 1.64 0.043 9.00
2.11 1.56 0.56 69.2 0.74 0.98 1.74 0.041 9.00 1.89 1.56 0.33 53.8
0.67 0.76
[0076] The tensile property values of the commercially produced
fibers are lower than that for laboratory produced ribbons from the
same alloy (Table 6). The main reason for tensile property
deviations appears to be due to a large degree of macrodefects (MD)
in commercially produced fiber that can be clearly seen in FIGS.
15a and 15b. Formation of these macrodefects appears to be a result
of non-optimized hyperquenching process parameters at the initial
commercial trial and can be eliminated by further process
optimization. As can be seen in FIG. 15b, the cross sectional area
is greatly reduced from the average value measured with a
micrometer, which leads to anomalously low tensile strength
values.
Case Example #5
[0077] Using high purity elements, 15 g alloy feedstocks of the
Alloy 1, Alloy 4, and Alloy 8 were weighed out according to the
atomic ratios provided in Table 1. The feedstock material was then
placed into the copper hearth of an arc-melting system. The
feedstock was arc-melted into an ingot using high purity argon as a
shielding gas. The ingot was flipped and re-melted several times to
ensure composition homogeneity. After mixing, the ingot was then
cast in the form of a finger approximately 12 mm wide by 30 mm long
and 8 mm thick. The resulting fingers were then placed in a
melt-spinning chamber in a quartz crucible with a hole diameter of
.about.0.81 mm. The ingots were melted in a using RF induction and
then ejected onto a 245 mm diameter copper wheel. The melt-spinning
parameters are provided in Table 2.
[0078] To examine the nanoscale structures in the melt-spinning
ribbons, TEM foils were prepared using mechanical grinding to less
than 10 .mu.m followed by chemo-mechanical polishing. They were
then ion milled until perforation using a Gatan Precision Ion
Polishing System (PIPS), which was operated at an ion beam energy
level of .about.4 keV. TEM observation was carried out in a JOEL
2010 TEM. The TEM micrographs of ribbon microstructures along with
the corresponding selected area diffraction patterns in the insets
are shown in FIGS. 16a through 16c. As it can be seen, the
nanoscale structures resulting from spinodal decomposition are
interconnected nanoscale phases in a metallic glass matrix which
can range in size from several nanometers to .about.100 nm. For the
studied alloys, it is contemplated, those examples of spinodal
decomposition in various forms were observed including
microconstituent bands, partial decomposition, and full
decomposition when uniform and periodic distribution of the
crystalline phases in the amorphous matrix is formed. Note that
this specific spinodal microconstituent with crystalline spinodally
formed phases in an amorphous matrix is representative of the
identified SGMM structure.
Case Example #6
[0079] Using the Taylor-Ulitovsky process, microwires from Alloy 3
with metal core diameter of 33 .mu.m, from Alloy 4 with metal core
diameter of .about.20 .mu.m and from Alloy 8 with metal core
diameter of .about.20 .mu.m were produced. Samples for TEM analysis
were prepared by first preparing a single layer of uniformly
aligned microwires array which was then fixed onto a TEM grid with
a 2 mm wide slot using very tiny drops of super glue. After curing,
the microwires were ion milled in a Gatan Precision Ion Polishing
System (PIPS), which was operated at an ion beam energy level of
.about.4 keV. The ion beam incident angle was 10.degree. first,
then reduced to 7.degree. after penetration, and finished up by
further reducing the angle to 4.degree. to assure appropriate thin
area for TEM examination. Since ion-milling is a slow polishing
process in which the material is gradually removed from the
currently outmost surface, TEM micrographs obtained from a sharp
nanoscale tip illustrate the microstructures at the microwire
center. Microstructures observed in the microwires are shown in
FIGS. 17ai, 17bi and 17ci.
[0080] The structure consists of a metallic glass matrix containing
a periodic arrangement of clusters which are from 1 to 15 nm thick
and 2 to 60 nm long. The periodic arrangement of clusters, their
shape, and their size are indicative that they formed from a
supersaturated glass matrix as a result of a spinodal
decomposition. The center of microwire has a nanoscale spinodal
glass matrix microconstituent structure, which has been frequently
observed in melt-spun ribbons of the same alloy. The corresponding
SAED patterns, shown in FIG. 17aii, 17bii, 17cii consist of
multiple diffraction rings, including both the first bright
amorphous halo of the glass matrix and the crystalline diffraction
rings of the clusters. The high diffraction intensity of the
amorphous halo indicates that the amorphous phase has a relatively
large volume fraction forming the matrix phase of microwires. The
relatively weak diffraction intensities of the crystalline
diffraction rings suggest that the nanocrystals are dispersed
inside the amorphous matrix.
Case Example #7
[0081] Using the planar flow casting process, foils from Alloy 8
were produced. Samples of less than 10 .mu.m thin for TEM analysis
were prepared using mechanical grinding followed by
chemo-mechanical polishing. They were then ion milled until
perforation using a Gatan Precision Ion Polishing System (PIPS),
which was operated at an ion beam energy level of .about.4 keV. TEM
observation was carried out in a JOEL 2010 TEM. The TEM micrograph
of the foil microstructure along with the corresponding selected
area diffraction pattern are shown in FIGS. 18a and 18b. The
structure consists of a metallic glass matrix containing a periodic
arrangement of clusters which are 5-30 nm in size. The periodic
arrangement of clusters, their shape, and their size are indicative
that they formed from a supersaturated glass matrix as a result of
spinodal decomposition. The corresponding SAED pattern suggests
that the most of the volume remains amorphous, with semicrystalline
clusters that formed and they are in the stage before forming
crystals.
Case Example #8
[0082] Using the hyperquenching process, fibers from Alloy 8 were
produced. Samples of less than 10 .mu.m thin for TEM analysis were
prepared using mechanical grinding followed by chemo-mechanical
polishing. They were then ion milled until perforation using a
Gatan Precision Ion Polishing System (PIPS), which was operated at
an ion beam energy level of .about.4 keV. TEM observation was
carried out in a JOEL 2010 TEM. The TEM micrograph of the fiber
microstructure along with the corresponding selected area
diffraction pattern are shown in FIGS. 19a and 19b. The structure
consists of a metallic glass matrix containing a periodic
arrangement of clusters which are crystalline. The periodic
arrangement of clusters, their shape, and their size are indicative
that they formed from a supersaturated glass matrix as a result of
spinodal decomposition. The corresponding SAED pattern consists of
multiple diffraction rings, including both the first bright
amorphous halo of the glass matrix and the crystalline diffraction
rings of the clusters. The high diffraction intensity of the
amorphous halo indicates that the amorphous phase has a relatively
large volume fraction forming the matrix phase of the fiber.
Case Example #9
[0083] Using high purity elements, a 15 g alloy feedstock of the
Alloy 1 was weighed out according to the atomic ratio's provided in
Table 1. The feedstock material was then placed into the copper
hearth of an arc-melting system. The feedstock was arc-melted into
an ingot using high purity argon as a shielding gas. The ingot was
flipped and re-melted several times to ensure composition
homogeneity. After mixing, the ingot was then cast in the form of a
finger approximately 12 mm wide by 30 mm long and 8 mm thick. The
resulting fingers were then placed in a melt-spinning chamber in a
quartz crucible with a hole diameter of .about.0.81 mm. The ingots
were melted in the crucible using RF induction and then ejected
onto a 245 mm diameter copper wheel at a tangential speed of 16
m/s. Melt-spun ribbons were tested in tension and the surface of a
selected tested ribbon was examined by SEM using secondary electron
imaging. After deformation, high shear band (SB) number per linear
meter was observed on the ribbon surface as shown in FIGS. 20a and
20b. It may be appreciated that in conventional metallic glasses
unconstrained loading conditions such as tensile testing may
usually result in one single runaway shear band that leads to
failure. The number of shear bands per linear meter are
1.06.times.10.sup.5 m.sup.-1 for FIG. 20A and 1.14.times.10.sup.5
m.sup.-1 for FIG. 20B.
Case Example #10
[0084] Using the Taylor-Ulitovsky process, a microwire from Alloy 2
was produced. The microwire was tested in tension and the surface
of the tested wire was examined by SEM using an EVO-60 scanning
electron microscope manufactured by Carl Zeiss SMT Inc. Typical
operating conditions were electron beam energy of 17.5 kV, filament
current of 2.4 A, and spot size setting of 800. Energy Dispersive
Spectroscopy was conducted with an Apollo silicon drift detector
(SDD-10) using Genesis software both of which are from EDAX. The
amplifier time was set to 6.4 micro-sec so that the detector dead
time was about 12-15%. After deformation, high number of shear
bands (SB) per linear meter was observed on the microwire surface
as shown in FIGS. 21a and 21b. Moreover, extensive necking (N) was
detected in the microwire prior to failure (FIG. 21b). In FIGS. 21a
and 21b, the number of shear bands (SB) per linear meter are
2.50.times.10.sup.5 m.sup.-1 and 6.30.times.10.sup.5 m.sup.-1 for
the uniformly deformed region and the necking (N) region in the
tensile tested microwire, respectively.
Case Example #11
[0085] Using the Planar Flow Casting process, a foil from Alloy 1
was produced. The foils were tested by 180.degree. bending and the
surface of the tested specimen was examined by SEM using an EVO-60
scanning electron microscope manufactured by Carl Zeiss SMT Inc.
Typical operating conditions were electron beam energy of 17.5 kV,
filament current of 2.4 A, and spot size setting of 800. Energy
Dispersive Spectroscopy was conducted with an Apollo silicon drift
detector (SDD-10) using Genesis software both of which are from
EDAX. The amplifier time was set to 6.4 micro-sec so that the
detector dead time was about 12-15%. After deformation, high shear
band density, or number of shear bands per unit measurement, was
observed on the foil surface as shown in FIG. 22. Again, as may be
appreciated, in conventional metallic glasses unconstrained loading
conditions such as tensile testing may usually result in one single
runaway shear band. Accordingly, when the foil herein was tested by
180.degree. bending, the number of shear bands per linear meter on
the tension side in FIG. 22 was 3.55.times.10.sup.5 m.sup.-1.
Case Example #12
[0086] Using the hyperquenching process, fibers from Alloy 8 were
produced. The fibers were tested by 180.degree. bending and the
surface of the tested fibers was examined by SEM using an EVO-60
scanning electron microscope manufactured by Carl Zeiss SMT Inc.
Typical operating conditions were electron beam energy of 17.5 kV,
filament current of 2.4 A, and spot size setting of 800. Energy
Dispersive Spectroscopy was conducted with an Apollo silicon drift
detector (SDD-10) using Genesis software both of which are from
EDAX. The amplifier time was set to 6.4 micro-sec so that the
detector dead time was about 12-15%. After deformation, high shear
band (SB) density, or number of shear bands per linear meter, was
observed on the fiber surface as shown in FIG. 23. In spite of the
extensive number of macrodefects (MD), crack initiation was not
observed from stress concentrations indicating that the shear band
deformation mechanisms were active to accommodate deformation in
the defected areas. The surface of the fibers as shown indicated a
number of shear bands per linear meter on the tension side of
6.12.times.10.sup.5 m.sup.-1.
Case Example #13
[0087] Using high purity elements, a 15 g alloy feedstock of Alloy
1 was weighed out according to the atomic ratios provided in Table
1. The feedstock material was then placed into the copper hearth of
an arc-melting system. The feedstock was arc-melted into an ingot
using high purity argon as a shielding gas. The ingot was flipped
and re-melted several times to ensure composition homogeneity.
After mixing, the ingot was then cast in the form of a finger
approximately 12 mm wide by 30 mm long and 8 mm thick. The
resulting fingers were then placed in a melt-spinning chamber in a
quartz crucible with a hole diameter of .about.0.81 mm. The ingots
were melted using RF induction and then ejected onto a 245 mm
diameter copper wheel traveling at a tangential velocity of 10.5
m/s. The ribbon was 1.33 mm wide and 0.07 mm thick. Melt-spun
ribbons were tested in tension and from selected samples TEM foils
were prepared from the gauge of tested specimen using mechanical
grinding to less than 10 .mu.m followed by chemo-mechanical
polishing. They were then ion milled until perforation using a
Gatan Precision Ion Polishing System (PIPS), which was operated at
an ion beam energy level of .about.4 keV. TEM observation was
carried out in a JOEL 2010 TEM.
[0088] Interactions of moving shear bands with the SGMM structure
result in Localized Deformation Induced Changes (LDIC). Identified
LDIC include in-situ nanocrystallization, grain/phase growth, and
phase changes. The TEM micrographs of the deformed ribbon showing
nanocrystallization and grain growth ahead of the propagating shear
band are presented in FIG. 24 represents an example of phase
transformations in the microstructure of deformed ribbon from Alloy
1 caused by propagating shear bands. The SAED patterns A, B, and C
in FIG. 25b, respectively, correspond to the three regions A, B,
and C in FIG. 25a. Changes in both diffraction rings and
diffraction spots in the SAED patterns taken from areas inside and
near propagating shear band as compared to that taken from
undeformed area confirm phase transformations induced by shear
deformation.
Case Example #14
[0089] Using high purity elements, 15 g alloy feedstocks of the
Alloy 1 and Alloy 4 were weighed out according to the atomic
ratio's provided in Table 1. The feedstock material was then placed
into the copper hearth of an arc-melting system. The feedstock was
arc-melted into an ingot using high purity argon as a shielding
gas. The ingot was flipped and re-melted several times to ensure
composition homogeneity. After mixing, the ingot was then cast in
the form of a finger approximately 12 mm wide by 30 mm long and 8
mm thick. The resulting fingers were then placed in a melt-spinning
chamber in a quartz crucible with a hole diameter of .about.0.81
mm. The ingots were melted using RF induction and then ejected onto
a 245 mm diameter copper. Melt-spinning parameters are specified in
Table 2. Melt-spun ribbon was tested in tension and TEM foils of
less than 10 .mu.m thin were prepared from the gauge of tested
specimen using mechanical grinding followed by chemo-mechanical
polishing. They were then ion milled until perforation using a
Gatan Precision Ion Polishing System (PIPS), which was operated at
an ion beam energy level of .about.4 keV. TEM observation was
carried out in a JOEL 2010 TEM.
[0090] The TEM studies show two distinct types of shear band
interactions ISBB and SBAI. In FIG. 26a, a TEM micrograph is shown
illustrating the ISBB mechanism whereby a shear band oriented
.about.40.degree. from the tensile axis (T) is observed in the
middle of the figure moving from left to right. The interaction
between the shear band and the SGMM structure is complex and in
FIG. 26b, the tip of a shear band is shown which clearly
illustrates that after the shear band is blunted, long range stress
fields are created in the direction of the long axis of the shear
band resulting in extended (up to several hundred nm) LDIC
occurring beyond the shear transformation zone. In FIGS. 27a and
27b, details on the SBAI mechanism can be seen, when two shear
bands, after interacting, split into four separate fine branches
which are quickly arrested after a short linear distance.
[0091] Thus, the SGMM structure has the inherent ability to stop a
propagating shear band (ISBB) and that once blunted, shear bands
which are subsequently activated through additional stress are
arrested through SBAI. It is contemplated that the culmination of
these complex interactions then allows for multiple shear banding
and global plasticity observed in the studied alloys in different
product forms.
Case Example #15
[0092] SGMM structure exhibits strain hardening during tensile
testing requiring progressively higher force to maintain continuous
plastic deformation. An example of stress-strain curves for each
type of studied product forms are shown in FIG. 28. The mechanical
properties of the product forms were obtained at room temperature
using microscale tensile testing. The testing was carried out in a
commercial tensile stage made by Ernest Fullam Inc., which was
monitored and controlled by a MTEST Windows software program. The
deformation was applied by a stepping motor through the gripping
system while the load was measured by a load cell that was
connected to the end of one gripping jaw. Displacement was obtained
using a Linear Variable Differential Transformer (LVDT) which was
attached to the two gripping jaws to measure the change of gauge
length. Before testing, the thickness and width of a tensile
specimen was carefully measured at least three times at different
locations in the gauge length. The average values were then
recorded as gauge thickness and width, and used as input parameters
for subsequent stress and strain calculation. The initial gauge
length for tensile testing was set at .about.7 to .about.9 mm with
the exact value determined after the product was fixed, by
accurately measuring the span between the front faces of the two
gripping jaws. All tests were performed under displacement control,
with a strain rate of .about.0.001 s.sup.-1.
[0093] The level of tensile strength and ductility depends on alloy
composition, geometrical parameters of product form, quality of
produced product (controlled by production process optimization for
each alloy) and testing conditions. Nevertheless, as the tensile
curves show, after the yield strength is exceeded, typically at 1.0
to 1.5% of elastic strain, the SGMM alloy continues to gain
strength until failure regardless the product form and quality.
Typically, shear deformation requires dilation and necessitates the
creation of free volume which promotes a local decrease in
viscosity leading to strain softening and catastrophic failure.
Case Example #16
[0094] Using the Taylor-Ulitovsky process, a microwire from Alloy 3
was produced with a metal core diameter at 20 .mu.m. The microwire
was tested in torsion by taking a 40 mm microwire segment and
fixing this to a beam. A dead load of 1.0 g mass was then attached
to the end of the microwire sample which corresponds to a load of
.about.32 MPa. The resulting torsional load was applied by manually
turning the dead load and the total number of turns were counted
and used to calculate the shear strain. The testing results are
presented in Table 18. As shown, the shear strain on breaking is
from 5.79% to 7.03%.
TABLE-US-00018 TABLE 18 Results of Torsion-Tension Testing on
Microwires Wire Break-to- Shear Core Gauge End Number of Strain
Test Diameter Length Length turns on on Breaking ID (.mu.m) (mm)
(mm) breaking (%) 1 20.0 60 55 57 5.97 2 20.0 40 38 41 6.44 3 20.0
50 45 56 7.03
[0095] The surfaces of the torsion tested microwires were examined
in an EVO-60 scanning electron microscope manufactured by Carl
Zeiss SMT Inc. For an Alloy 3 microwire that was tested under
unconstrained tension-torsion loading, at least three levels of
shear bands involving shear band formation, shear band blunting and
shear band arresting with existing shear bands, were formed (FIG.
29). The number of shear bands per linear meter was calculated and
was at 2.25.times.10.sup.6 m.sup.-1. It should be noted that an
even higher level of shear banding may be present but not revealed
due to the spatial resolution available in the SEM. Thus, the shear
band density calculation is conservative.
Shear Band Density
[0096] As can be seen from the above, the alloy chemistry selection
and processing conditions to provide the macroscopic plastic
deformation in metallic glass alloys or metallic glass matrix
composites result in shear band deformation. A shear band, with a
certain thickness in the range of 10 nm to 100 nm, including all
values and ranges therein, is now formed as the result of the
focused shear deformation between two neighboring volumes that are
separated by the band itself. Since it is a through thickness
deformation, the number of shear bands per linear meter that is
developed herein may also be quantified and associated with the
indicated alloys as the volume fraction of the shear bands in a
macroscopically deformed sample.
[0097] The quantification of the number of shear bands per linear
unit, such as linear meter, as an additional characteristic
installed in the alloys disclosed herein may now be identified when
materials are subjected to uniaxial loading conditions when the
majority of shear bands are roughly parallel. In this case, the
shear band density may now be quantified as the number of shear
bands that are crossed by a linear length in a direction that is
locally perpendicular to the shear band traces on the surface. The
number-per-unit-length definition (m.sup.-1) can also be applied to
shear bands that have a roughly uniform orientation in materials
with a thin and wide cross section under uniaxial loading. With
more complex stress states such as a uniaxial load with torsion,
the shear bands will have multiple orientations and even higher
shear band densities which now can be identified using a similar
approach.
[0098] In unconstrained loading, such as in tension, shear bands in
metallic glasses or metallic glass composite materials may be
relatively low. Typically, failure can occur with the nucleation
and resulting propagation of a single shear band with no measurable
global plasticity. Since the typical gauge length is in the range
from 9 mm to 40 mm, the number of shear bands per linear meter may
be understood herein to be from 2.5.times.10.sup.1 m.sup.-1 to
1.1.times.10.sup.2 m.sup.-1.
[0099] In materials including SGMM structure and the alloy
chemistries as identified herein at least two mechanisms have been
developed to promote the creation of relatively high shear band
densities: ISBB and SBAI. As shown by the case examples above,
relatively high number of shear bands per linear meter may be
exhibited in the range of 10.sup.5 to 10.sup.6 m.sup.-1 upon
failure when tensile force is applied at a strain rate of 0.001
s.sup.-1. It is contemplated that achieving relatively lower shear
band densities in the SGMM structure is also achievable since shear
bands are continuously generated after the yield strength is
exceeded until failure. To develop shear band densities, a number
of shear bands per linear meter, in the 10.sup.2 to 10.sup.5
m.sup.-1 range in materials with the SGMM structure, the
deformation may be stopped at the intermediate stage before
failure. Thus, the shear band density range for the SGMM materials
disclosed herein is a shear band density, a number of shear bands
per linear meter, of greater than 1.1.times.10.sup.2 m.sup.-1, such
as in the range of 10.sup.2 m.sup.-1 to 10.sup.7 m.sup.-1,
including all values and ranges therein, in increments of 10
m.sup.-1. Accordingly, the present invention relates to the
metallic alloy chemistries herein, which are susceptible to SGMM
structural formation, together with the ability to undergo ISBB
and/or SBAI, to provide shear band densities, a number of shear
bands per linear meter, of greater than 1.1.times.10.sup.2 m.sup.-1
to 10.sup.7 m.sup.-1.
[0100] The foregoing description of several methods and embodiments
has been presented for purposes of illustration. It is not intended
to be exhaustive or to limit the claims to the precise steps and/or
forms disclosed, and obviously many modifications and variations
are possible in light of the above teaching. It is intended that
the scope of the invention be defined by the claims appended
hereto.
* * * * *