U.S. patent application number 15/207544 was filed with the patent office on 2017-04-20 for refractory metal ceramics and methods of making thereof.
This patent application is currently assigned to The Government of the United States of America, as represented by the Secretary of the Navy. The applicant listed for this patent is The Government of the United States of America, as represented by the Secretary of the Navy, The Government of the United States of America, as represented by the Secretary of the Navy. Invention is credited to Teddy M. Keller, Manoj K. Kolel-Veetil, Matthew Laskoski, Andrew P. Saab.
Application Number | 20170107157 15/207544 |
Document ID | / |
Family ID | 48870482 |
Filed Date | 2017-04-20 |
United States Patent
Application |
20170107157 |
Kind Code |
A1 |
Keller; Teddy M. ; et
al. |
April 20, 2017 |
REFRACTORY METAL CERAMICS AND METHODS OF MAKING THEREOF
Abstract
A composition having nanoparticles of a refractory-metal carbide
or refractory-metal nitride and a carbonaceous matrix. The
composition is not in the form of a powder. A composition
comprising a metal component and an organic component. The metal
component is nanoparticles or particles of a refractory metal or a
refractory-metal compound capable of decomposing into refractory
metal nanoparticles. The organic component is an organic compound
having a char yield of at least 60% by weight or a thermoset made
from the organic compound. A method of combining particles of a
refractory metal or a refractory-metal compound capable of reacting
or decomposing into refractory-metal nanoparticles with an organic
compound having a char yield of at least 60% by weight to form a
precursor mixture.
Inventors: |
Keller; Teddy M.; (Fairfax
Station, VA) ; Saab; Andrew P.; (Washington, DC)
; Laskoski; Matthew; (Springfield, VA) ;
Kolel-Veetil; Manoj K.; (Alexandria, VA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
The Government of the United States of America, as represented by
the Secretary of the Navy |
Arlington |
VA |
US |
|
|
Assignee: |
The Government of the United States
of America, as represented by the Secretary of the Navy
Arlington
VA
|
Family ID: |
48870482 |
Appl. No.: |
15/207544 |
Filed: |
July 12, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14245111 |
Apr 4, 2014 |
9403723 |
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15207544 |
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13749794 |
Jan 25, 2013 |
8822023 |
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14245111 |
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61693930 |
Aug 28, 2012 |
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61669201 |
Jul 9, 2012 |
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61640744 |
May 1, 2012 |
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61590852 |
Jan 26, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C04B 35/58035 20130101;
C04B 35/6269 20130101; C04B 2235/38 20130101; C04B 2235/663
20130101; C04B 2235/658 20130101; C04B 2235/44 20130101; C01P
2002/72 20130101; C04B 35/5622 20130101; C04B 2235/80 20130101;
C04B 35/66 20130101; C01B 21/0617 20130101; C04B 2235/404 20130101;
C01P 2004/80 20130101; C04B 2235/6562 20130101; C04B 35/657
20130101; C04B 2235/3839 20130101; C04B 2235/3843 20130101; C01B
21/0765 20130101; C04B 35/83 20130101; C04B 2235/3886 20130101;
C04B 2235/5454 20130101; C04B 35/5611 20130101; C04B 35/524
20130101; C04B 2235/5248 20130101; C04B 2235/425 20130101; C04B
2235/524 20130101; C04B 35/62675 20130101; C04B 2235/3847 20130101;
C04B 2235/6581 20130101; C04B 2235/5288 20130101; C04B 35/5626
20130101; C04B 2235/526 20130101; C04B 35/80 20130101; C04B 2235/46
20130101; C04B 35/58007 20130101; C04B 35/58014 20130101; C01P
2004/64 20130101; C01B 32/914 20170801; C01B 21/062 20130101; C01B
21/0761 20130101; C04B 2235/48 20130101; C01P 2004/03 20130101;
C04B 35/52 20130101; C04B 35/62645 20130101; C04B 35/76 20130101;
C04B 2235/6586 20130101; C04B 35/806 20130101; C04B 2235/422
20130101; C04B 35/58028 20130101; C01B 32/921 20170801; B82Y 30/00
20130101; C04B 35/522 20130101; C04B 35/5607 20130101; C04B 35/6265
20130101; C04B 35/62695 20130101 |
International
Class: |
C04B 35/58 20060101
C04B035/58; C04B 35/80 20060101 C04B035/80; C04B 35/76 20060101
C04B035/76; C04B 35/56 20060101 C04B035/56; C04B 35/524 20060101
C04B035/524 |
Claims
1. A composition comprising: a refractory-metal hydride; and an
organic compound having a char yield of at least 60% by weight.
2-3. (canceled)
4. The composition of claim 1, wherein the refractory-metal hydride
is titanium hydride, zirconium hydride, hafnium hydride, tungsten
hydride, niobium hydride, molybdenum hydride, chromium hydride,
tantalum hydride, or vanadium hydride.
5. The composition of claim 1, wherein the organic compound:
contains only carbon and hydrogen; contains aromatic and acetylene
groups; contains only carbon, hydrogen, and nitrogen or oxygen;
contains no oxygen; or contains a heteroatom other than oxygen.
6. The composition of claim 1, wherein the organic compound is
1,2,4,5-tetrakis(phenylethynyl)benzene or a prepolymer thereof,
N,N'-(1,4-phenylenedimethylidyne)-bis-(3-ethynylaniline),
dianilphthalonitrile, or resorcinol phthalonitrile.
7. (canceled)
8. The composition of claim 1, wherein the composition comprises a
material selected from the group consisting of fibers, carbon
fibers, ceramic fibers, and metal fibers.
9. A composition comprising: a refractory-metal hydride; and a
thermoset made from an organic compound having a char yield of at
least 60% by weight.
10. The composition of claim 9, wherein the refractory-metal
hydride is titanium hydride, zirconium hydride, hafnium hydride,
tungsten hydride, niobium hydride, molybdenum hydride, chromium
hydride, tantalum hydride, or vanadium hydride.
11. The composition of claim 9, wherein the organic compound:
contains only carbon and hydrogen; contains aromatic and acetylene
groups; contains only carbon, hydrogen, and nitrogen or oxygen;
contains no oxygen; or contains a heteroatom other than oxygen.
12. The composition of claim 9, wherein the organic compound is
1,2,4,5-tetrakis(phenylethynyl)benzene or a prepolymer thereof,
N,N'-(1,4-phenylenedimethylidyne)-bis-(3-ethynylaniline),
dianilphthalonitrile, or resorcinol phthalonitrile.
13. The composition of claim 9, wherein the composition comprises a
material selected from the group consisting of fibers, carbon
fibers, ceramic fibers, and metal fibers.
14. A composition comprising: nanoparticles or particles of a
refractory metal; and a thermoset made from an organic compound
having a char yield of at least 60% by weight; wherein the
composition comprises at least 10% by weight of the nanoparticles
or particles of the refractory metal.
15. The composition of claim 14, wherein the refractory metal is
titanium.
16. The composition of claim 14, wherein the refractory metal is
selected from the group consisting of a group IV-VI transition
metal, zirconium, hafnium, tungsten, niobium, molybdenum, chromium,
tantalum, and vanadium.
17. The composition of claim 14, wherein the organic compound:
contains only carbon and hydrogen; contains aromatic and acetylene
groups; contains only carbon, hydrogen, and nitrogen or oxygen;
contains no oxygen; or contains a heteroatom other than oxygen.
18. The composition of claim 14, wherein the organic compound is
1,2,4,5-tetrakis(phenylethynyl)benzene or a prepolymer thereof,
N,N'-(1,4-phenylenedimethylidyne)-bis-(3-ethynylaniline),
dianilphthalonitrile, or resorcinol phthalonitrile.
19. The composition of claim 14, wherein the composition comprises
a material selected from the group consisting of fibers, carbon
fibers, ceramic fibers, and metal fibers.
20. The composition of claim 14, wherein the composition comprises
at least 70% by weight of the nanoparticles or particles of the
refractory metal.
21. A composition comprising: nanoparticles or particles of a
refractory metal; and an organic compound having a char yield of at
least 60% by weight; wherein the composition comprises at least 10%
by weight of the nanoparticles or particles of the refractory
metal.
22. The composition of claim 21, wherein the refractory metal is
titanium.
23. The composition of claim 21, wherein the refractory metal is
selected from the group consisting of a group IV-VI transition
metal, zirconium, hafnium, tungsten, niobium, molybdenum, chromium,
tantalum, and vanadium.
24. The composition of claim 21, wherein the metal component is
selected from the group consisting of particles of the refractory
metal, tungsten powder, and tantalum powder.
25. The composition of claim 21, wherein the organic compound:
contains only carbon and hydrogen; contains aromatic and acetylene
groups; contains only carbon, hydrogen, and nitrogen or oxygen;
contains no oxygen; or contains a heteroatom other than oxygen.
26. The composition of claim 21, wherein the organic compound is
1,2,4,5-tetrakis(phenylethynyl)benzene or a prepolymer thereof,
N,N'-(1,4-phenylenedimethylidyne)-bis-(3-ethynylaniline),
dianilphthalonitrile, or resorcinol phthalonitrile.
27. The composition of claim 21, wherein the composition comprises
a material selected from the group consisting of fibers, carbon
fibers, ceramic fibers, and metal fibers.
28. The composition of claim 21, wherein the composition comprises
at least 70% by weight of the nanoparticles or particles of the
refractory metal.
Description
[0001] This application is a divisional application of pending U.S.
patent application Ser. No. 14/245,111 filed on Apr. 4, 2014, which
a divisional application of pending U.S. Pat. No. 8,822,023 issued
on Sep. 2, 2014, which claims the benefit of U.S. Provisional
Application No. 61/590,852, filed on Jan. 26, 2012, U.S.
Provisional Application No. 61/640,744, filed on May 1, 2012, U.S.
Provisional Application No. 61/669,201, filed on Jul. 9, 2012, and
U.S. Provisional Application No. 61/693,930, filed on Aug. 28,
2012. The provisional applications and all other publications and
patent documents referred to throughout this nonprovisional
application are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present disclosure is generally related to synthesis of
refractory metal ceramics, such as titanium carbide and titanium
nitride.
DESCRIPTION OF RELATED ART
[0003] Refractory transition metal carbides (MC) and nitrides have
the highest known melting points (2600-3900.degree. C.) and also
outstanding hardness, chemical inertness, wear resistance,
electrocatalytic activity, and neutron absorption ability. Films,
fibers, and powders of these ceramics have been made from polymeric
precursors, but large monolithic shapes elude the polymeric method.
Refractory MCs are typically prepared by powder metallurgy methods
such as hot press sintering. Ordinarily, metal carbide ceramics
made by these techniques, which are both energy and time intensive,
result in brittle materials, owing partly to the large granular
structure and the inconsistency in the MC particle sizes. Powdered
metal nitrides can be produced from metal particles in a flow of
nitrogen but have to be formulated into shaped components under
pressure and high temperatures.
[0004] Since the late 1960s, there has been an interest in high
temperature ceramic materials for such applications as
grinding/machining, ball bearings, armors, fibers, and turbine
blades but structural applications have been lacking due to their
brittleness and weakness in shear and tension. More recently, there
has been a resurgence of interest in ultra-high temperature
materials for hypersonic vehicles (Mach 5-20) with new propulsion
and structural concepts. These vehicles include ballistic missiles,
hypersonic cruise missiles, re-entry vehicles, space access
vehicles, interceptor missiles, and hypersonic cruise aircraft,
which can be easily divided into single-use expendable and reusable
systems. These expendable and reusable space vehicles, next
generation rocket engines, and hypersonic spacecraft need tough
materials and structural components capable of operating at
temperatures in excess of 2200.degree. C. and must meet several
requirements simultaneously, such as high melting temperature, high
strength, and environmental resistance (oxidative resistance). A
hypersonic commercial aircraft would be able to travel from New
York to Los Angeles in less than an hour. Thus, current increasing
interest in hypersonic vehicles and weapons points to the need for
new ultra-high temperature materials for wing leading edges and
nose tips along with propulsion system components.
[0005] For these applications, progress will come when materials
are developed that can be easily processed into shaped components
with the required thermomechanical and thermochemical
characteristics and properties and that can perform without some
form of cooling at temperatures exceeding 2200.degree. C. Such
materials do not currently exist. The refractory interstitial
transition metal carbides are extremely hard, inert, and refractory
materials. Unfortunately, they are also brittle and difficult to
machine.
[0006] There is current interest in metal carbides with small
particle size and high surface area such as tungsten carbide (WC)
due to their potential application as catalysts. Selected MCs such
as WC with outstanding catalytic properties similar to Pt promise
to be an inexpensive alternative to the expensive noble metals such
as Pt and Pd with possibly even superior properties due to their
ability to withstand high temperatures and resistance to poisoning,
which is common with the noble metals. The anodic chemistry of the
direct methanol fuel cell (DMFC) requires the oxidation of methanol
and the decomposition of water to produce protons, electrons, and
CO.sub.2. Strong chemisorption of CO on the noble metals makes
these electrocatalysts susceptible to CO poisoning, blocking the
active site for methanol oxidation. Consequently, the discovery of
less expensive catalysts such as WC, which is more CO tolerant, has
helped to commercialize the DMFC.
BRIEF SUMMARY
[0007] Disclosed herein is a composition comprising nanoparticles
of a refractory-metal carbide or refractory-metal nitride and a
carbonaceous matrix. The composition is not in the form of a
powder.
[0008] Also disclosed herein is a composition comprising a metal
component and an organic component. The metal component is selected
from nanoparticles or particles of a refractory metal and a
refractory-metal compound capable of decomposing into
refractory-metal nanoparticles. The organic component is selected
from an organic compound having a char yield of at least 60% by
weight and a thermoset made from the organic compound.
[0009] Also disclosed herein is a method comprising combining
particles of a refractory metal or a refractory-metal compound
capable of reacting or decomposing into refractory-metal
nanoparticles with an organic compound having a char yield of at
least 60% by weight to form a precursor mixture.
[0010] Also disclosed herein is a method comprising: providing a
precursor mixture of particles of a refractory metal or a
refractory-metal compound capable of decomposing into
refractory-metal nanoparticles and an organic compound; heating the
precursor mixture in an inert atmosphere at elevated pressure and
at a temperature that causes decomposition of the refractory-metal
compound to form refractory-metal nanoparticles to form a metal
nanoparticle composition; and heating the metal nanoparticle
composition in an inert atmosphere, argon, or nitrogen at a
temperature that causes formation of a ceramic comprising
nanoparticles of a refractory-metal carbide or a refractory-metal
nitride in a carbonaceous matrix. The organic compound has a char
yield of at least 60% by weight when heated at the elevated
pressure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] A more complete appreciation will be readily obtained by
reference to the following Description of the Example Embodiments
and the accompanying drawings.
[0012] FIG. 1 schematically illustrates a process for forming the
disclosed compositions.
[0013] FIG. 2 schematically illustrates metal nanoparticles 10
embedded in a thermoset matrix 20.
[0014] FIG. 3 schematically illustrates the transfer 40 of carbon
atoms from the carbon matrix 30 to the nanoparticles 50.
[0015] FIG. 4 schematically illustrates metal carbide nanoparticles
60 in a carbonaceous matrix 70.
[0016] FIG. 5 shows an X-ray diffraction analysis (XRD) of a sample
containing TiC nanoparticles.
[0017] FIG. 6 shows an XRD of a sample containing TiN
nanoparticles.
[0018] FIG. 7 shows an XRD of a sample containing ZrC
nanoparticles.
[0019] FIG. 8 shows an XRD of a sample containing ZrN
nanoparticles.
[0020] FIG. 9 shows an XRD of a sample containing HfC
nanoparticles.
[0021] FIG. 10 shows an XRD of a sample containing TiC
nanoparticles after heating to 1600.degree. C.
[0022] FIG. 11 shows a scanning electron micrograph (SEM) of a
sample containing TiC nanoparticles.
[0023] FIG. 12 shows an XRD of a sample containing WC
nanoparticles.
[0024] FIG. 13 shows an SEM of a sample containing WC
nanoparticles.
DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS
[0025] In the following description, for purposes of explanation
and not limitation, specific details are set forth in order to
provide a thorough understanding of the present disclosure.
However, it will be apparent to one skilled in the art that the
present subject matter may be practiced in other embodiments that
depart from these specific details. In other instances, detailed
descriptions of well-known methods and devices are omitted so as to
not obscure the present disclosure with unnecessary detail. Any
numerical range disclosed herein includes every number within the
range as well as those within rounding error of the end point of
the range.
[0026] Disclosed herein is (1) a method for the in situ formation
of refractory metal carbide (Groups IV-VI) ceramics with or without
a carbon matrix in one step affording a shaped composition with
structural integrity, (2) various refractory metal
nanoparticle-precursor/thermoset compositions and metal-carbide and
metal carbide-carbon matrix compositions at multiple stages, (3)
the nanoparticle metal-carbide and nanoparticle metal
carbide-carbon matrix compositions, (4) nanoparticle metal
nitride-carbon matrix compositions, (5) fiber reinforced
metal-carbide and metal carbide-carbon matrix composites, and (6)
fiber reinforced metal nitride-carbon matrix composites.
[0027] The methods may produce refractory metal (Ti, W, Nb, Zr, Mo,
Cr, V, Ta, and Hf) carbides and nitrides in shaped solid
configurations from metal nanoparticles. Mixed phases can also be
produced. The ceramics are produced as nanoparticles. When a) any
metal compound that decomposes into highly reactive metal
nanoparticles is combined with b) carbon precursors that melt and
only contain carbon and hydrogen, the combination may be thermally
converted to c) a solid shape containing high yields of pure metal
carbides and/or metal nitrides. The appropriate metal nanoparticles
are formed in situ from the thermal decompositions of metal
carbonyls and metal hydrides within the melt of the carbon
precursor. The carbon sources may be melt processable
aromatic-containing acetylenes or low molecular weight polymers
that exhibit extremely high char yields. The carbon precursor may
contain only C and H to insure that heteroatoms are not
incorporated into the interstitial sites of the metal nanoparticles
during the reaction to produce the metal carbide and/or metal
nitride. The metal carbides or metal nitrides may form between
600-1000.degree. C. under inert conditions from reaction of the
highly reactive metal nanoparticles with either the carbon
precursor (degradation above 500.degree. C.) or nitrogen gas,
respectively, but in some cases the reaction can be made to occur
faster at higher temperatures. The temperatures at which the
synthetic process occurs may be well below those normally
associated with the formation of carbide and nitride ceramics. When
an excess of the carbon precursor is used, the individual formed
ceramic particles may be glued or bound together with the resulting
nanostructured or amorphous elastic carbon to afford structural
integrity.
[0028] In the methods disclosed herein (FIG. 1), metal compounds
are combined with a carbon precursor. The carbon precursors are
compounds such as polymers or resins with functional unsaturation
to interact with the metal nanoparticles that form from the metal
compounds. The unsaturations also permit the carbon precursor to
undergo conversion from the melt to form thermosets or crosslinked
polymers. A typical composition includes the carbon precursor and
the metal compound or multiple metal compounds. Upon heating this
composition, the carbon precursor melts at its melting point and
may be thermally converted to a shaped solid thermoset 20 through
reaction of the unsaturated sites. It is possible that during this
step or a subsequent step the metal compound thermally decomposes
into metal nanoparticles 10 or the metal powder reacts with the
organic component to form nanoparticles which are embedded in the
solid thermoset (FIG. 2). Alternatively, the formation of the metal
nanoparticles may occur later during the next step in the process,
which is extended heat treatment at higher temperatures. Thermal
treatment of the thermoset above 500.degree. C. results in
carbonization of the carbon precursor 30 yielding carbon atoms that
react 40 in an argon atmosphere with the interstitial sites of the
metal nanoparticles 50 affording the metal carbides 60, which are
embedded in the excess carbon 70 (FIGS. 3-4). When the same
reaction is performed in a flow of nitrogen or when the organic
compound contains nitrogen, metal nitride-carbon matrix
compositions are also formed in a stoichiometric ratio. Depending
on the shape and thickness of the composition, both metal nitride
and metal carbide may form with the metal carbide on the interior
part of composition where the nitrogen cannot be in intimate
contact.
[0029] Reaction of metal salts and decomposition to metal
nanoparticles may occur at lower temperatures with reaction to the
ceramics occurring by 1200.degree. C. but higher temperatures may
be needed at least to 1600.degree. C. for metal powders of micron
size. Smaller size particles may react faster and be totally
consumed at lower temperatures relative to the larger particle size
powders. The particle size of the metal carbide/nitride can be
controlled as a function of the upper temperature treatment with
higher exposure temperatures affording larger particle size
ceramics.
[0030] Regardless of the ratio of metal compound to carbon source,
the metal carbides or nitrides may form as nanoparticles. This is a
highly desirable result, as it is generally accepted that
homogeneous nanoparticle composites of ceramics will have better
properties than their much more common microparticle counterparts.
An excess of carbon atoms can be made available for reaction with
the metal content and to ensure the formation of a carbon matrix in
which the refractory metal carbides are bound, or the reaction can
be conducted stoichiometrically to yield only the metal carbide.
The amount of metal carbide and carbon within the resulting
composition can be varied based on the quantity of each individual
component (metal compound and melt processable carbon compound)
mixed for usage in the precursor composition. When the reaction is
performed in a nitrogen atmosphere, the metal nanoparticle may
preferentially react with the nitrogen relative to the carbon
affording the corresponding metal nitrides in pure form.
[0031] Carbon, ceramic, and metal fibers may be incorporated into
various mixtures of precursor compositions composed of metal
compounds of Groups IV-VI and the acetylene-containing aromatic
compounds or polymers (carbon source) and the resulting
fiber-containing mixture is converted to a shaped solid at
temperatures below 500.degree. C. followed by heating to
temperatures around 1000-1200.degree. C. yielding a fiber
reinforced metal carbide-carbon matrix composite. The precursor
composition (metal salt and carbon precursor) described above are
mixed with continuous fibers or chopped fibers and heated until
conversion to the shaped thermoset forms. Further heating above
500.degree. C. in an inert atmosphere (argon) results in the
formation of the fiber reinforced refractory metal carbide-carbon
matrix composites. Depending on the ceramic being formed, the
tough, solid shaped composite can be used for structural
applications in excess of 3000.degree. C. The composite may be
exposed to an upper temperature for which it is going to be used so
that the physical properties may remain intact and not change. The
precursor composition can contain a combination of different
refractory metal compounds that will lead to a mixture of ceramics
in the composite, which could be beneficial for specific
applications.
[0032] As noted above, when the metal compound and carbon precursor
composition are heated in a nitrogen atmosphere, metal nitride
ceramics may form with a direct incorporation of nitrogen into the
lattices of the metal atoms/nanoparticles. Thus, by changing the
atmosphere for performing the reaction, one can selectively form
either the metal-carbide carbon-matrix composition or the
metal-nitride carbon-matrix composition or combination thereof.
When the fiber experiments are carried out in a nitrogen
atmosphere, fiber reinforced refractory metal nitride-carbon matrix
composites will be formed especially on the outer surface. The
composite may have outstanding oxidative stability and temperature
capabilities in excess of 3000.degree. C.
[0033] The process is outlined in FIG. 1 and schematically
illustrated in FIGS. 2-4. Any reactions described are not limiting
of the presently claimed methods and compositions. It is speculated
that the nanoparticle form of the refractory metal activates its
reaction with the carbon source, thereby lowering the temperature
of metal carbide or metal nitride formation. Moreover, by varying
the amount of metal compound that forms reactive metal
nanoparticles relative to the carbon precursor, the amount of metal
carbide or metal nitride can be changed with respect to the amount
of carbon matrix in order to vary the properties of the resulting
composite. The metal carbide or metal nitride carbon-matrix
composites are expected to show enhanced toughness, owing to the
presence of the relatively elastic carbon, which would exist in
forms ranging from amorphous to nanotube to graphitic carbon.
[0034] The native presence of an "elastic" carbon matrix may allow
for toughening of the inherently brittle sintered ceramics. The
carbon may permit operation of the toughened ceramic at extremely
high temperatures, owing to carbon's high melting point
(>3000.degree. C.). Ceramic/carbon-matrix compositions are
currently sought for these reasons, and the present method may
permit straightforward preparation of these composites in a single
step for the first time, in contrast to the traditional means of
first forming the ceramic powder and then preparing the
carbon-matrix composite under sintering conditions. Also, the ratio
of ceramic to carbon is easily tuned based only on the ratio of
metal-compound or metal powder to carbon-precursor.
[0035] Fiber-reinforced refractory metal carbide and metal nitride
carbon matrix composites may exhibit outstanding mechanical
properties for usage under extreme environmental high temperature
conditions. Finely divided fiber reinforced refractory metal
carbide carbon composites can allow the consolidation of fully
dense shaped solid components with extreme fracture resistance for
uses in high stress and temperature applications such as advanced
engine components for hypersonic vehicles and automobiles, where
increased operation temperature and mechanical integrity could
translate into tremendous economic advantages. Such tough, easily
shaped ceramic composites are critical to the next generation of
jet engines, which are being designed to operate at higher internal
temperatures and stresses than those in current service, and in
advanced automobile engines and supporting components. High
temperature ship deck plates could be readily fabricated for
aircraft carriers needing the superior heat resistant properties of
the metal carbide and/or metal nitride ceramic-carbon composites.
Also, lightweight, tough, and hard ceramics easily made in
controllable forms could be very important for the fabrication of
superior military armor; again fabricated in a mold in a shaped
structure. Tungsten carbide (WC) is currently used as warheads for
munitions due to its superior hardness and high density and would
be more economical to produce by the WC formulated from the
precursor compositions disclosed herein. The ability to fabricate
tough, shaped refractory metal carbide or metal nitride components
in one step enhances their importance due to the economic
advantages and the elimination of machining to a shaped
component.
[0036] In the first step of the method, two components are combined
and may be thoroughly mixed. One is a metal component which may be
a refractory-metal compound capable of decomposing into refractory
metal nanoparticles or particles of a refractory metal. Any
refractory metal may be used, including but not limited to a group
IV-VI transition metal, titanium, zirconium, hafnium, tungsten,
niobium, molybdenum, chromium, tantalum, or vanadium. When a pure
metal is used, it may be in the form of nanoparticles or other
particles such as a powder. When such metal particles are used, the
metal may directly react with the organic component. Suitable
powders include, but are not limited to, tungsten and tantalum.
[0037] Instead of pure metal, a compound containing the metal atom
may be used. Such compounds decompose at elevated temperatures,
releasing the metal atoms so that they may react with the organic
component. Suitable such compounds include, but are not limited to,
a salt, a hydride, a carbonyl compound, or a halide of the
refractory metal. Examples include titanium hydride, zirconium
hydride, and hafnium hydride. Other examples and embodiments of
types of compounds which may be used with the metals disclosed
herein may be disclosed in U.S. Pat. Nos. 6,673,953; 6,770,583;
6,846,345; 6,884,861; 7,722,851; 7,819,938; 8,277,534.
[0038] The other component is an organic compound that has a char
yield of at least 60% by weight. The char yield may also be as high
as at least 70%, 80%, 90%, or 95% by weight. The char yield of a
potential compound may be determined by comparing the weight of a
sample before and after heating to at least 1000.degree. C. for at
least 1 hr in an inert atmosphere such as nitrogen or argon. Any
such compounds with high char yields may be used as the charring
may play a role in the mechanism of the reactions. This char yield
may be measured at an elevated pressure to be used when a heating
step is also performed at such pressure. Thus, a compound having a
low char yield at atmospheric pressure but having a high char yield
under the conditions that the disclosed methods are performed may
be suitable.
[0039] Certain organic compounds may exhibit any of the following
characteristics, including mutually consistent combinations of
characteristics: containing only carbon and hydrogen; containing
aromatic and acetylene groups; containing only carbon, hydrogen,
and nitrogen or oxygen; containing no oxygen; and containing a
heteroatom other than oxygen. It may have a melting point of at
most 400.degree. C., 350.degree. C., 300.degree. C., 250.degree.
C., 200.degree. C. or 150.degree. C. and the melting may occur
before polymerization or degradation of the compound. Examples of
organic compounds include, but are not limited to,
1,2,4,5-tetrakis(phenylethynyl)benzene (TPEB),
N,N'-(1,4-phenylenedimethylidyne)-bis-(3-ethynylaniline) (PDEA),
N,N'-(1,4-phenylenedimethylidyne)-bis(3,4-dicyanoaniline)
(dianilphthalonitrile), and 1,3-bis(3,4-dicyanophenoxy)benzene
(resorcinol phthalonitrile). Prepolymers may also be used, such as
a prepolymer of TPEB or other suitable organic compounds. Different
compounds can be blended together and/or reacted to a prepolymer
stage before usage as the organic compound of the precursor
composition. The presence of nitrogen atoms in the organic compound
may produce metal nitrides in the ceramic without the use of a
nitrogen atmosphere.
[0040] More than one metal, metal compound, and/or organic compound
may be used. Two or more different metals may be used to produce
two different metal carbides and/or nitrides in the ceramic. Also,
in some cases only one compound may be used when the metal
component and the organic component are the same compound. Such
compounds may be high in carbon and hydrogen to produce a high char
yield, but also have a refractory metal bound to the compound.
[0041] An optional third component in the precursor materials is a
plurality of fibers or other fillers. Examples of fibers include,
but are not limited to, carbon fibers, ceramic fibers, and metal
fibers. The fibers may be of any dimension that can be incorporated
into the mixture and may be cut or chopped to shorter
dimensions.
[0042] The precursor mixture, which may be mixed in a melt stage,
then undergoes a heating step to form a metal nanoparticle
composition. This may be performed while the mixture is in a mold.
This will allow the final product to have the same shape as the
mold, as the mixture will melt if not already liquid and fill the
mold during the heating, and retain its shape when the ceramic is
formed. The precursor mixture is heated in an inert atmosphere at a
temperature that causes decomposition of the refractory-metal
compound to form refractory-metal nanoparticles. If the organic
compound is volatile, the heating may be performed under pressure
to avoid evaporation of the organic compound. As used herein, this
heating step includes the formation of nanoparticles from a metal
powder. As the reaction proceeds from the metal powder, the metal
particles will become smaller. It is not necessary to verify that
the nanoparticles are formed in order to continue with the method.
However, any known technique for detecting nanoparticles such as
SEM or x-ray diffraction analysis (XRD) may be used if desired to
verify that the metal component suitably produces nanoparticles.
Suitable heating temperatures include, but are not limited to,
150-500 or 600.degree. C.
[0043] Heating the precursor may also cause the polymerization of
the organic compound to a thermoset. The metal nanoparticles 10
would then be dispersed throughout the thermoset 20 as shown in
FIG. 2. The organic compound may also polymerize before the
nanoparticles are formed. A thermoset having the refractory-metal
compound or particles (including nanoparticles) of refractory metal
dispersed throughout may be used as a final product. The thermoset
may also be machined to a desired shape, followed by heating to
form a ceramic as described below.
[0044] The metal source may be homogeneously distributed or
embedded in the thermoset as an intermediate shaped solid. At this
stage, the composition may have a shape that it will retain upon
further heating and conversion to the ceramic from reaction of the
metal source with the developing carbon matrix.
[0045] The precursor mixture may be consolidated to a shaped solid
component under pressure to promote intimate contact of the
reactants to provide a very dense ceramic solid or to densify the
final product. The precursor mixture may be compacted under
exterior pressure, removed from the pressure, and then heated to a
thermoset followed by conversion to the ceramic. Alternatively, the
precursor mixture may be compacted under exterior pressure and the
pressure maintained while heating to the thermoset and ceramic.
[0046] In a second heating step, the metal nanoparticle composition
is heated to form a ceramic. The heating is performed at a
temperature that causes formation of nanoparticles of a
refractory-metal carbide or a refractory-metal nitride 60 in a
carbonaceous matrix 70 (FIG. 4). The carbonaceous matrix may
comprise graphitic carbon, carbon nanotubes, and/or amorphous
carbon. If an inert atmosphere such as argon is used, metal carbide
nanoparticles may be formed. If nitrogen is present, metal nitride
nanoparticles may be formed. There may be a higher concentration of
nitrides on the surface than in the interior. Suitable heating
temperatures include, but are not limited to, 500-1900.degree.
C.
[0047] Nanoparticles that may be formed include, but are not
limited to, titanium carbide, titanium nitride, zirconium carbide,
zirconium nitride, hafnium carbide, hafnium nitride, tungsten
carbide, tungsten nitride, tantalum carbide, and tantalum nitride.
The presence and composition of the metal carbide or nitride
particles may be verified by any known technique for detecting
nanoparticles such as SEM or XRD. The nanoparticles may have an
average diameter of less than 100 nm, 50 nm, or 30 nm. They may be
generally spherical in shape or may be non-spherical, such as
nanorods.
[0048] The ceramic may include any amount of nanoparticles,
including but not limited to, at least 5%, 10%, 20%, 30%, 40%, 50%,
60%, 70%, 80%, 90%, 95%, or 99% by weight of nanoparticles. The
percentage of nanoparticles may be in part determined by the molar
ratio of metal to carbon atoms in the precursor mixture. At a 1:1
ratio, nearly all of the carbon may be incorporated into the
nanoparticle, leaving a small amount or trace of carbonaceous
matrix. With higher amounts of organic compound, the fraction of
nanoparticles is lower and the fraction of carbonaceous matrix is
higher. By this method, variations in the ratio of metal to organic
may be used, affording a mixture of metal carbide when performed in
an inert atmosphere such as argon and metal nitride when performed
in a nitrogen atmosphere. When metal nitrides are made, raising the
amount of carbon in the precursor mixture may lower the amount of
metal nitride in the ceramic.
[0049] The ceramic is not formed as a powder and may be in the form
of a solid, unbroken mass. It may contain less than 20% by volume
of voids or as low as 10%, 5%, or 1%. A WC-carbon ceramic may be
made with less than 50% voids. It may have the same shape as the
precursor mixture or it may take on the shape of a mold it was
placed in during the heating. The ceramic may retain its shape in
that it does not crumble when handled and may not change shape or
break without the use of extreme force. The ceramic composition may
be tough, hard, and have structural integrity. The degree of such
properties may depend on the amount of ceramic to carbon in the
solid ceramic solid composition. Any shape may be formed to make an
article useful for incorporation into an apparatus. The article may
be large enough to have a minimum size of at least 1 cm in all
dimensions. That is, the entire surface of the article is at least
5 mm from the center of mass of the article. Larger articles may be
made, such as having a minimum size of at least 10 cm in all
dimensions. Also, the composition may have smaller sizes, such as 1
mm, 2 mm, or 5 mm.
[0050] A third heating step may also be performed, where the
ceramic is heated in an oxygen-containing atmosphere to form an
oxide of the refractory metal on the surface of the ceramic. For
example, titanium oxide may be formed on the surface. Such surface
oxidation may protect the interior of the ceramic from further
oxidation.
[0051] The following examples are given to illustrate specific
applications. These specific examples are not intended to limit the
scope of the disclosure in this application. Any other appropriate
methods and materials disclosed in U.S. Provisional Application
Nos. 61/590,852; 61/640,744; 61/669,201; 61/693,930 may be used.
Any carbon source, metal compound, and/or other parameter disclosed
therein may be used in any combination in the presently disclosed
method, and may be combined with any material and/or parameter
disclosed in the present application.
Example 1
[0052] Formulation of Precursor Composition of TiH.sub.2 and
TPEB--
[0053] TPEB (0.1016 g; 0.2125 mmol) and TiH.sub.2 (0.2008 g; 4.0224
mmol) were thoroughly mixed and used as the precursor composition
for the formation of refractory nanoparticle TiC embedded or bonded
with the excess of carbon that behaves as a matrix material. The
ratio of the two reactants can be readily varied by the described
formulation method.
Example 2
[0054] Formation of Refractory TiC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1400.degree. C. Under an Argon
Atmosphere--
[0055] A sample (5.8911 mg) of the precursor composition prepared
in Example 1 was weighed into a TGA ceramic pan and directly heated
at 10.degree. C. under a flow (100 cc/min) of argon to 1400.degree.
C. yielding a solid ceramic material with a weight retention of
89.24%. During the heat treatment, the sample melted at about
194.degree. C. (endothermic transition; TPEB) and exhibited an
exothermic transition peaking at about 292.degree. C. (cure to
thermoset solid polymer). The solid ceramic was removed from the
TGA pan and characterized by XRD and was found to have formed
nanoparticle sized TiC in an excess of carbon as the matrix. The
TiC carbon solid composition was formed in one step and exhibited
structural integrity. FIG. 5 shows a typical XRD of a TiC sample
made by the method of this example.
Example 3
[0056] Formation of Refractory TiC Solid Ceramic in One Step by
Controlled Heating to 1200.degree. C. Under an Argon
Atmosphere--
[0057] A sample (62.1426 mg) of the precursor composition prepared
in Example 1 was heated under an argon atmosphere at 5.degree.
C./min to 250.degree. C. and held at this temperature for 2 hr to
consolidate to a solid shaped thermoset polymer. During the heat
treatment to 250.degree. C., the sample showed an endothermic
transition at about 195.degree. C. attributed to the melting point
of TPEB. The isothermal heat treatment at 250.degree. C. resulted
in the reaction of the ethynyl units in the TPEB and conversion to
the shaped thermoset polymer. The solid polymeric sample composed
of TiH.sub.2 and the polymeric thermoset was slowly heated at
1.degree. C./min to 1200.degree. C. and held at this temperature
for 6 hr affording a weight retention of 89.78%. Above 400.degree.
C., degradation of the TiH.sub.2 occurred to Ti nanoparticles and
H.sub.2 and the H.sub.2 vaporized from the sample. Further heating
above 500.degree. C. to 1200.degree. C. resulted in the reaction of
the highly reactive Ti nanoparticles with the developing carbon
atoms being formed from the carbonization of TPEB during the heat
treatment resulting in the formation of TiC nanoparticles embedded
in excess carbon formed during the simple carbonization process.
The refractory TiC ceramic carbon matrix composite was formed in
one step. XRD analysis showed high yield of TiC nanoparticles and a
small amount of crystalline carbon as the products formed during
the heat treatment.
Example 4
[0058] Formation of Refractory TiC Solid Ceramic in One Step by
Controlled Heating to 1400.degree. C. Under an Argon
Atmosphere--
[0059] A sample (67.200 mg) of the precursor composition prepared
in Example 1 was heated under an argon atmosphere at 5.degree.
C./min to 250.degree. C. and held at this temperature for 2 hr to
consolidate to a solid shaped thermoset polymer. During the heat
treatment to 250.degree. C., the sample showed an endothermic
transition at about 195.degree. C. attributed to the melting point
of TPEB. The isothermal heat treatment at 250.degree. C. resulted
in the reaction of the ethynyl units in the TPEB and conversion to
the shaped thermoset polymer. The solid sample composed of
TiH.sub.2 and the thermoset polymer was slowly heated at 1.degree.
C./min to 1400.degree. C. and held at this temperature for 4 hr
affording a weight retention of 89.33%. Above 400.degree. C.,
degradation of the TiH.sub.2 occurred to Ti nanoparticles and
H.sub.2 and the H.sub.2 vaporized from the sample. Further heating
above 500.degree. C. to 1400.degree. C. resulted in the reaction of
the highly reactive Ti nanoparticles with the developing carbon
atoms being formed from the carbonization of TPEB during the heat
treatment resulting in the formation of TiC nanoparticles embedded
in excess carbon formed during the simple carbonization process.
The refractory TiC ceramic carbon matrix composite was formed in
one step. XRD analysis showed high yield of TiC nanoparticles and a
small amount of crystalline carbon as the products formed during
the heat treatment.
Example 5
[0060] Formation of Refractory TiC Solid Ceramic in One Step by
Controlled Heating of 2.degree. C./min to 1400.degree. C. Under an
Argon Atmosphere--
[0061] A sample (64.7660 mg) of the precursor composition prepared
in Example 1 was heated in a TGA chamber under an argon atmosphere
at 5.degree. C./min to 250.degree. C. and held at this temperature
for 2 hr to consolidate to a solid shaped thermoset polymer. During
the heat treatment to 250.degree. C., the sample showed an
endothermic transition at about 195.degree. C. attributed to the
melting point of TPEB. The isothermal heat treatment at 250.degree.
C. resulted in the reaction of the ethynyl units in the TPEB and
conversion to the shaped thermoset polymer. The solid sample
composed of TiH.sub.2 and the thermoset polymer was slowly heated
at 2.degree. C./min to 1400.degree. C. and held at this temperature
for 4 hr affording a weight retention of 89.77%. Above 400.degree.
C., degradation of the TiH.sub.2 occurred to Ti nanoparticles and
H.sub.2 and the H.sub.2 vaporized from the sample. Further heating
above 500.degree. C. to 1400.degree. C. resulted in the reaction of
the highly reactive Ti nanoparticles with the developing carbon
atoms being formed from the carbonization of TPEB during the heat
treatment resulting in the formation of TiC nanoparticles embedded
in excess carbon formed during the simple carbonization process.
The refractory TiC ceramic carbon matrix composite was formed in
one step. XRD analysis showed high yield of TiC nanoparticles and a
small amount of crystalline carbon as the products formed during
the heat treatment.
Example 6
[0062] Formation of Stable TiO.sub.2 on Outer Surface as Film from
Exposure of TiC Solid Ceramic to Flow of Air--
[0063] The TiC carbon composite sample (56.2200 mg) prepared in
Example 5 was cooled and further heated in the TGA chamber in a
flow of air (100 cc/min) at 5.degree. C./min to 1400.degree. C. The
sample started to slowly exotherm above 500.degree. C. peaking at
about 644.degree. C. with a slight increase in weight. As the
heating was continued to 1400.degree. C., an increase in weight of
20% was observed on this small sample attributed to oxidation
(white layer) on the outer surface of the sample. XRD analysis
confirmed the formation of TiO.sub.2 (white layer) on the outer
surface. Below this surface, a black surface was intact and
attributed to the original TiC-carbon composition.
Example 7
[0064] Controlled Oxidation of TiC Carbon Composite--
[0065] The sample (68.2060 mg) formed during the oxidation of
Example 6 was cooled and reheated at 10.degree. C./min to
1400.degree. C. under a flow of air (100 cc/min). Basically, no
change in the weight was observed indicating that no further
oxidation was occurring after the initial oxidation to form the
film (TiO.sub.2) on the outer surface. The TiO.sub.2 was behaving
as a barrier protecting the inner portion of the sample against
further oxidation.
Example 8
[0066] Melt Formulation of Solid Precursor Composition of TiH.sub.2
and TPEB--
[0067] TPEB (0.600 g; 1.255 mmol) was melted at 255.degree. C. in
an aluminum planchet treated with a silicone mold release.
TiH.sub.2 (1.65 g; 33.1 mmol) was added to the melt and thoroughly
mixed until the mixture thickened (polymerization of the acetylene
units to thermoset polymer). Various precursor polymeric
compositions (TiH.sub.2 and TPEB) can be formulated by this method
by varying the ratio of the two reactants (TPEB and TiH.sub.2).
Example 9
[0068] Formation of Refractory TiC Solid Ceramic Carbon Composition
in One Step by Heating at 2.degree. C./min to 1000.degree. C. Under
an Argon Atmosphere--
[0069] The thermoset sample (1.98 g) prepared in Example 8 was
heated in a tube furnace at 2.degree. C./min to 1000.degree. C.
yielding the solid ceramic material with a weight retention of 95%.
The sample was characterized by XRD and was found to form pure
nanoparticle sized TiC embedded in an excess of carbon as the
matrix. The TiC nanoparticle carbon solid composition was formed in
one step and retained its structural integrity.
Example 10
[0070] Formation of Refractory TiN Solid Ceramic Carbon Composition
in One Step by Controlled Heating to 1400.degree. C. Under a
Nitrogen Atmosphere--
[0071] A sample (5.1780 mg) of a precursor composition prepared as
in Example 1 was weighed into a TGA ceramic pan and heated at
10.degree. C. under a flow (100 cc/min) of nitrogen to 1400.degree.
C. yielding a solid material with a weight retention of 89.24%.
During the heat treatment, the sample melted at about 194.degree.
C. (endothermic transition; TPEB) and exhibited an exothermic
transition peaking at about 292.degree. C. attributed to the cure
to solid thermoset polymer. After the heat treatment at
1400.degree. C., the solid ceramic was removed from the TGA pan and
characterized by XRD and was found to contain TiN nanoparticles
embedded or bonded in an excess of carbon as the matrix. The TiN
carbon solid composition was formed in one step in the nitrogen
atmosphere. In contrast, when the reaction was run under an argon
atmosphere, the TiC nanoparticles (embedded in excess carbon) were
formed from reaction of the Ti nanoparticles with the carbon atoms
during the carbonization process. FIG. 6 shows a typical XRD of a
TiN sample made by the method of this example.
Example 11
[0072] Formation of Refractory TiN Solid Ceramic in One Step by
Controlled Heating at 2.degree. C./min to 1400.degree. C. Under a
Nitrogen Atmosphere--
[0073] A sample (77.4586 mg) of the precursor composition prepared
as in Example 1 was heated in a TGA chamber under a nitrogen
atmosphere at 5.degree. C./min to 250.degree. C. and held at this
temperature for 2 hr to consolidate to a solid shaped thermoset
polymer. At this time, the solid polymer sample, composed of TPEB
and TiH.sub.2, was slowly heated at 2.degree. C./min to
1400.degree. C. and held at this temperature for 3 hr affording a
solid ceramic carbon composition with a weight retention of 92.94
wt. During the heat treatment, the sample showed an endothermic
transition at about 195.degree. C. attributed to the melting point
of TPEB. The isothermal heat treatment at 250.degree. C. resulted
in the reaction of the ethynyl units in the TPEB and conversion to
a shaped solid thermoset polymer. Further heating above 400.degree.
C. resulted in the degradation of the TiH.sub.2 to Ti nanoparticles
and H.sub.2, of which the H.sub.2 vaporized from the sample as
formed. Further heating above 500.degree. C. to 1400.degree. C.
resulted in the reaction of the highly reactive Ti nanoparticles
with the developing carbon atoms being formed from degradation of
TPEB during the carbonization process resulting in the formation of
TiN nanoparticles embedded in excess carbon formed. The refractory
TiN ceramic carbon matrix composition was formed in one step. XRD
analysis of the solid ceramic carbon matrix composition showed high
yield of nanoparticle TiN nanoparticles and crystalline carbon as
the products from the heat treatment.
Example 12
[0074] Formation of Solid Precursor Composition of TiH.sub.2 and
PDEA by Melt Mixing--
[0075] N,N'-(1,4-phenylenedimethylidyne)-bis-(3-ethynylaniline)
(PDEA) (0.516 g; 1.394 mmol) was melted at 160.degree. C. in an
aluminum planchet treated with a silicone mold release. TiH.sub.2
(1.65 g; 33.1 mmol) was added to the melt, thoroughly mixed, and
heated under an argon atmosphere until the mixture thickened from
polymerization of the terminal acetylene units to a thermoset
polymer. The solid thermoset polymer composition was heated at
160.degree. C. for 1 hr was cooled, removed from the mold, and used
for the formation of refractory nanoparticle TiC and TiN
compositions.
Example 13
[0076] Conversion of Solid Precursor Composition TiH.sub.2 and PDEA
to Refractory TiC/TiN Solid Ceramic in One Step by Heating at
10.degree. C./min to 1000.degree. C. Under an Argon
Atmosphere--
[0077] A sample (1.896 g) prepared as in Example 12 was heated
under an atmosphere of argon in a tube furnace at 2.degree. C./min
to 1000.degree. C. yielding the solid ceramic material with a
weight retention of 95%. The sample was characterized by XRD and
was found to contain both TiC and TiN embedded in an excess of
carbon as the matrix. The TiC and TiN nanoparticle carbon solid
composition was formed in one step and retained its structural
integrity. When another small sample was heated in a nitrogen
atmosphere, only TiN nanoparticles embedded in carbon were
formed.
Example 14
[0078] Formulation of Solid Precursor Thermoset Polymeric
Composition of TiH.sub.2 and Dianilphthalonitrile by Melt
Mixing--
[0079] Dianilphthalonitrile (0.600 g; 1.56 mmol) was melted at
300.degree. C. in an aluminum planchet treated with a silicone mold
release. TiH.sub.2 (1.66 g; 33.2 mmol) and 3 weight % p-BAPS
(curing additive) were added, thoroughly mixed, and heated at
300.degree. C. until the mixture thickened from polymerization of
the terminal phthalonitrile units to a thermoset polymer. Once
solidified by heating at 300.degree. C. for 1 hr, the solid
polymeric mass was cooled, removed from the mold, and used for the
formation of refractory nanoparticle TiC and TiN nanoparticles
embedded or bonded within the excess carbon that behaves as a
matrix material. The ratio of the two reactants can be varied by
this described method and will yield a thermoset polymer with
homogeneous distribution of the TiH.sub.2 within the domain of the
polymer. The overall physical properties of the polymer can be
easily varied with varying amounts of the reactants.
Example 15
[0080] Conversion of Solid Precursor Thermoset Polymeric
Composition of TiH.sub.2 and Dianilphthalonitrile to Refractory TiC
and TiN Solid Carbon Ceramic in One Step by Heating at 10.degree.
C./min to 1000.degree. C. Under an Argon Atmosphere--
[0081] A polymeric sample (2.068 g) prepared as in Example 14 was
heated under an argon atmosphere in a tube furnace at 2.degree.
C./min to 1000.degree. C. yielding the solid ceramic material with
a weight retention of 92.1%. The ceramic sample was characterized
by XRD and was found to contain nanoparticle-containing TiC and TiN
embedded in an excess of carbon as the matrix. The TiC and TiN
carbon solid ceramic composition was formed in one step and
retained its structural integrity.
Example 16
[0082] Formulation of Solid Precursor Composition of TiH.sub.2 and
Resorcinol Phthalonitrile by Melt Mixing--
[0083] Resorcinol phthalonitrile (0.500 g; 1.381 mmol) was melted
at 300.degree. C. in an aluminum planchet treated with a silicone
mold release. TiH.sub.2 (1.65 g; 33.1 mmol) and 3 weight % p-BAPS
were added, thoroughly mixed, and heated at 300.degree. C. under an
argon atmosphere until the mixture thickened from polymerization of
the terminal phthalonitrile units to a thermoset polymer. Once
solidified by heating at 300.degree. C. for 1 hr, the solid
polymeric mass was cooled, removed from the mold, and used for the
formation of refractory nanoparticle TiC and TiN carbon
compositions.
Example 17
[0084] Conversion of Solid Precursor Thermoset Polymeric
Composition of TiH.sub.2 and Resorcinol Phthalonitrile to
Refractory TiC and TiN Solid Ceramic in One Step by Heating at
10.degree. C./min to 1000.degree. C. Under an Argon
Atmosphere--
[0085] A polymeric sample (1.978 g) prepared as in Example 16 was
heated in a tube furnace at 2.degree. C./min to 1000.degree. C.
yielding the solid ceramic material with a weight retention of
91.5%. The ceramic sample was characterized by XRD and was found to
contain nanoparticle-containing TiC and TiN embedded in carbon as
the matrix. The TiC and TiN carbon solid shaped composition was
formed in one step and retained its structural integrity.
Example 18
[0086] Formulation and Formation of Solid Cone-Shaped Thermoset
Polymeric Composition of TiH.sub.2 and TPEB by Melt Mixing--
[0087] TPEB (3.61 g; 7.552 mmol) was melted at 255.degree. C. in an
aluminum foil mold that had been pressed into a conical shape and
treated with a silicone mold release. TiH.sub.2 (7.18 g; 143.7
mmol) was added, thoroughly mixed, and heated under an argon
atmosphere until the mixture thickened by polymerization of the
acetylene units to a thermoset polymer. Once the composition had
solidified (30 min), the solid shaped polymeric mass was cooled and
removed from the mold. The ratio of the two reactants can be easily
varied by the method described in this Example 18 for formulation
to a thermoset polymer. Using the various solid thermoset polymeric
composition containing varying amounts of the two reactants, the
overall physical properties of the corresponding TiC-carbon matrix
composition, by heating the polymeric compositions above
500.degree. C. under a flow of argon, can be readily changed. In
addition, the amounts of each reactant can be changed to afford the
formation of just TiC nanoparticles or TiC nanoparticles embedded
in varying amounts of carbon.
Example 19
[0088] Conversion of Solid Cone-Shaped Thermoset Polymeric
Composition of TiH.sub.2 and TPEB to Refractory TiC Solid
Cone-Shaped Ceramic in One Step by Heating at 10.degree. C./min to
1000.degree. C. Under an Argon Atmosphere--
[0089] A thermoset polymer sample (9.962 g) prepared as in Example
18 was heated in a tube furnace at 2.degree. C./min to 1000.degree.
C. yielding the solid ceramic material with a weight retention of
91.2%. The ceramic sample was characterized by XRD and was found to
contain TiC nanoparticles embedded in an excess of carbon as the
matrix. The refractory TiC ceramic carbon solid composition was
formed in one step and retained its structural integrity. This
example shows that any shaped configuration containing refractory
metal carbide in carbon as matrix can be formed from a refractory
metal source that degrades or decomposes to metal nanoparticles
that react with the developing carbon atoms of a carbon source
(resin or polymer) during the elevated heat treatment under inert
conditions.
Example 20
[0090] Formulation of Precursor Composition of ZrH.sub.2 and
TPEB--
[0091] TPEB (0.0.0974 g; 0.203 mmol) and ZrH.sub.2 (0.500 g; 5.361
mmol) were thoroughly mixed as powders and used as the precursor
for the formation of refractory ZrC or ZrN nanoparticles embedded
or bonded with the slight excess carbon that behaves as a matrix
material. The ratio of the two reactants can be varied to form
various concentrations of powdered precursor composition.
Example 21
[0092] Formation of Refractory ZrC Solid Ceramic Composition in One
Step by Heating at 10.degree. C./min to 1400.degree. C. Under an
Argon Atmosphere--
[0093] A sample (20.9090 mg) of the precursor composition prepared
in Example 20 was weighed into a TGA ceramic pan and heated at
10.degree. C. under a flow (100 cc/min) of argon to 1400.degree. C.
yielding a solid material with a weight retention of 94.34%. During
the heat treatment, the sample melted at about 194.degree. C.
(endothermic transition; TPEB) and exhibited an exothermic
transition peaking at about 292.degree. C. attributed to the cure
to a solid thermoset polymer. After cooling from 1400.degree. C. to
room temperature, the solid ceramic composition was removed from
the TGA pan, characterized by XRD and was found to contain
nanoparticle sized ZrC in an excess of carbon as the matrix. The
shaped solid ceramic refractory ZrC carbon composite was formed in
one step and exhibited structural integrity. FIG. 7 shows a typical
XRD of a ZrC sample made by the method of this example.
Example 22
[0094] Formation of Refractory ZrC Solid Ceramic in One Step by
Controlled Heating of 2.degree. C./min to 1400.degree. C. Under an
Argon Atmosphere--
[0095] A sample (124.1630 mg) of the powdered composition prepared
as in Example 20 was heated in a TGA chamber under an argon
atmosphere at 5.degree. C./min to 250.degree. C. and held at this
temperature for 2 hr to consolidate to a solid shaped thermoset
polymer. During the heat treatment, the sample showed an
endothermic transition at about 195.degree. C. attributed to the
melting point of TPEB. The isothermal heat treatment at 250.degree.
C. resulted in the reaction of the ethynyl units in the TPEB and
conversion to the shaped solid thermoset polymer. The resulting
thermoset polymer contained a homogeneous distribution of ZrH.sub.2
embedded in the domain of the polymer. Further heating above
500.degree. C. resulted in the degradation of the ZrH.sub.2 to Zr
nanoparticles and H.sub.2; the H.sub.2 vaporized from the sample as
formed. Heating from 500.degree. C. to 1400.degree. C. resulted in
the reaction of the highly reactive Zr nanoparticles with the
developing carbon atoms being formed from degradation of TPEB
during the simple carbonization process resulting in the formation
of ZrC nanoparticles embedded in excess carbon. The solid thermoset
polymer sample was slowly heated at 2.degree. C./min to
1400.degree. C. and held at this temperature for 4 hr affording a
weight retention of 93.77 wt of a solid ceramic solid. The
refractory ZrC ceramic carbon matrix composition is formed in one
step. XRD analysis showed high yield of ZrC nanoparticles and a
small amount of crystalline carbon as the products formed during
the heat treatment.
Example 23
[0096] Mixing and Conversion of Precursor Compositions of
TiH.sub.2/TPEB and ZrH.sub.2/TPEB to Refractory TiC and ZrC in
Carbon Matrix in One Step by Heating in Argon Atmosphere to
1000.degree. C.--
[0097] A sample (30.1234 mg) of TiH.sub.2/TPEB powdered composition
prepared as in Example 1 and a sample (55.2685 mg) of
ZrH.sub.2/TPEB powdered composition prepared as in Example 20 were
thoroughly mixed and placed in a TGA pan. The resulting mixture was
heated at 2.degree. C. under a flow (100 cc/min) of argon to
1200.degree. C. yielding a solid material with a weight retention
of 94.34%. During the heat treatment, the sample melted at about
194.degree. C. (endothermic transition; TPEB) and exhibited an
exothermic transition peaking at about 292.degree. C. attributed to
the cure of the TPEB to solid thermoset polymer. After cooling from
1200.degree. C. to room temperature, the solid ceramic material was
removed from the TGA pan, characterized by XRD and was found to
contain nanoparticle sized TiC and ZrC in an excess of carbon as
the matrix. The shaped solid ceramic refractory TiC and ZrC carbon
composition was formed in one step and exhibited structural
integrity.
Example 24
[0098] Formation of Refractory ZrN Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1400.degree. C. Under an Argon
Atmosphere--
[0099] A sample (31.51895 mg) of the precursor composition prepared
as in Example 20 was weighed into a TGA ceramic pan and heated at
10.degree. C. under a flow (100 cc/min) of nitrogen to 1400.degree.
C. yielding a solid material with a weight retention of 96.5%.
During the heat treatment, the sample melted at about 194.degree.
C. (endothermic transition; TPEB) and exhibited an exothermic
transition peaking at about 292.degree. C. attributed to the cure
of TPEB to solid thermoset polymer. After cooling from 1400.degree.
C. to room temperature, the solid ceramic material was removed from
the TGA pan, characterized by XRD, and was found to contain
nanoparticle sized ZrN embedded in an excess of carbon as the
matrix. The shaped solid ZrN carbon composite was formed in one
step and exhibited structural integrity. ZrN was formed rather than
ZrC because of the nitrogen atmosphere, which was the source of the
nitrogen in the refractory ZrN nanoparticles. FIG. 8 shows a
typical XRD of a ZrN sample made by the method of this example.
Example 25
[0100] Melt Formulation of Solid Precursor Thermoset Polymeric
Composition of ZrH.sub.2 and TPEB--
[0101] TPEB (0.792 g; 1.66 mmol) was melted at 255.degree. C. in an
aluminum planchet treated with a silicone mold release. ZrH.sub.2
(3.00 g; 32.2 mmol) was added to the melt, thoroughly mixed, and
heated at 255.degree. C. under an inert atmosphere until the
mixture thickened from polymerization of the acetylene units of
TPEB to a thermoset polymer. Once solidification (30 min) had
occurred to a shaped thermoset polymer, the solid polymer mass was
cooled and removed from the mold. By the method described, the
ratio of the two reactants (TPEB and ZrH.sub.2) can be varied,
which will affect the overall physical properties of the thermoset
polymer containing a homogeneous distribution of ZrH.sub.2 within
the domain of the polymeric thermoset.
Example 26
[0102] Conversion of Solid Precursor Thermoset Polymeric
Composition of ZrH.sub.2 and TPEB to Refractory ZrC Solid Ceramic
in One Step by Heating at 10.degree. C./min to 1000.degree. C.
Under an Argon Atmosphere--
[0103] A sample (3.156 g) of solid thermoset composition prepared
as in Example 25 was placed in a tube furnace and heated under an
argon atmosphere at 2.degree. C./min to 1000.degree. C. yielding
the solid ceramic material with a weight retention of 94%. The
sample was characterized by XRD and was found to contain a
homogeneous distribution of ZrC nanoparticles in an excess of
carbon as the matrix. The ZrC nanoparticle carbon solid composition
was formed in one step and retained its solid structural
integrity.
Example 27
[0104] Conversion of Solid Precursor Thermoset Polymeric
Composition of ZrH.sub.2 and TPEB to Refractory ZrN Solid Ceramic
in One Step by Heating at 10.degree. C./min to 1000.degree. C.
Under a Nitrogen Atmosphere--
[0105] Another polymeric sample (4.523 g) prepared as in Example 25
was placed in a tube furnace and heated under a nitrogen atmosphere
at 2.degree. C./min to 1000.degree. C. yielding the solid ceramic
material with a weight retention of 99%. The sample was
characterized by XRD and was found to form a ZrN nanoparticle
carbon composition. At least the ZrN was present on the outer
surfaces in an excess of carbon as the matrix. The ZrN nanoparticle
carbon solid composition was formed in one step and the sample
retained its solid structural integrity. A large thick sample would
probably contain ZrN on the outer part of the sample and ZrC in the
interior part of the sample.
Example 28
[0106] Formulation of Precursor Composition of HfH.sub.2 and
TPEB--
[0107] TPEB (0.0.0974 g; 0.203 mmol) and HfH.sub.2 (0.500 g; 5.361
mmol) were thoroughly mixed in the powder form and used as the
precursor for the formation of shaped solid HfH.sub.2 polymeric
compositions.
Example 29
[0108] Formulation of Precursor Composition of HfH.sub.2 and
TPEB--
[0109] TPEB (87 mg; 0.182 mmol) and HfH.sub.2 (1.00 mg; 5.54 mmol)
were thoroughly mixed and used as the precursor for the formation
of refractory nanoparticle HfC embedded or bonded with the slight
excess carbon that behaves as a matrix material. The ratio of the
two reactants can be easily varied which will affect the overall
physical properties of the corresponding HfH.sub.2 thermoset
polymers, which are readily converted to HfC-carbon matrix
compositions by heating the polymeric compositions above
500.degree. C. in an argon atmosphere. In addition, the amounts of
each reactant can be changed to afford basically the formation of
just HfC in which the ratio of Hf atoms to carbon atoms is 1:1.
Example 30
[0110] Formation of Refractory HfC Solid Ceramic Composition in One
Step by Heating at 10.degree. C./min to 1400.degree. C. Under an
Argon Atmosphere--
[0111] A sample (71.8978 mg) of the precursor mixture prepared in
Example 28 was weighed into a TGA ceramic pan and heated at
10.degree. C. under a flow (100 cc/min) of argon to 1400.degree. C.
yielding a solid material with a weight retention of 98.45%. During
the heat treatment, the TPEB in the precursor mixture melted at
about 194.degree. C. (endothermic transition; TPEB) and exhibited
an exothermic transition peaking at about 292.degree. C. attributed
to the cure of TPEB to a solid thermoset polymer. After cooling
from 1400.degree. C. to room temperature, the solid ceramic
material was removed from the TGA pan, characterized by XRD and was
found to contain nanoparticle sized HfC in an excess of carbon as
the matrix. The shaped solid ceramic refractory HfC carbon
composite was formed in one step and exhibited structural
integrity. FIG. 9 shows a typical XRD of a HfC sample made by the
method of this example.
Example 31
[0112] Formation of Refractory HfN Solid Ceramic Composition in One
Step by Heating at 10.degree. C./min to 1400.degree. C. Under an
Argon Atmosphere--
[0113] A sample (75.7452 mg) of the precursor mixture prepared in
Example 28 was weighed into a TGA ceramic pan and heated at
10.degree. C. under a flow (100 cc/min) of nitrogen to 1400.degree.
C. yielding a solid material with a weight retention of 99.34%.
During the heat treatment, the TBEB in the precursor mixture melted
at about 194.degree. C. (endothermic transition; TPEB) and
exhibited an exothermic transition peaking at about 292.degree. C.
attributed to the cure of TPEB to a solid thermoset polymer. After
cooling from 1400.degree. C. to room temperature, the solid ceramic
was removed from the TGA pan, characterized by XRD and was found to
contain nanoparticle sized HfN in an excess of carbon as the
matrix. The shaped solid ceramic refractory HfN carbon composite
was formed in one step and exhibited structural integrity.
Example 32
[0114] Formation of Refractory HfC Solid Ceramic Composition in One
Step by Heating at 10.degree. C./min to 1400.degree. C. Under an
Argon Atmosphere--
[0115] A sample (71.8978 mg) of the precursor mixture prepared in
Example 29 was weighed into a TGA ceramic pan and heated at
5.degree. C. under a flow (100 cc/min) of argon to 1400.degree. C.
yielding a solid material with a weight retention of 98.89%. After
cooling from 1400.degree. C. to room temperature, the solid ceramic
material was removed from the TGA pan, characterized by XRD and was
found to contain nanoparticle sized HfC in an excess of carbon as
the matrix. The shaped solid ceramic refractory HfC carbon
composite was formed in one step and exhibited structural
integrity.
Example 33
[0116] Formulation of Solid Precursor Composition of Tungsten
Powder (.about.600-900 nm Particle Size) and TPEB by Melt
Mixing--
[0117] TPEB (0.680 g; 1.422 mmol) was melted at 250.degree. C. in
an aluminum planchet treated with a silicone mold release. Tungsten
powder (2.00 g; 10.87 mmol) was added, thoroughly mixed, and heated
at 250.degree. C. until the mixture thickened attributed to the
polymerization of the acetylene units of TPEB to thermoset polymer.
On solidification (30 min) of the TPEB to the thermoset polymer,
the solid shaped polymer mass was cooled and removed from the
mold.
Example 34
[0118] Formation of Refractory WC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1000.degree. C. Under an Argon
Atmosphere--
[0119] A sample (2.542 g) of the polymeric composition prepared in
Example 33 was heated in a tube furnace at 2.degree. C./min to
1000.degree. C. yielding the solid ceramic material with a weight
retention of 95%. The sample was characterized by XRD and was found
to contain WC in a large excess of carbon as the matrix along with
some unreacted tungsten. The WC carbon solid composite was formed
in one step. Nanoparticle-sized tungsten or small-sized tungsten
powder would be expected to increase the yield of WC and
potentially eliminate the presence of unreacted tungsten. Heating
of the sample at a higher temperature (1200.degree. C.) reduced the
amount of unreacted tungsten and increased the amount of WC present
in the sample.
Example 35
[0120] Formulation of Precursor Composition of TiH.sub.2 and TPEB
with Excess Carbon Source (TPEB)--
[0121] TPEB (2.10 g; 4.39 mmol) and TiH.sub.2 (4.95 g; 99.1 mmol)
were thoroughly mixed in the powder form and used as the precursor
for the formation of refractory nanoparticle TiC in a carbon matrix
carbon fiber composite.
Example 36
[0122] Formulation of TiH.sub.2 Carbon Fiber Polymeric
Composite--
[0123] Into a 0.5 inch diameter mold formed from aluminum foil was
placed the precursor composition (1.7541 g of the TPEB and
TiH.sub.2 mixture) prepared in Example 35. The mixture was heated
to 220.degree. C. (melt) and chopped carbon fibers were added and
mixed into the composition. The resulting carbon fiber-precursor
composition was heated under a flow of argon at 250.degree. C. for
1 hr resulting in solidification to a shaped carbon
fiber-containing polymeric thermoset.
Example 37
[0124] Conversion of the TiH.sub.2 Carbon Fiber Polymeric Composite
to TiC Carbon Fiber Ceramic Composite--
[0125] The solid shaped carbon fiber polymeric composite prepared
in Example 36 with a homogeneous distribution of the TiH.sub.2 was
removed from the mold, placed in an oven, and heated under a flow
of argon at 3.degree. C./min to 1000.degree. C. and held at the
temperature for 2 hr. The resulting ceramic-carbon reinforced
composite was cooled at 3.degree. C./min back to room temperature.
The solid composite sample was characterized by XRD and found to
contain refractory TiC nanoparticles embedded in carbon matrix and
carbon fibers.
Example 38
[0126] Formation of Refractory ZrH.sub.2 Carbon Fiber Polymeric
Composite--
[0127] Into a 0.5 inch diameter mold fabricated from aluminum foil
was placed a precursor composition (1.9545 g of the TPEB and
ZrH.sub.2 mixture) prepared as in Example 20. The composition was
heated to 220.degree. C. (melt) and chopped carbon fibers were
added and mixed into the liquid composition. The resulting carbon
fiber-precursor composition was heated under a flow of argon at
250.degree. C. for 1 hr resulting in solidification to a shaped
carbon fiber-containing polymeric thermoset. The solid shaped
carbon fiber polymeric composite with a homogeneous distribution of
the ZrH.sub.2 was removed from the mold.
Example 39
[0128] Conversion of the ZrH.sub.2 Carbon Fiber Polymeric Composite
to ZrC Carbon Fiber Ceramic Composite--
[0129] The solid shaped carbon fiber polymeric composite prepared
in Example 38 was placed in an oven and heated under a flow of
argon at 3.degree. C./min to 1200.degree. C. and held at the
temperature for 2 hr. The resulting ceramic-carbon fiber reinforced
composite was cooled at 3.degree. C./min back to room temperature.
The solid ceramic-carbon fiber composite sample was characterized
by XRD and found to contain refractory ZrC nanoparticles embedded
in carbon matrix and carbon fibers.
Example 40
[0130] Formation of Refractory HfH.sub.2 Carbon Fiber Polymeric
Composite--
[0131] Into a 0.5 inch diameter mold fabricated from aluminum foil
was placed a precursor composition (2.5564 g of the TPEB and
HfH.sub.2 mixture) prepared as in Example 29. The composition was
heated to 220.degree. C. (melt) and chopped carbon fibers were
added and mixed into the liquid composition. The resulting carbon
fiber-precursor composition was heated under a flow of argon at
250.degree. C. for 1 hr resulting in solidification to a shaped
carbon fiber-containing polymeric thermoset. The solid shaped
carbon fiber polymeric composite with a homogeneous distribution of
the HfH.sub.2 was removed from the mold.
Example 41
[0132] Conversion of the HfH.sub.2 Carbon Fiber Polymeric Composite
to HfC Carbon Fiber Ceramic Composite--
[0133] The solid shaped carbon fiber polymeric composite prepared
in Example 40 was placed in an oven and heated under a flow of
argon at 3.degree. C./min to 1200.degree. C. and held at the
temperature for 4 hr. The resulting ceramic-carbon fiber reinforced
composite was cooled at 3.degree. C./min back to room temperature.
The solid ceramic-carbon fiber composite sample was characterized
by XRD and found to contain refractory HfC nanoparticles embedded
in carbon matrix and carbon fibers.
Example 42
[0134] Formulation of Precursor Composition of Tantalum Powder
(9-12 Micron Particle Size) and TPEB with Excess Carbon Source
(TPEB)--
[0135] TPEB (0.340 g; 0.711 mmol) and tantalum powder (1.00 g; 5.53
mmol) were thoroughly mixed and used as the precursor composition
for the formation of refractory nanoparticle TaC embedded or bonded
with the excess carbon that behaves as a matrix material.
Example 43
[0136] Conversion of Precursor Composition of Tantalum Powder (9-12
Micron Particle Size) and TPEB by Heating at 1200.degree. C. for 6
Hr Under Flow of Argon--
[0137] A sample (0.7567 g) of the precursor composition prepared in
Example 42 was heated at 3.degree. C./min under a flow of argon to
1200.degree. C. and held at this temperature for 6 hr. The solid
sample was cooled to room temperature. The solid ceramic sample was
characterized by XRD and found to contain refractory TaC, carbon,
and unreacted Ta.
Example 44
[0138] Formulation of Prepolymer Composition of TPEB--
[0139] TPEB (7.00 g; 14.6 mmol) was placed in an aluminum planchet
and heated at 250.degree. C. for 30 minutes or until the mixture
was viscous to stir with a metal spatula. The mixture was cooled,
broken into small pieces, and ball milled for 2 minutes resulting
in a fine black powder.
Example 45
[0140] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer and Formation of Shaped Pellet--
[0141] TPEB prepolymer form Example 44 (0.300 g; 0.627 mmol) and
TiH.sub.2 (0.825 g; 16.5 mmol) were ball milled for 5 minutes
resulting in a deep red-black fine powder. The powder was placed in
a 13 mm pellet press and pressed to 10,000 pounds for 1 minute.
Example 46
[0142] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer to Solid Shaped Thermoset--
[0143] The pellet from Example 45 was placed in a furnace, heated
at 20.degree. C./min under an argon atmosphere to 210.degree. C.,
and held at this temperature for 10 hr (overnight) resulting in the
formation of a tough shaped polymeric thermoset solid. The
TiH.sub.2 was homogeneously dispersed in the solid thermoset.
Example 47
[0144] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer to Solid Shaped Thermoset--
[0145] Another pellet prepared as in Example 45 was placed in a
furnace, heated at 20.degree. C./min under an argon atmosphere to
250.degree. C., and held at this temperature for 2 hr resulting in
the formation of a tough shaped polymeric thermoset solid.
Example 48
[0146] Formation of Refractory TiC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0147] The shaped polymeric thermoset solid (1.12 g) from Example
46 was placed in a 3'' tube furnace, heated at 2.degree. C./min
under a flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr yielding a solid dense ceramic with weight
retention of 92.1%. The solid ceramic was removed from the furnace,
characterized by XRD, and found to form nanoparticle sized TiC in
an excess of carbon as the matrix. The TiC carbon solid composition
was formed in one step and exhibited great structural integrity,
hardness, and toughness. FIG. 10 shows a typical XRD of a TiC
sample made by the method of this example.
Example 49
[0148] Heat Treatment of Refractory TiC Solid Ceramic by Heating to
1900.degree. C. Under Vacuum--
[0149] The 1600.degree. C. treated ceramic pellet (0.839 g) from
Example 48 was placed in a graphitic furnace, heated at 10.degree.
C./min under a vacuum (10) to 1900.degree. C., and held at
1900.degree. C. for 2 hr yielding a solid dense ceramic with a
weight retention of 95.8%. Upon cooling, the solid ceramic was
removed from the furnace, characterized by XRD, and found to form
larger nanoparticle sized TiC in an excess of carbon as the matrix.
FIG. 11 shows a typical SEM of a TiC sample made by the method of
this example.
Example 50
[0150] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer, Formation of Shaped Pellet, and Direct Conversion to
Refractory TiC Solid Ceramic Carbon Composition in One Step--
[0151] TPEB prepolymer (0.305 g, 0.627 mmol) prepared as in Example
44 and TiH.sub.2 (0.828 g; 16.5 mmol) were ball milled for 5
minutes resulting in a deep red-black fine powder. The powder was
placed in a 13 mm pellet press and pressed to 10,000 pounds for 1
minute. The pellet was then placed in a furnace, heated at
20.degree. C./min under an argon atmosphere to 250.degree. C., and
held at this temperature for 30 minutes followed by heating at
2.degree. C./min under a flow (100 cc/min) of argon to 1200.degree.
C. and holding at 1200.degree. C. for 3 hr yielding a solid dense
ceramic with weight retention of 94.8%. Upon cooling, the solid
ceramic was removed from the furnace, characterized by XRD, and
found to form nanoparticle sized TiC in an excess of carbon as the
matrix. The TiC carbon solid composition was formed in one step and
exhibited great structural integrity, hardness, and toughness.
Example 51
[0152] Formulation of Precursor Composition of Tungsten Powder and
TPEB Prepolymer and Pellet Formation--
[0153] TPEB prepolymer from Example 44 (0.150 g; 0.314 mmol) and
tungsten powder (1.95 g; 10.6 mmol) were ball milled for 5 minutes
resulting in a deep red-black fine powder. The powder was placed in
a 13 mm pellet press and pressed to 10,000 pounds for 10 sec.
Example 52
[0154] Conversion of Precursor Composition of Tungsten Powder and
TPEB Prepolymer to Solid Shaped Thermoset--
[0155] The pellet from Example 51 was placed in a furnace, heated
at 20.degree. C./min under an argon atmosphere to 225.degree. C.,
and held at this temperature for 10 hr (overnight) resulting in the
formation of a tough shaped polymeric solid. The tungsten powder
was homogeneous dispersed in the solid thermoset.
Example 53
[0156] Formation of Refractory WC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0157] The cured thermoset pellet (2.03 g) from Example 52 was
placed in a 3'' tube furnace, heated at 2.degree. C./min under a
flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr yielding a solid dense ceramic with weight
retention of 96.25%. Upon cooling, the solid ceramic was removed
from the furnace, characterized by XRD, and found to form
nanoparticle sized pure WC in an excess of carbon as the matrix.
All of the tungsten had reacted. The WC carbon solid composition
was formed in one step and exhibited structural integrity,
hardness, and toughness. FIG. 12 shows a typical XRD of a WC sample
made by the method of this example. FIG. 13 shows a typical SEM of
a WC sample made by the method of this example.
Example 54
[0158] Heat Treatment of Refractory WC Solid Ceramic to
1900.degree. C. Under Vacuum--
[0159] The 1600.degree. C. treated solid ceramic pellet (1.95 g)
from Example 53 was placed in a graphitic furnace, heated at
10.degree. C./min under a vacuum (10) to 1900.degree. C., and held
at 1900.degree. C. for 2 hr yielding a weight retention of 99.7%.
Upon cooling, the solid ceramic was removed from the furnace,
characterized by XRD, and found to form larger nanoparticle sized
WC in an excess of carbon as the matrix relative to the heat
treatment to 1600.degree. C. as formed in Example 53. The WC carbon
solid still exhibited great structural integrity, hardness, and
retained toughness.
Example 55
[0160] Formulation of Precursor Composition of HfH.sub.2 and TPEB
Prepolymer--
[0161] TPEB prepolymer from Example 44 (0.217 g; 0.454 mmol) and
hafnium hydride (2.49 g; 13.8 mmol) were ball milled for 5 minutes
resulting in a deep red-black fine powder. The powder was placed in
a 13 mm pellet press and pressed to 10,000 pounds for 10 sec.
Example 56
[0162] Conversion of Precursor Composition of HfH.sub.2 and TPEB
Prepolymer to Solid Shaped Thermoset--
[0163] The pellet from Example 55 was placed in a furnace, heated
at 20.degree. C./min under an argon atmosphere to 225.degree. C.,
and held at this temperature for 10 hr (overnight) resulting in the
formation of a tough shaped polymeric solid. The hafnium hydride
powder was homogeneous dispersed in the solid thermoset.
Example 57
[0164] Formation of Refractory HfC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0165] The cured thermoset pellet (2.68 g) from Example 56 was
placed in a 3'' tube furnace, heated at 2.degree. C. min.sup.-under
a flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr yielding a solid dense ceramic with weight
retention of 98.5%. Upon cooling, the solid ceramic was removed
from the furnace, characterized by XRD, and found to form
nanoparticle sized pure HfC in an excess of carbon as the matrix.
The HfC carbon solid composition was formed in one step and
exhibited structural integrity, hardness, and toughness.
Example 58
[0166] Heat Treatment of Refractory HfC Solid Ceramic by Heating to
and at 1900.degree. C. Under Vacuum--
[0167] The 1600.degree. C. treated HfC-carbon composition/pellet
(1.95 g) from Example 57 was placed in a graphitic furnace, heated
at 10.degree. C./min under a vacuum (10.sup.-4) to 1900.degree. C.,
and held at 1900.degree. C. for 2 hr yielding a solid dense ceramic
with a weight retention of 96.6%. Upon cooling, the solid ceramic
was removed from the furnace, characterized by XRD, and found to
form larger nanoparticle sized HfC in an excess of carbon as the
matrix. The HfC carbon solid exhibited great structural integrity,
hardness, and toughness.
Example 59
[0168] Formulation of Precursor Composition of ZrH.sub.2 and TPEB
Prepolymer--
[0169] TPEB prepolymer from Example 44 (0.132 g; 0.276 mmol) and
zirconium hydride (0.500 g; 5.36 mmol) were ball milled for 5
minutes resulting in a deep red-black fine powder. The powder was
placed in a 13 mm pellet press and pressed to 8,000 pounds for 10
sec.
Example 60
[0170] Conversion of Precursor Composition of ZrH.sub.2 and TPEB
Prepolymer to Solid Shaped Thermoset--
[0171] The pellet from Example 59 was placed in a furnace, heated
at 20.degree. C./min under an argon atmosphere to 210.degree. C.,
and held at this temperature for 10 hr (overnight) resulting in the
formation of a tough shaped polymeric solid. The zirconium hydride
powder was homogeneously dispersed in the solid thermoset.
Example 61
[0172] Formation of Refractory ZrC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0173] The cured thermoset pellet (0.630 g) from Example 60 was
placed in a 3'' tube furnace, heated at 2.degree. C./min under a
flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr yielding a solid dense ceramic with weight
retention of 93.5%. Upon cooling, the solid ceramic was removed
from the furnace, characterized by XRD, and found to form
nanoparticle sized pure ZrC in an excess of carbon as the matrix.
The ZrC carbon solid composition was formed in one step and
exhibited structural integrity, hardness, and toughness.
Example 62
[0174] Heat Treatment of Refractory ZrC Solid Ceramic by Heating to
1900.degree. C. Under Vacuum--
[0175] The 1600.degree. C. treated ceramic pellet (0.589 g) from
Example 61 was placed in a graphitic furnace and heated at
10.degree. C./min under a vacuum (10) to 1900.degree. C. for 2 hr
yielding a solid dense ceramic with a weight retention of 96.9%.
The solid ceramic was removed from the furnace, characterized by
XRD, and found to form larger nanoparticle sized ZrC in an excess
of carbon as the matrix. The ZrC carbon solid exhibited great
structural integrity, hardness, and toughness.
Example 63
[0176] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer Containing Chopped Fibers--
[0177] TPEB prepolymer from Example 44 (3.825 g; 8.00 mmol) and
TiH.sub.2 (10.52 g; 211 mmol) were ball milled for 5 minutes
resulting in a deep red-black fine powder. Chopped fibers (1.00 g,
1/4'' length) were added and the solid mixture was placed in 100 mL
of acetone and stirred for 6 hr. The solvent was removed and the
solid mixture was placed in a 21/2'' pellet die and pressed to
10,000 pounds for 1 minute.
Example 64
[0178] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer Containing Chopped Fibers to Thermoset--
[0179] The 21/2'' pellet from Example 63 was placed in a furnace,
heated at 20.degree. C./min under an argon atmosphere to
210.degree. C., and held at this temperature for 10 hr (overnight)
resulting in the formation of a tough shaped polymeric carbon fiber
reinforced thermoset solid. The titanium hydride powder was
homogeneous dispersed in the solid thermoset-carbon fiber
composite.
Example 65
[0180] Formation of Refractory Carbon Fiber Reinforced TiC Solid
Ceramic in One Step by Heating at 10.degree. C./min to 1600.degree.
C. Under an Argon Atmosphere--
[0181] The carbon fiber-containing shaped polymeric thermoset
pellet (14.9 g) from Example 64 was placed in a 3'' tube furnace
and heated at 2.degree. C./min under a flow (100 cc/min) of argon
to 1600.degree. C. yielding a solid dense carbon fiber reinforced
ceramic with weight retention of 96.1%. Upon cooling, the solid
carbon fiber reinforced ceramic was removed from the furnace,
characterized by XRD, and found to form nanoparticle sized TiC in
the carbon-carbon fiber composite. The TiC carbon-carbon fiber
solid composition exhibited great structural integrity with the
inclusion of the fiber reinforcement.
Example 66
[0182] Formulation of Precursor Composition of ZrH.sub.2 and TPEB
Prepolymer Containing Chopped Fibers--
[0183] TPEB prepolymer from Example 44 (2.64 g; 5.52 mmol) and
ZrH.sub.2 (10.00 g; 107 mmol) were ball milled for 5 minutes
resulting in a deep red-black fine powder. Chopped fibers (0.50 g,
1/4'' length) were added and the solid mixture was placed in 100 mL
of acetone and stirred for 4 hr. The solvent was removed and the
solid mixture was placed in a 21/2'' pellet die and pressed to
10,000 pounds for 1 minute.
Example 67
[0184] Conversion of Precursor Composition of ZrH.sub.2 and TPEB
Prepolymer Containing Chopped Fibers to Thermoset--
[0185] The 21/2'' pellet from Example 66 was placed in a furnace,
heated at 20.degree. C./min under an argon atmosphere to
210.degree. C. and held at this temperature for 10 hr (overnight)
resulting in the formation of a tough shaped carbon fiber
reinforced polymeric solid. The zirconium hydride powder was
homogeneous dispersed in the solid thermoset-carbon fiber
composite.
Example 68
[0186] Formation of Refractory ZrC Solid Carbon Fiber Reinforced
Ceramic in One Step by Heating at 10.degree. C./min to 1600.degree.
C. Under an Argon Atmosphere--
[0187] The carbon fiber-containing shaped polymeric thermoset
pellet (12.48 g) from Example 67 was placed in a 3'' tube furnace
and heated at 2.degree. C./min under a flow (100 cc/min) of argon
to 1600.degree. C. yielding a solid dense carbon fiber reinforced
ceramic with weight retention of 96.7%. The solid carbon fiber
reinforced ceramic was removed from the furnace, characterized by
XRD, and found to form nanoparticle sized ZrC in the carbon-carbon
fiber composite. The ZrC carbon-carbon fiber solid composition
exhibited great structural integrity with the inclusion of the
fiber reinforcement.
Example 69
[0188] Formulation of Precursor Composition of Tungsten Powder and
TPEB Prepolymer Containing Chopped Fibers--
[0189] TPEB prepolymer from Example 44 (1.5 g; 3.14 mmol) and
tungsten powder (19.5 g; 106 mmol) were ball milled for 5 minutes
resulting in a deep red-black fine powder. Chopped fibers (1.50 g,
1/4'' length) were added and the solid mixture was placed in 100 mL
of acetone and stirred for 6 hr. The solvent was removed and the
solid mixture was placed in a 21/2'' pellet die and pressed to
12,000 pounds for 1 minute.
Example 70
[0190] Conversion of Precursor Composition of Tungsten Powder and
TPEB Prepolymer Containing Chopped Fibers to Thermoset--
[0191] The 21/2'' pellet from Example 69 was placed in a furnace,
heated at 20.degree. C./min under an argon atmosphere to
210.degree. C., and held at this temperature for 10 hr (overnight)
resulting in the formation of a tough shaped carbon fiber
reinforced polymeric solid. The tungsten powder was homogeneous
dispersed in the solid thermoset-carbon fiber composite.
Example 71
[0192] Formation of Refractory WC Solid Carbon Fiber Reinforced
Ceramic in One Step by Heating at 10.degree. C./min to 1600.degree.
C. Under an Argon Atmosphere--
[0193] The carbon fiber-containing shaped polymeric thermoset
pellet (21.15 g) from Example 70 was placed in a 3'' tube furnace
and heated at 2.degree. C./min under a flow (100 cc/min) of argon
to 1600.degree. C. yielding a solid dense carbon fiber reinforced
ceramic with weight retention of 98.1%. The solid carbon fiber
reinforced ceramic was removed from the furnace, characterized by
XRD, and found to form nanoparticle sized WC in the carbon-carbon
fiber composite. The WC carbon-carbon fiber solid composition
exhibited great structural integrity with the inclusion of the
fiber reinforcement.
Example 72
[0194] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer at a 1C:1Ti Atom Ratio and Formation of Shaped
Pellet--
[0195] TPEB prepolymer form Example 44 (0.100 g; 0.209 mmol) and
TiH.sub.2 (0.398 g; 7.94 mmol) were finely ground with a mortar and
pestle. The powder was placed in an IR pellet press maker from
Harrick Scientific Products and was pressed to form a thin pellet
under vacuum.
Example 73 (Prophetic)
[0196] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer (1C:1Ti) to Solid Shaped Thermoset--
[0197] The pellet from Example 72 contained in the IR pellet press
maker is treated to 300.degree. C. in a vacuum oven for 2 hr to
complete crosslinking of the prepolymer and released from the IR
pellet press maker. The crosslinked pellet is further gradually
thermally treated under vacuum to 500.degree. C. and it held at
this temperature for 2 hr.
Example 74 (Prophetic)
[0198] Formation of Refractory TiC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0199] The shaped polymeric thermoset solid from Example 73 is
placed in a 3'' tube furnace, heated at 2.degree. C./min under a
flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr. The solid ceramic is removed from the
furnace and characterized by XRD, and is expected to form
nanoparticle sized TiC in an excess of carbon as the matrix.
Example 75
[0200] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer at a 1C:0.9Ti Atom Ratio and Formation of Shaped
Pellet--
[0201] TPEB prepolymer form Example 44 (0.100 g; 0.209 mmol) and
TiH.sub.2 (0.359 g; 7.15 mmol) were finely ground with a mortar and
pestle. The powder was placed in an IR pellet press maker and was
pressed to form a thin pellet under vacuum.
Example 76 (Prophetic)
[0202] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer (1C:0.9Ti) to Solid Shaped Thermoset--
[0203] The pellet from Example 75 contained in the IR pellet press
maker is treated to 300.degree. C. in a vacuum oven for 2 hr to
complete crosslinking of the prepolymer and released from the IR
pellet press maker. The crosslinked pellet is further gradually
thermally treated under vacuum to 500.degree. C. and it was held at
this temperature for 2 hr.
Example 77 (Prophetic)
[0204] Formation of Refractory TiC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0205] The shaped polymeric thermoset solid from Example 76 is
placed in a 3'' tube furnace, heated at 2.degree. C./min under a
flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr. The solid ceramic is removed from the
furnace, characterized by XRD, and is expected to form nanoparticle
sized TiC in an excess of carbon as the matrix.
Example 78
[0206] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer at a 1C:0.8Ti Atom Ratio and Formation of Shaped
Pellet--
[0207] TPEB prepolymer form Example 44 (0.100 g; 0.209 mmol) and
TiH.sub.2 (0.319 g; 6.35 mmol) were finely ground with a mortar and
pestle. The powder was placed in an IR pellet press maker and was
pressed to form a thin pellet under vacuum.
Example 79 (Prophetic)
[0208] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer (1C:0.8Ti) to Solid Shaped Thermoset--
[0209] The pellet from Example 78 contained in the IR pellet press
maker is treated to 300.degree. C. in a vacuum oven for 2 hr to
complete crosslinking of the prepolymer and released from the IR
pellet press maker. The crosslinked pellet is further gradually
thermally treated under vacuum to 500.degree. C. and held at this
temperature for 2 hr.
Example 80 (Prophetic)
[0210] Formation of Refractory TiC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0211] The shaped polymeric thermoset solid from Example 79 is
placed in a 3'' tube furnace, heated at 2.degree. C./min under a
flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr. The solid ceramic is removed from the
furnace, characterized by XRD, and is expected to form nanoparticle
sized TiC in an excess of carbon as the matrix.
Example 81
[0212] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer at a 1C:0.7Ti Atom Ratio and Formation of Shaped
Pellet--
[0213] TPEB prepolymer form Example 44 (0.100 g; 0.209 mmol) and
TiH.sub.2 (0.279 g; 5.56 mmol) were finely ground with a mortar and
pestle. The powder was placed in an IR pellet press maker and was
pressed to form a thin pellet under vacuum.
Example 82 (Prophetic)
[0214] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer (1C:0.7Ti) to Solid Shaped Thermoset--
[0215] The pellet from Example 81 contained in the IR pellet press
maker is treated to 300.degree. C. in a vacuum oven for 2 hr to
complete crosslinking of the prepolymer and released from the IR
pellet press maker. The crosslinked pellet is further gradually
thermally treated under vacuum to 500.degree. C. and held at this
temperature for 2 hr.
Example 83 (Prophetic)
[0216] Formation of Refractory TiC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0217] The shaped polymeric thermoset solid from Example 83 is
placed in a 3'' tube furnace, heated at 2.degree. C./min under a
flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr. The solid ceramic is removed from the
furnace, characterized by XRD, and is expected to form nanoparticle
sized TiC in an excess of carbon as the matrix.
Example 84
[0218] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer at a 1C:0.6Ti Atom Ratio and Formation of Shaped
Pellet--
[0219] TPEB prepolymer form Example 44 (0.100 g; 0.209 mmol) and
TiH.sub.2 (0.239 g; 4.76 mmol) were finely ground with a mortar and
pestle. The powder was placed in an IR pellet press maker and was
pressed to form a thin pellet under vacuum.
Example 85 (Prophetic)
[0220] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer (1C:0.6Ti) to Solid Shaped Thermoset--
[0221] The pellet from Example 84 contained in the IR pellet press
maker is treated to 300.degree. C. in a vacuum oven for 2 hr to
complete crosslinking of the prepolymer and released from the IR
pellet press maker. The crosslinked pellet is further gradually
thermally treated under vacuum to 500.degree. C. and it was held at
this temperature for 2 hr.
Example 86 (Prophetic)
[0222] Formation of Refractory TiC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0223] The shaped polymeric thermoset solid from Example 85 is
placed in a 3'' tube furnace, heated at 2.degree. C./min under a
flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr. The solid ceramic is removed from the
furnace, characterized by XRD, and is expected to form nanoparticle
sized TiC in an excess of carbon as the matrix.
Example 87
[0224] Formulation of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer at a 1C:0.5Ti Atom Ratio and Formation of Shaped
Pellet--
[0225] TPEB prepolymer form Example 44 (0.100 g; 0.209 mmol) and
TiH.sub.2 (0.199 g; 3.97 mmol) were finely ground with a mortar and
pestle. The powder was placed in an IR pellet press maker and was
pressed to form a thin pellet under vacuum.
Example 88 (Prophetic)
[0226] Conversion of Precursor Composition of TiH.sub.2 and TPEB
Prepolymer (1C:0.5Ti) to Solid Shaped Thermoset--
[0227] The pellet from Example 87 contained in the IR pellet press
maker is treated to 300.degree. C. in a vacuum oven for 2 hr to
complete crosslinking of the prepolymer and released from the IR
pellet press maker. The crosslinked pellet is further gradually
thermally treated under vacuum to 500.degree. C. and it was held at
this temperature for 2 hr.
Example 89 (Prophetic)
[0228] Formation of Refractory TiC Solid Ceramic in One Step by
Heating at 10.degree. C./min to 1600.degree. C. Under an Argon
Atmosphere--
[0229] The shaped polymeric thermoset solid from Example 88 is
placed in a 3'' tube furnace, heated at 2.degree. C./min under a
flow (100 cc/min) of argon to 1600.degree. C., and held at
1600.degree. C. for 2 hr. The solid ceramic is removed from the
furnace, characterized by XRD, and is expected to form nanoparticle
sized TiC in an excess of carbon as the matrix.
[0230] Obviously, many modifications and variations are possible in
light of the above teachings. It is therefore to be understood that
the claimed subject matter may be practiced otherwise than as
specifically described. Any reference to claim elements in the
singular, e.g., using the articles "a," "an," or "the" is not
construed as limiting the element to the singular.
* * * * *