Rapid solid-state synthesis of refractory materials

A process for producing a refractory material having the form TB.sub.o, e.g. zirconium nitride (ZrN), includes a first step of mixing a first salt having the form TX.sub.n, e.g. zirconium tetrachloride (ZrCl.sub.4) and a second salt having the form A.sub.m B, e.g. lithium nitride (Li.sub.3 N) in a ratio of n/m in a container. The process also includes a second step of igniting the mixture of the first and second salts, e.g. ZrCl.sub.4 and Li.sub.3 N, whereby the refractory material, e.g. ZrN, is produced along with byproducts having forms nAX and (n/m-o)B, e.g. 4LiCl and (1/6)N.sub.2, respectively. The process further includes a third step of separating the refractory material from the byproducts by solvent extraction. The stoichiometric ratio of the second salt to the first salt is n/m, e.g. 4/3. T is selected from the group consisting of transition metals, e.g. zirconium, and tetrelides, i.e. carbon, silicon, germanium, tin and lead. X is selected from the halide group consisting of fluorine, chlorine, bromine and iodine. A is selected from the group consisting of alkali metals, i.e. lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals, i.e. beryllium, magnesium, calcium, strontium and barium. B is a base selected from the group consisting of pnictides, i.e. nitrogen, hosphorus, arsenic, antimony and bismuth, and tetrelides, i.e. carbon, silicon, germanium, tin and lead, m and n are integers and o is a fraction, e.g. 3/3=1.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to metathesis reactions between two or more 
solid compounds and more particularly to metathesis reactions between two 
salt compounds for synthesizing refractory materials within seconds. 
2. Description of the Prior Art 
There has been a great need to find new methods of synthesizing refractory 
materials. Especially important are methods which enable refractory 
material to be synthesized more easily than by use of traditional high 
temperature reactions between elements. Since solid-solid diffusion 
between elements is slow, traditional syntheses generally require 
temperature of from 500.degree. C. to greater than 3000.degree. C. and 
time periods of from days to many weeks in order to produce desired 
refractory materials. Even after extensive heating for long periods of 
time these refractory materials may still contain unreacted starting 
materials, unwanted phases and/or poor stoichiometry. 
U.S. Pat. No. 4,279,737, entitled Hydro-Desulfurization Over Catalysts 
Comprising Chalcogenides of Group VIII Prepared by Low Temperature 
Precipitation from Nonaqueous Solution, issued to Russell R. Chianelli and 
Theresa Pecoraro on Jul. 21, 1981, teaches a method which is described for 
the preparation of chalcogenides of ruthenium, rhodium, osmium and iridium 
transition metals of the Periodic Table of the Elements which includes 
mixing in the absence of an aqueous solvent a Group VIII transition metal 
salt with a source of chalcogenide. The chalcogenide is selected from the 
group consisting of sulfur, selenium, tellurium and mixtures thereof, 
yielding a precipitate of the formula MX.sub.y wherein M is selected from 
the group consisting of ruthenium, rhodium, osmium and iridium, X is 
sulfur, selenium, tellurium and mixtures thereof and y is a number ranging 
from about 0.1 to about 3, preferably 0.1 to about 2.5. By the practice of 
the nonaqueous synthesis technique, Group VIII chalcogenides are prepared 
which are finely divided, have a high surface area, small particle size 
and small crystallite size which are also free of excess sulfur, water 
and/or hydrolysis products. This technique also permits the preparation of 
a heretofore unobtainable composition, layered stoichiometric osmium 
disulfide. The precipitates which result as a consequence of the instant 
process may be cleansed of any anion salt coproduct by any technique 
common to the art, pumping under vacuum being one such technique, washing 
with a suitable solvent being another. Compounds of the formula MX.sub.y 
wherein M, X and y are as defined above, prepared by the low temperature, 
nonaqueous precipitation technique herein disclosed are superior 
sulfur-tolerant catalysts in catalytic processes, for example, 
hydrodesulfurization, hydrodenitrogenation, hydroconversion, 
hydrogenation. 
U.S. Pat. No. 4,288,422, entitled Method of Preparing Chalcogenides of 
Group VIII by Low Temperature Precipitation from Nonaqueous Solution, the 
Products Produced by Said Method and Their Use as Catalysts, issued to 
Russell R. Chianelli and Theresa A. Pecoraro on Sep. 8, 1981, teaches a 
method which described for the preparation of chalcogenides of ruthenium, 
rhodium, osmium and iridium transition metals of the Periodic Table of the 
Elements which includes mixing in the absence of an aqueous solvent a 
Group VIII transition metal salt with a source of chalcogenide. The 
chalcogenide is selected from the group consisting of sulfur, selenium, 
tellurium and mixtures thereof, yielding a precipitate of the formula 
MX.sub.y wherein M is selected from the group consisting of ruthenium, 
rhodium, osmium and iridium, X is sulfur, selenium, tellurium and mixtures 
thereof and y is a number ranging from about 0.1 to about 3, preferably 
0.1 to about 2.5. By the practice of the nonaqueous synthesis technique, 
Group VIII chalcogenides are prepared which are finely divided, have a 
high surface area, small particle size and small crystallite size which 
are also free of excess sulfur, water and/or hydrolysis products. Layered 
stoichiometric osmium disulfide is prepared by this technique. The 
precipitates may be cleansed of any anion salt coproduct by any technique 
common to the art. Compounds of the formula MX.sub.y thus prepared are 
superior sulfur-tolerant catalysts in catalytic processes, for example, 
hydro-desulfurization, hydrodenitrogenation, hydroconversion, 
hydrogenation. 
U.S. Pat. No. 4,308,171, entitled Method of Preparing Di and Poly 
Chalcogenides of Group VIIb by Low Temperature Precipitation from 
Nonaqueous Solution and Small Crystallite Size Stoichiometric Layered 
Dichalcogenides of Rhenium and Technetium, issued Martin B. Dines, Russell 
R. Chianelli and Theresa A. Pecoraro on Dec. 29, 1981, teaches a method 
whereby finely divided, small particle (0.1 micron or less) small 
crystallite (about 50 Angstrom times 100 Angstrom or less) chalcogenides 
of manganese, rhenium and technetium are described. These compositions are 
prepared by mixing in the absence of an aqueous solvent, a manganese, 
rhenium or technetium salt with a source of chalcogenide yielding a 
precipitate. The manganese, rhenium or technetium salt and the source of 
chalcogen can be mixed either neat or in the presence of a nonaqueous 
aprotic solvent. The precipitate which results before removal of the anion 
salt is a finely divided product. In the case of rhenium dichalcogenide 
the product possesses a layered structure. The anion salt may be removed 
by any technique common to the art, pumping under vacuum being one such 
technique, washing with a suitable solvent being another. A method is 
described for the preparation of di- and poly-chalcogenides of the formula 
MX.sub.y wherein M is a metal selected from the group consisting of 
manganese, rhenium and technetium, X is a chalcogen selected from the 
group consisting of sulfur, selenium, tellurium and mixtures thereof, and 
y is a number ranging from about 1.5 to about 4, preferably about 2, 
comprising the low temperature, nonaqueous precipitation of said MX.sub.y 
compounds from mixtures of the salts of the manganese, rhenium and 
technetium. The precipitation occurs in the absence of aqueous solvents. 
The process of the instant invention permits the preparation of materials 
uncontaminated by water, oxygen or hydrolysis products. 
U.S. Pat. No. 4,323,480, entitled Method of Preparing Di and Poly 
Chalcogenides of Group IVb, Vb, Molybdenum and Tungsten Transition Metals 
by Low Temperature Precipitation from Non-aqueous Solution and the Product 
Obtained by Said Method, issued to Martin B. Dines and Russell R. 
Chianelli on Apr. 6, 1982, teaches the finely divided, high surface area, 
small crystallite (0.1 micron or less) di- and poly-transition metal 
chalcogenides are prepared by mixing in the absence of an aqueous solvent 
a transition metal salt with a source of chalcogen yielding a precipitate. 
The salt and the chalcogen source can be mixed either neat or in the 
presence of a nonaqueous solvent. The precipitate which results before 
removal of the anion salt is a finely divided product. 
U.S. Pat. No. 4,368,115, entitled Catalysts Comprising Layered 
Chalcogenides of Group IVb-Group VIIb Prepared by a Low Temperature 
Nonaqueous Precipitate Technique, issued to Russell R. Chianelli, Theresa 
A. Pecoraro and Martin B. Dines on Mar. 11, 1981, teaches processes for 
the catalytic treatment of hydrocarbon feedstreams containing organic 
sulfur which include contacting the feedstream with a catalyst for a time 
at a temperature and pressure sufficient to effect the desired catalytic 
change on the feedstream. The improvement includes using as the catalyst a 
layered composition of the formula MX.sub.y wherein M is a transition 
metal selected from the group consisting of Group IVb, Vb, VIb, VIIb and 
uranium, X is a chalcogen selected from the group consisting of sulfur, 
selenium, tellurium, and mixtures thereof, y is a number ranging from 
about 1.5 to about 3. The catalyst is prepared by reacting neat or in the 
presence of a nonaqueous solvent a Group IVb to VIIb or uranium metal 
salt, and a source of sulfide, selenide or telluride ions, and mixing the 
reactants at temperatures below 400.degree. C. and at atmospheric 
pressures. The catalyst may be isolated by filtration and washing with 
excess solvent (when one is used) or by vacuum pumping any volatile 
coproduced anion salt. Preferably the chalcogenide is sulfur and y is 
about 1.5 to about 2. The catalytic processes which are benefited by the 
use therein of the above-described compositions are hydrodesulfurization, 
hydrodenitrogenation, hydroconversion and hydrogenation run in the 
presence of hydrogen or a hydrogen donor solvent. 
U.S. Pat. No. 4,399,115, entitled Synthesis of Silicon Nitride, issued to 
Kimihiko Sato, Kunihiko Terase and Hitoshi Kijimuta on Aug. 16, 1983, 
teaches a process for synthesizing silicon nitride by reacting a silicon 
halide and ammonia at a high temperature, which is characterized in that 
at least while the reaction product is amorphous, hydrogen and chlorine 
are burned in the reaction zone where a halogen containing inorganic 
silicon compound and ammonia are reacting, and the reaction of the 
reactants is effected by the heat of combustion thus obtained. 
U.S. Pat. No. 4,416,863, entitled Method for Synthesizing Amorphous Silicon 
Nitride, issued to Kimihiko Sato, Kunihiko Terase, Hitoshi Kijimuta and 
Yukinori Ohta on Nov. 22, 1983, teaches a method for synthesizing 
amorphous silicon nitride in which wherein silicon halide and ammonia are 
reacted in a reaction vessel at a high temperature in the absence of 
oxygen to synthesize powder of amorphous silicon nitride. The powder is 
then separated from a gas containing therein gaseous ammonia halide which 
has been produced simultaneously with the amorphous silicon nitride by use 
of a collecting means, includes directly mixing, in advance of the 
separation, cool gas containing therein neither oxygen nor moisture into 
the gas to cool down the powder and gas so that both substances may be put 
in the collecting means without deposition of ammonium halide to the inner 
wall of the reaction vessel, and other component parts. 
U.S. Pat. No. 4,731,235, entitled Method of Making Silicon Nitride, issued 
to John L. Schrader, Jr. and Patience G. Dowd on Mar. 15, 1988, teaches 
the manufacture of silicon nitride powder by the vapor phase reaction of a 
silicon halide with ammonia at an elevated temperature in a flowing 
system, oxygen content of the silicon nitride is controlled by preventing 
entry of room air into the reaction means and by feeding wet nitrogen into 
the system at about the exit end of the reaction means. 
U.S. Pat. No. 4,812,301, entitled Production of Titanium Nitride, Carbide, 
and Carbonitride Powders, issued to Charles F. Davidson, Monte B. Shirts 
and Donna D. Harbuck on Mar. 14, 1989, teaches a process for producing 
substantially oxygen-free titanium carbide, nitride or carbonitride in 
powder form which includes treating a gas phase reaction mixture of 
titanium halide, desirably TiCl.sub.4, a reductant vapor, desirably sodium 
or magnesium, and a reactive gas capable of furnishing carbon, nitrogen or 
mixtures thereof at the reaction temperature, desirably nitrogen, methane 
or ammonia, to a temperature in the range from 500.degree. C. to 
1250.degree. C., preferably 800.degree. C. to 1100.degree. C., whereby the 
titanium halide is substantially simultaneously reduced and carbided, 
nitrided or carbonitrided. The process may also be practiced using 
volatile metal halides of metals such as zironium, hafnium, vanadium, 
niobium, tantalum and silicon for forming substantially oxygen-free 
carbides, nitrides or carbonitrides thereof in powder form. 
U.S. Pat. No. 4,859,443, entitled Preparation of Silicon Nitride Powder, 
issued to Laszlo Marosi on Aug. 22, 1989, teaches about a silicon nitride 
powder which is prepared in a gas-phase reaction by reacting silicon 
tetrachloride with ammonia at above 500.degree. C. in a fluidized bed of 
silicon nitride particles. An amorphous silicon nitride having a BET 
specific surface area of greater than 50 m.sup.2 /g is used at the 
beginning of the reaction. The resulting silicon nitride is then separated 
from the ammonium chloride simultaneously formed. 
U.S. Pat. No. 4,859,639, entitled Process of Making Amorphous Silicon 
Nitride Powder, issued to Hans-Josef Sterzel on Aug. 22, 1990, teaches in 
amorphous silicon nitride powder, from 0.5 to 40 mol % of the silicon are 
replaced by one or more of the elements boron, aluminum, yttrium, 
lanthanum, titanium, zirconium, tungsten and molybdenum. The powder is 
obtained by reacting the halides of the corresponding elements, which are 
dissolved in an inert organic solvent in the particular ratio desired, 
with ammonia. The solid reaction product formed is separated off from the 
liquid phase and treated at from 800.degree. C. to 1000.degree. C. The 
powder is particularly suitable as a starting material for the production 
of sintered articles. 
U.S. Pat. No. 4,929,432, entitled Process for Producing Crystalline Silicon 
Nitride Powder, issued to Wei-Ming Shen on May 29, 1990, teaches a process 
for producing crystalline silicon nitride powder by a gas phase reaction 
of ammonia (NH.sub.3) and silane (SiH.sub.4) with a molar ratio of 7:1 or 
above at a temperature of 900.degree. C. or above and the heating the 
as-reacted amorphous powders at a temperature of 1350.degree. C. to 
1800.degree. C. to convert the powders to a highly pure and submicron 
crystalline silicon nitride powder comprising at least a 90% 
alpha-Si.sub.3 N.sub.4 phase. 
U.S. Pat. No. 4,944,930, entitled Synthesis of Fine-Grained Alpha-Silicon 
Nitride by a Combustion Process, issued to J. Holt, Donald D. Kingman and 
Gregory M. Bianchini on Jul. 31, 1990, teaches a combustion synthesis 
process for the preparation of alpha-silicon nitride and composites 
thereof is disclosed. Preparation of the alpha-silicon nitride comprises 
the steps of dry mixing silicon powder with an alkali metal azide, such as 
sodium azide, cold-pressing the mixture into any desired shape, or loading 
the mixture into a fused, quartz crucible, loading the crucible into a 
combustion chamber, pressurizing the chamber with nitrogen and igniting 
the mixture using an igniter pellet. The method for the preparation of the 
composites includes dry mixing silicon powder (Si) or silicon dioxide 
(SiO.sub.2), with a metal or metal oxide, adding a small amount of an 
alkali metal azide such as sodium azide, introducing the mixture into a 
suitable combustion chamber, pressurizing the combustion chamber with 
nitrogen, igniting the mixture within the combustion chamber, and 
isolating the alpha-silicon nitride formed as a reaction product. 
SUMMARY OF INVENTION 
In view of the foregoing factors and conditions which are characteristic of 
the prior art it is the primary object of the present invention to provide 
metathesis reactions between two salt compounds for synthesizing 
refractory materials within seconds. 
It is another object of the present invention to provide metathesis 
reactions which can produce refractory materials very rapidly while 
requiring only a small amount of heat or energy to initiate them. 
It is still another object of the present invention to provide metathesis 
reactions which can produce refractory materials very rapidly and in which 
the starting materials and their byproduct are chosen to be soluble in 
certain solvents so that they can be readily removed resulting in 
refractory materials of high purity. 
It is yet another object of the present invention to provide metathesis 
reactions which can produce refractory materials of controlled particle 
size and crystallinity very rapidly. 
It is still yet another object of the present invention to provide 
metathesis reactions which can produce high quality solid solution 
refractory materials. 
In accordance with the present invention an embodiment of a process for 
producing a refractory material having the form TB.sub.o, e.g. zirconium 
nitride (ZrN) is described. The process includes a first step of mixing a 
first salt having the form TX.sub.n, e.g. zirconium tetrachloride 
(ZrCl.sub.4) and a second salt having the form A.sub.m B, e.g. lithium 
nitride (Li.sub.3 N) in a ratio of n/m in a container. The process also 
includes a second step of igniting the mixture of the first and second 
salts, e.g. ZrCl.sub.4 and Li.sub.3 N, whereby the refractory material, 
e.g. ZrN, is produced along with byproducts having forms nAX and (n/m-o)B, 
e.g. 4LiCl and (1/6)N.sub.2, respectively. The process further includes a 
third step of separating the refractory material from the byproducts by 
solvent extraction. The stoichiometric ratio of the second salt to the 
first salt is n/m, e.g. 4/3. T is selecting from the group consisting of 
transition metals, e.g. zirconium, and tetrelides, i.e. carbon, silicon, 
germanium, tin and lead. X is selected from the halide group consisting of 
fluorine, chlorine, bromine and iodine. A is selected from the group 
consisting of alkali metals, i.e. lithium, sodium, potassium, rubidium and 
cesium, and alkaline earth metals, i.e. beryllium, magnesium, calcium, 
strontium and barium. B is a base selected from the group consisting of 
pnictides, i.e. nitrogen, phosphorus, arsenic, antimony and bismuth, and 
tetrelides, i.e. carbon, silicon, germanium, tin and lead, m and n are 
integers and o is a fraction, e.g. 3/3=1. 
Other claims and many of the attendant advantages will be more readily 
appreciated as the same becomes better understood by reference to the 
following detailed description. 
The features of the present invention which are believed to be novel are 
set forth with particularity in the appended claims.

DESCRIPTION OF THE PREFERRED EMBODIMENT 
In order to best understand the present invention it is necessary to refer 
to the following description of the preferred embodiment. A process for 
producing a refractory material having the form TB.sub.o includes a first 
step of mixing a first salt having the form TX.sub.n and a second salt 
having the form A.sub.m B in a container. The process also includes a 
second step of igniting the mixture of the first and second salts whereby 
the refractory material is produced along with byproducts having forms nAX 
and (n/m-o)B. The process further includes a third step of separating the 
refractory material from the byproducts by solvent extraction. The 
stoichiometric ratio of the second salt to the first salt is n/m. T is 
selected from the group consisting of transition metals, e.g. zirconium 
and tetrelides, i.e. carbon, silicon, germanium, tin and lead. X is from 
the halide group consisting of fluorine, chlorine, bromine and iodine. A 
is selected from the group consisting of alkali metals, i.e. lithium, 
sodium, potassium, rubidium and cesium, and alkaline earth metals, i.e. 
beryllium, magnesium, calcium, strontium and barium. B is a base selected 
from the group consisting of pnictides, i.e. nitrogen, phosphorus, 
arsenic, antimony and bismuth, and tetrelides, i.e. carbon, silicon, 
germanium, tin and lead, m and n are integers and o is a fraction, e.g. 
3/3=1. 
EXAMPLE 1 
Rapid Solid-State Synthesis of Zirconium Nitride, ZrN 
A mortar and pestle was used to mix 0.991 gram of zirconium tetrachloride 
(ZrCl.sub.4) and 0.204 gram of lithium nitride (Li.sub.3 N) in order to 
form the reactant mixture with a stoichiometric ratio of Li.sub.3 N to 
ZrCl.sub.4 of 4/3. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting brown product 
was washed with methanol, dried and then ground with a mortar and pestle. 
The product was further washed with ten percent nitric acid, water and 
acetone on a vacuum filter. The powder was then dried on a vacuum line. 
The resulting product was pure ZrN with a cubic lattice spacing of 4.57 
Angstroms as determined by X-ray powder diffraction. Use of the Scherrer 
equation gave a calculated particle size of 200-250 Angstroms. See 
Elements of X-ray Diffraction written by B. D. Cullity, Addison-Wesley, 
Reading, Mass., 1956. The product yield was fifty five percent (0.2488 
gram out of 0.4475 gram theoretically possible). A pressed disc indicated 
metallic type conductivity. A balanced equation is as follows: 
EQU ZrCl.sub.4 +4/3 Li.sub.3 N.fwdarw.ZrN+4LiCl+1/6N.sub.2 
EXAMPLE 2 
Rapid Solid-State Synthesis of Zirconium Nitride, ZrN 
A mortar and pestle was used to mix 4.434 gram of zirconium tetrachloride 
(ZrCl.sub.4) and 0.882 gram of lithium nitride (Li.sub.3 N) in order to 
form the reactant mixture with a stoichiometric ratio of Li.sub.3 N to 
ZrCl.sub.4 of 4/3. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting yellow-brown 
product was washed with methanol, dried and then ground with a mortar and 
pestle. The product was further washed with ten percent nitric acid, 
methanol, water and acetone on a vacuum filter. The powder was then dried 
on a vacuum line. The resulting light-brown product was pure ZrN with a 
cubic lattice spacing of 4.57 Angstroms as determined by X-ray powder 
diffraction. Use of the Scherrer equation gave a calculated particle size 
of 500-600 Angstroms. The product yield was ninety-one percent (1.822 
grams out of 1.998 grams theoretically possible). A pressed disc indicated 
metallic type conductivity. A balanced equation is as follows: 
EQU ZrCl.sub.4 +4/3 Li.sub.3 N.fwdarw.ZrN+4LiCl+1/6N.sub.2 
EXAMPLE 3 
Rapid Solid-State Synthesis of Titanium Nitride, TiN 
A mortar and pestle was used to mix 0.5807 gram of titanium tetraiodide 
(TiI.sub.4) and 0.0526 gram of lithium nitride (Li.sub.3 N) in order to 
form the reactant mixture with a stoichiometric ratio of Li.sub.3 N to 
ZrCl.sub.4 of 4/3. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting black product 
was washed with methanol, water, and dried with acetone on a vacuum 
filter. The resulting product was pure TiN with a cubic lattice spacing of 
4.22 Angstroms as determined by X-ray powder diffraction. Use of the 
Scherrer equation gave a calculated particle size of 200-250 Angstroms. A 
balanced equation is as follows: 
EQU TiI.sub.4 +4/3 Li.sub.3 N.fwdarw.TiN+4LiI+1/6N.sub.2 
EXAMPLE 4 
Rapid Solid-State Synthesis of Hafnium Nitride, HfN 
A mortar and pestle was used to mix 0.6765 gram of hafnium tetrachloride 
(HfCl.sub.4) and 0.0980 gram of lithium nitride (Li.sub.3 N) in order to 
form the reactant mixture with a stoichiometric ratio of Li.sub.3 N to 
ZrCl.sub.4 of 4/3. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting black product 
was washed with methanol and water and dried with acetone on a vacuum 
filter. The resulting product was pure HfN with a cubic lattice spacing of 
4.52 Angstroms as determined by X-ray powder diffraction. Use of the 
Scherrer equation gave a calculated particle size of approximately 150 
Angstroms. A balanced equation is as follows: 
EQU HfCl.sub.4 +4/3 Li.sub.3 N.fwdarw.HfN+4LiCl+1/6N.sub.2 
EXAMPLE 5 
Rapid Solid-State Synthesis of Silicon Nitride, Si.sub.3 N.sub.4 
A mortar and pestle was used to mix 0.1984 gram of silicon tetraiodide 
(SiI.sub.4) and 0.0340 gram of lithium nitride (Li.sub.3 N) in order to 
form the reactant mixture with a stoichiometric ratio of Li.sub.3 N to 
ZrCl.sub.4 of 4/3. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting grey product 
was washed with methanol and water to remove lithium iodide, and dried 
with acetone on a vacuum filter. The resulting light-grey product was 
amorphous as determined by X-ray powder diffraction. No crystallinity was 
observed even after heating the sample to 900.degree. C. under vacuum. A 
balanced equation is as follows: 
EQU 3SiI.sub.4 +4Li.sub.3 N.fwdarw.Si.sub.3 N.sub.4 +12LiCl 
EXAMPLE 6 
Rapid Solid-State Synthesis of Zirconium Phosphide, ZrP 
A mortar and pestle was used to mix 0.3181 gram of zirconium tetrachloride 
(ZrCl.sub.4) and 0.1819 gram of sodium phoside (Na.sub.3 P) in order to 
form the reactant mixture with a stoichiometric ratio of Na.sub.3 P to 
ZrCl.sub.4 of 4/3. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting grey-black 
product was washed with methanol and water on a vacuum filter. The powder 
was then dried on a vacuum line. The resulting product was pure ZrP with a 
cubic lattice spacing of 5.29 Angstroms as determined by X-ray powder 
diffraction. The product yield was approximately forty-five percent. A 
balanced equation is as follows: 
EQU ZrCl.sub.4 +4/3 Na.sub.3 P.fwdarw.ZrP+4NaCl+1/12P.sub.4 
EXAMPLE 7 
Rapid Solid-State Synthesis of Molybdenum Carbide, Mo.sub.2 C 
A mortar and pestle was used to mix 0.5145 gram of molybdenum pentachloride 
(MoCl.sub.5) and 0.3292 gram of sodium acetylide (Na.sub.2 C.sub.2) in 
order to form the reactant mixture with a stoichiometric ratio of Na.sub.2 
C.sub.2 to MoCl.sub.5 of 5/2. The reactant mixture was placed in a 45 
milliliter stainless steel container. A screw top cap was placed on the 
stainless steel container. The screw top cap had two insulated leads 
protruding therethrough, which held a nichrome filament in the reactant 
mixture. An external electric charge was applied to the leads for no more 
than two seconds thereby igniting the reactant mixture. The resulting 
black product was washed with methanol, water and acetone on a vacuum 
filter. The powder was then dried on a vacuum line. The resulting product 
contained Mo.sub.2 C as determined by X-ray powder diffraction. The 
product yield was fifty percent (0.1456 gram out of 0.2938 gram 
theoretically possible). A balanced equation is as follows: 
EQU MoCl.sub.5 +5/2Na.sub.2 C.sub.2 .fwdarw.1/2Mo.sub.2 C+5NaCl+9/2C 
EXAMPLE 8 
Rapid Solid-State Synthesis of Silicon Carbide, SiC 
A mortar and pestle was used to mix 0.3556 gram of carbon tetraiodide 
(CI.sub.4) and 0.0514 gram of magnesium silicide (Mg.sub.2 Si) in order to 
form the reactant mixture with a stoichiometric ratio of Mg.sub.2 Si to 
CI.sub.4 of 1/1. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting black product 
was washed with methanol, water, dried and then ground with a mortar and 
pestle., The product was further washed with ten percent HF/HNO.sub.3 (to 
remove Si impurities), methanol, water and acetone on a vacuum filter. The 
resulting product contained silicon carbide, SiC, as indicated by X-ray 
powder diffraction. A balanced equation is as follows: 
EQU Mg.sub.2 Si+CI.sub.4 .fwdarw.SiC+2MgI.sub.2 
EXAMPLE 9 
Rapid Solid-State Synthesis of Zirconium Disilicide, ZrSi.sub.2 
A mortar and pestle was used to mix 0 3551 gram of zirconium tetrachloride 
(ZrCl.sub.4) and 0.1005 gram of magnesium silicide (Mg.sub.2 Si) in order 
to form the reactant mixture with a stoichiometric ratio of Mg.sub.2 Si to 
ZrCl.sub.4 of 1/1. The reactant mixture wa placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting black product 
was washed with methanol, water, acetone, and air dried. The product was 
further washed with ten percent nitric acid (to remove trace metal 
impurities), water and acetone on a vacuum filter. The resulting product 
was single phase ZrSi.sub.2 as determined by X-ray powder diffraction. A 
balanced equation is as follows: 
EQU ZrCl.sub.4 +Mg.sub.2 Si.fwdarw.1/2ZrSi.sub.2 +2MgCl.sub.2 +1/2Zr 
EXAMPLE 10 
Rapid Solid-State Synthesis of Molybdenium Disilicide, MoSi.sub.2 
A mortar and pestle was used to mix 0.2980 gram of molybdenum pentachloride 
(MoCl.sub.5) and 0.0987 gram of magnesium silicide (Mg.sub.2 Si) in order 
to form the reactant mixture with a stoichiometric ratio of Mg.sub.2 Si to 
MoCl.sub.5 of 5/4. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting black product 
was washed with methanol, water and air dried. The product was further 
washed with aqua regia (to remove molybdenum (Mo) metal impurities), and 
acetone on a vacuum filter. The resulting product was single phase 
MoSi.sub.2 as determined by X-ray powder diffraction. A balanced equation 
is as follows: 
EQU MoCl.sub.5 +5/4 Mg.sub.2 Si.fwdarw.5/8 MoSi.sub.2 +5/2 MgCl.sub.2 +3/8 Mo 
EXAMPLE 11 
Rapid Solid-State Synthesis of Iron Silicide, FeSi 
A mortar and pestle was used to mix 0.4481 gram of iron (III) chloride 
(FeCl.sub.3) and 0.20254 gram of magnesium silicide (Mg.sub.2 Si) in order 
to form the reactant mixture with a stoichiometric ratio of Mg.sub.2 Si to 
FeCl.sub.3 of 3/4. The reactant mixture was placed in a 45 milliliter 
stainless steel container. A screw top cap was placed on the stainless 
steel container. The screw top cap had two insulated leads protruding 
therethrough, which held a nichrome filament in the reactant mixture. An 
external electric charge was applied to the leads for no more than two 
seconds thereby igniting the reactant mixture. The resulting black product 
was washed with methanol, water and acetone on a vacuum filter. The 
product was further washed with ten percent nitric acid to remove trace 
metal impurities. The resulting product was single phase FeSi as 
determined by X-ray powder diffraction. A balanced equation is as follows: 
EQU FeCl.sub.3 +3/4Mg.sub.2 Si.fwdarw.3/4 FeSi+3/2 MgCl.sub.2 +1/4Fe 
Other examples of this invention can be generated using different 
combinations of elements T, X, A and B. The element T is selected from the 
group of transition metals, including scandium (Sc), titanium (Ti), 
vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), 
nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium 
(Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), 
palladium (Pd), silver (Ag), cadmium (Cd), lanthanum (La), hafnium (Hf), 
tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), 
platinum (Pt), gold (Au), mercury (Hg) and tetrelides, consisting of 
carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb). The 
element X is selected from the halide group, consisting of fluorine (F), 
chlorine (Cl), bromine (Br) and iodine (I). The element A is selected from 
the group of alkali metals and alkaline earth metals, consisting of 
lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), 
beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium 
(Ba). The element B is selected a base from the group of pnictides, 
consisting of nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb) 
and bismuth (Bi), and tetrelides, consisting of carbon (C), silicon (Si), 
germanium (Ge), tin (Sn) and lead (Pb). 
From the foregoing it can be seen that a process for producing the 
refractory material has been described. Accordingly it is intended that 
the foregoing disclosure shall be considered only as an illustration of 
the principle of the present invention.