Note: Descriptions are shown in the official language in which they were submitted.
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CAR~3CIN--CONTAINING BLACR GLASS MONOLITHS
B_CKGROUND OF THE INVENTION
Ceramics have been known for many hundreds of
years and hav~ been u~ed as coatings or a~ fabricated parts
and are employed wherever their charact~ristics SUC}I as
durability, nonporo~ityr electrical conductivity or
nonconductivity, and heat protection are required. One of
th~ more recent ceramic material~ i~ a silicon-carbon-oxygen
system, named as a black glass, which can find use in
certain situat~on~ where extremely high temperatures are
present.
Traditionally; the introduction of carbon in
glasses was made by impregnating porou~ glas~ with a
concentrated solution of an organic compound and
subsequently firing in a reducin~ or n~u~ral atmosphere.
The carbon-containiDg product is generally regarded as a
composite containing carbon and ~ilica. Elme~ and Meissner
( ~ , 59, 2~6, 1976) of
Corning Gla~ Work~ repor~ed that the annealing poin~ of
recon~tructea 96% sllicon dioxide glasse~ is markedly
increa~d by in~orporating carbon in porous glass. Furfuryl
alcohol w~ u~d a~ the pyrolyzabl~ organic compound. They
attributed th0 increa8e of about 100C in annealing point to
the effect of hydroxyl removal from ~he internal ~urface of
the porou~ gla~ by hydroxyl reaction wi~h carbo~. The
resistivi~s of sample~ with le~3 ~han ~% carbon content
approaohed that of the gla~ wh~reas the electrical
re~istivi~ie~ of carbon-~ontain~ng silica with ear~on
be~ween 4.5-7% are in the rangs of 1-3 ohm-cm, thu~
producinq elec~rically conduotive glas~e~. The highest
carbon cont~n~ i~ th~ final gla~ses ~hey could produce is
~.5~%O
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Smith ~ Cra~dall reported in U.S Patent 3,378,431
a method of making carbon--containing Iylass by hot~pressing
to sintering temperature a mixture of colloidal silica and
an organic compound known in khe txadle as "Carbowax'~
~polyethylene glycol) in an oxygen-free atmosphere. The
black gla~s ob~ain~d from the mix~ure of 33~ "Carbowax" and
67~ silicon dioxide show~d the presenc~ o~ 1.2~ by weight of
carbon. A devitriication-r2sistant bonded ma~s of vitreous
silicon dioxide and carbon physically in~eparable and
micro~copically indis~inguishable from cilica waY ob~ained.
The black glasq has a low thermal diffuivity and more
resistance t~ cry~tallization than pur~ vitreous silica.
Devitxi~ication temperature increased by 150C to 1250C as
compared with colloidal silica.
Carbon-modified ~ilica glas~ ha~ been used as a
composite matrix by Larsen, Harada and Nakamum (Report No.
AFWAS-TR~3-4134, December, 1983~ Wrigh~-Patterson hFB,
Ohio)~ In producing fiber-r~inforced composite~, the
proces.~ng sequence include~ slurry impregnation of silicon
carbide fiber in an a~ueous slurry of a carbowax
Ipolyeth~lene glycol) and a silicon-contain~ng compound
know~ in the trade a Cab-0-Sil (a ~illcon dioxide powder
manufactur~d by Gabot), layout o~ prepregyed fiber tow~, and
hot-pressing. The compo~ites thu~ obtained exhibited high
porosity and brittle fracture indicativ~ of low toughness.
They con~lud~d that the sllicon carbid~/blaGk gla~s fib~r
compo~ite i~ a promising ma~erlal, although the proper~y
goal~ were no~ achiev~d. There i su~pi~ion ~ha~ ~he
silicon carbide fiber~ may hav~ degraded.
More rec~ntly, formation of carbonaceou~ ceramics
has be~n carri~d out through the use o~ the sol-gPl process.
January di~lose~ in U.S. Patent No. 4,472,510 ~h~ use of
th~ sol g~l proce~s to form monolithic glass~s containing
carbo~ ~hrough pyrolysis of the gel~ of
org~no~ilse~quio2carles ~ metal oxide3 and metal alkoxide3 .
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~onomann in Great ~ritain Patent 1,3~9,576 disclosed the
formation of silicon and quartz fi~ers using silses~uioxanes
as precur~ors. Their gelling process used selected
organosilicon compounds for the prepara~tion of the ceramic
precursor ba ed on ~he following reaotion:
- Si-OR ~ ~2 ~ - Si-OH ~ RO~ (l)
_ Si-OH + HO-Si-- ~ - Si-O-~Si- ~ ~2~ (2)
in which R represents an organio radical such as alkyl
groups and aryl groups such a~ phenyl group.
The uniqueness o the sol-ael process is the
ability to obtain homogeneous, purer glassy Products b~ low
temperature processe Al~o, the use of a liquia svl as the
starting materials allows the preparation of intractable
monoliths of complicated shape~ utilizing a li~uid path.
The advantages of su~h a procedure over the powder
consolidation techniques, such as sinter~ng and hot
isostatic pressing, are th~ir formabilitY of complicated
shape~ and low temperatur~ operationO ~owever, monolithic
black glas~e~ produced via hydroly~is and condensation of
organoalkoxy~ilane~ are not practical because of the
requirement for ~ery long dxyins periods and delicate
gelling conditions. For example, ~anuary prepared a~0.~6
cubic centimoter methyltrim~thoxy~ilane gel monolith over a
drYing period of about three weeks, which, upon pyrolysis,
yielded a carbon containing black gla~s monolith of density
1.6 gram~ p~r milllliter.
The very slow drying rate is n~c~ssary for
reducing crack-~ during the gelation period. These cracks
form as a result of the non-uniform surface tensions created
by the evaporation of tha ~pli~-of~ wa~er or al~ohol
mol~cule3 in th~ hydroly~is (1) and condensation ~2~
reaction~. In th~ ln~tant in~ention, a hydrosilvlation
reaction w~ u~d ~or the gelation ~rocess in plac~ of the
hydrolysis~ond~nsation routP~ The hvdro~ilylation involves -`
addition of ~ilan~ H) to vinyl silane (Si~C~=C~) to
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form an ethylene linkage as illustrated in the following
equation:
- Si-H + CH2 - CH Si ~ SiC~CH2Si ~ (3)
The features of the hydrosilylation reaction are such that
there is neither a small molecule reac~ion product nor a
weight los~ during yelation and that ~he carbons in the
ethylene linkage are bonded to the silicon a~om~O This
gelation reaction completely eliminates the drying problem
inherent in the hydrolysi~ of organoalkoxysilan~ process.
We also unexpectedly found that cyclosiloxan~ gels cro3s-
linked by hydro~ilylation reaction produced upon pyroly~is
to high temperature in a non oxidizing atmo~phere high
carbon content, high yield and high den8ity black glasses.
Monomann in Great ~ritain Patent 1,359,576
disclosed the u e of a phenyl group rather than a methyl
group as R i~ order to increase the carbon content of their
products. By choosing phenyl group a~ R, the carbon weight
percent can be increased to as high as ca. 30%. How0ver, we
have shown in our simulation exp~riments that thP carbon
present ~arted to oxidize at 550C in flowing air and was
completely removed before 1000C. Th~refore, the carbon
derived fro~ pyroly~i~ of the phenyl group ~s free carbon
susceptible to oxidatio~ while our inv~ntion produces carbon
content~ with the carbon bonded to silicon rather than
~iexi~ting as fr~e carboD, resulting in a carbon-containing
material that i~ oxidation resi~tant up ~o about 1400C.
Okamura ~t al. reported in U.S. 4,618~591 a method
of making silicon carbide-carbon compo~it~ mold~d product by
using polycarbosilane as ~he precursor for 2 matrix
material~ The polycarbosilane on pyrolysis ~orms
microcry~t~lline silicon carhide with inclusion of low
oxyg~n perc~ntage, as indicated by their X-ray diffraction
patt~rn~. In contxadistinction to this work~ this inYention
produce~ materials that have different composltion ranges
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~02337~
and that are overwhelmingly amorphous with a few small
diffraction p~3aks different from silicon carbide.
N. ~?arada and M. Tana}ta ln U.S~ Patent 3,~57,717
described and claim~d an organopoly~iloxane gel prepared
from cyclosiloxanes and H . Lamoreaux in U . S . Patents Nos .
3 ,197, 432 and 3 ,197, 433 claimed the prodllc~ gel from
reaotins eyclosiloxane~ conkaining hydxogens and vinyl
gxoups. The basi~ idea of reac~ing silyl hydrogen groups
with silyl vinyl groups i~ found in U ~ S, Patent~ Nos .
3,439,014 and 3,271,362.
The ~ability of a . oluble polymer was s~udied by
thermogravimetric analysi~ by A. Zhdanov e~ alO and reported
i n the ~,
Serie~ A, 16 ~10~, 2345-50 (1974). They precipitated the
highly branched, soluble polymer from the reaction mixture
as powders by adding aleohols into the reaction vessel
before the gel point . Their polymer wa~ dif ferent ~rom a
network gel produced from a sol-gel process in that it
contained a large amount of unr~acted Si-E~ and Si-CH=C~?2
group~ ansS wa~ readily ~oluble in aromati~ ~olvents. P,lso,
the polym~r powd~r did no~ melt when heated up to snoc.
They heatQd the ~oluble polymer~ at 1 nc per minute up to a
m~ximum of 780C in both Argon and air an~ reported the
thermogravimetric results a~ to weight loss at various
stages oiE hea~ing and 2~3 to the ~e)tal weigh~ lo~s involved.
No weight chang~ wa~ observed beyond 7S0C wh~n hea~d in
Argon at a rat~ of 10C/min. with a final yield of 879~. The
Russian~ did no1: eharac~erlze ~he re~u~tan~ product of ~his
analy~is and appeared to have no in~erest iD thi~ product.
In eontradi~tinetiorl to this prior work, this
invention i~ eoneern~d with the produot of pyroly~i~ of the
qel polymer~ ~ormed from eyelo~iloxanes as w~ll as with the
pro.-ess to produe~ sueh a produet. Th~ prc~duet of our
invention i~ a hardS ~la~y material whl~h w~ call a black
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glas~ having carbon directly ~onded to silicon and which is
very useful when cast as a monolith, or one pie~e object.
BRIEF SUMMARY OF T~E INVEMTION
This invention relates to a composi~ion of matter
in which ~reater amount~ of carbon are incorporated by
bonding to ~ilicon than were possibl2 utilizing prior art.
More ~pecifically, the invention is co~cerned wi~h a carbon-
containing black gla~ composition of matter in which about
10% to about 40% carbon is incorporated by we~ght to produce
an oxidatively stable and high melting subqtance.
Ag was hereinbe~ore di3cus3ed, there ls a need for
a thermally stable, oxidative-resistant, and
devitrification-resi~tant black gla~. Such a matsrial
would find high temperature u~ and would be economically
attractive when pr~pared by the present method in whic:h a
polymer would be foxmed at a low temperature followed by
pyroly~is at temperatur~ ln the range of abou~ 700C to
about 1400C. Our invention ha~ the advantag~ of producing
a silica modif~ed glas~ having a higher melting point than
cristobalite and having greater r2si~ t:ance to
devitrif~c~tion than pure vi reou~ silica and previou~ly
kno~m carbon-c:ont~lning gla~es. Our inv~nt:Lon also yields
a car~on-~onta~r.iRg gla~s having higher th~rmal ~tabili~y in
air than kno~n nonoxlde ceramic~ containing carbon.
It i3 therefore an object o~ this invention to
provi;d2 an amorphou~ carbon ;con~a~ning 3ili ::a-ba~ed cexamic
with a high me~lting point that is r~ tant to oxidation and
crys~alli~a~iorl l
a further object of ~he pre~ent in~ention to
provide a proceR~ whereby any moldable shape can be obtained
in the form of a black glass monolith.
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It is a still further object: of the pxesent
invention to provid~ a proces~ in whic:h a filled ~lack glass
monolith can be produced.
IA one aspe~t, an embodim~nt: of ~his invention
resides in a carbon-containing black gla33 ceramic
composition o~ matter having the empirical formula SiCx0y
wherein x rznges from about 0.5 to ab~ut 2.0, and y ranges
from about 0.5 to about 3Ø
Another aspect of this invention is found in a
process to produ~e a black gla~s comprising making a polymer
by reacting, i~ the presenca of a catalytic ~f~ective amount
of a hydro~ilylation cataly~t, (a) a cyclosiloxane monomer
of formula
~ ' ~
where n ~ an integer from 3 to abou~ 20, R is hydrogen, and
R' is an alken~ of from 2 to about 70 carbon atoms in which
on~ vinyl carbo~ i~ direc~ly bonded to silicon or ~)
reacting of ~wo or more d~ffeE~nt cycloslloxane monomers of
the formula and the n int~ger range where for at least one
monom~r R i~ ~ydrogen and R' i~ an alkyl group having ~rom 1
to ~bout 20 Garbon a~om~, and for the oth~r monomer~ R is an :.
alXene oP from 2 ~o about 20 carbon a~oms in which one-vinyl
carbon is dir~¢tly bonded to ~ilicon and R~ is an alkyl
group of from 1 to about 20 caxbon atoms, hea~.ing the
resulting polymer in a non-oxidizi~g atmosphere to a
tempera~ure in ~he range of from abou~ 800C to about 1400C
: to produ~e a bl~ck glas~.
Other object~ and embodimen~ will be found in the
following further detailed des~ription of the pre~en~
invention.
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D~TAILED DESCRIPTION OF THE INVENTION
As hereinbefor~ set for~h, the present invention
is conc~rned with carbon-containing black glass compositions
of matter having varying percents by weigh~ of carbon, w.ith
high melting points, resistant to devitrifica~ic)n, and
possessing oxidative stability.
A carbon-containing black glass compositioD of
matter may be prepared by any method kno~ in the art.
Examples of this art would be the physical blending a~d
sintering of mixtures of silica and pyrolyzable orqanic
compounds or the sol-gel proces~. The ~ol-gel process is
very attracti~re due to the homogensity of the sol produced,
the ease of forming a gel from the sol, and the fact that
such a pro~ess ca~ be carried out at low temp~ratures,
thereby reducing production costs. As described in ~he
bac}cground o~ the invention, other WOEICer8 have been able to
prepare a polymer from cyclosiloxane~, and, in some cases,
forrn thi~ };olymer into a monol~ th, but no prior work has
shown th~ manu~ac~ure of a black glass mox~olith, eithe:r
filled or ua~illed, util~zing the cyclosiloxane polymer
method. Our invention, ~hereore, comprise3 the pyrolysis
in a~a lnert at~o.~phere of a polymer made from t:yc~losiloxanes
to tempera~cur~ of about 1400C to produce a hard, glassy
material whlch we call a black glas~. ~he shape o~ thi~
black gla~s deriv~s dlrectly from the shape o~ the precursor
polymer with th~ strength dependent on whether th~ monomer
is filled with ~ powdex, whisker, or fiber prior to
polymeri~ation. A ~onol~thic shape can he produced
u~ilizi~g a molding or an ex~rusion step prior to or
conco~i~ant wi~h a final polymeriza~ion. ~f~er the polymer
is ~haped, t~e pol~mer ls pyrolyzed up ~o about 1400~C to
for~ a blacX gla~ with retention of the b~ic ~tarting
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~23~78
shape~ but with decreased dimensions due to thermal
shrinkage.
The polymer precursor of the present invention is
prepared in one instance at reaction conditions by
subjec~ing a cyclosiloxane mixture con~aining cyclosiloxanes
of from 3 to about 20 silicon atoms to h~a~ing to a
~emperatur~ in the range of from about 10C to about 300C
in the presenc~ of a platinum hydrosilylation catalyst
present at 1-200 ppm for a time ln the range of from about I
minute to about 600 minutes. The poly~er is then placed in
nitrog~n and pyrolyzed at a temperature in the range from
about 800C to about 1400C for a time in the range of from
about 1 hour to about 300 hours to produce the black glass.
The polymer formation step from the monomer takes advantage
of the fact that a silicon~hydride will react with a
~ilicon~villyl group to form a silicon-carbon-carbon-silicon
bonded chain~ thexeby forming a network polym~r. For ~his
reason, each monomer cyclo~iloxan~ mu~t contain ~ither a
silicon-hydrid~ bond or a silicon-vinyl bondO For purposes
of thi~ application and the appended claim~ a silicon-
hydride bond refer~ ~o the presence of a silicon atom bonded
directly to a hydrogen atom and a silicon-vinyl bond refers
to the pr~sen~ of a ~ con atom bonded directly to a
carbon a~o~, call~d an alkene carbon, that i~ doubly bonded
to a~oth~r carbon atom in an alken~ moiety.
Co~v~rsion of the gel polym~r ~o black gl~ss takes
place..b~tween 430C and g50C~ Three major pyrolysis stPps
were iden~ified by ~hermogravimetric ana~ysis at 430-700C,
680~800C and 780-g50C. The yield of the gel-gla~s
conversion is 83~; the hlrd pyrolysis mech~ni~m o~ourring
between 785C ~nd ~50~C contributed the final 2.5% weight
los~ ~o ths final produc~. Thu~, the pyrolysis chemis~ry of
th~ gel polymer in thi~ invention i~ dis~inctly diff~rent
from that reported by A. Zhdanov et al. in ~ha~ ~heir
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soluble polymer did not have any reacti.on above 78~C in a
~ast heating of 600C per hour. As discussed hereinbefore,
thiq soluble cyclosiloxane precursor is al~o chemicall~
different from a gel polymerO ~he gel polymers in this
invention cannot be dissolved in solvents such a~ toluene.
The invention can be prac~iced by u~ilizin~ a
polymer pr~cursor cyclosiloxane wherein both the recluisite
silicon-hydride bond and the silicon-vinyl bond are present
in one molecule. For example, 1,3,5,7-tetravinyl-, 1,3,S,7-
tetrahydrocyclotetrasiloxane would operate within the scope
of this invention since this molecule has the basic
requirement of a silicon~hy~ride bond and a silicon~vinyl
bond and would polymerize to give a black gla~s polvmer
precursor of use in this inv~ntion.
One of the most us~ful method~ utili~ed in the
process of this invention is to fabricate the polymer
precursor into a monolith using procedures liXe tape
casting, in~ection molding/ rea~t~on in~ection molding, and
compr~sion molding. For instance, ~he polymer orming
cyclosiloxane mixture may he introd-lced into a mold and then
heated to form the polym~r monollth black yla~ precur50r or
extruded through a heated dle to form a precursor polvmer
monolith~ The monoli~h would then be pyrolyze~ up to about
1 400C to form the! black glaY3 mon~lith~
A1 o considered as wlthin the s~o~e of thi~
inv2n~ion is impx~gnating ths black gla~ product of thi3
invention with cyclo~iloxane monomer rea~ion mixture, the
best results coming from pre sure or vacuum impr~nation
with subsequent pyrolysi~ to afford a black glass product
with less cracks and voids and with yreater density.
Impregnation can be rep~ated to furth~r increase the density
of the black gla~ produ~t of this inventionO
2337~
While the reaction works best if platinum is the
hydrosilylation ~atalyst, other catalysts such a~ cobalt and
manganese carbonyl will perform adequately, The ca~alyst
can be dispersed as a solid or can be used as a ~olution
when added to the ~yclosiloxane monomer.
Cy~losiloxane~ are the preferred ~ilicon
containing compounds ox ef~ecting the gel monoliths~
Examples of cyclosiloxanes include, but are not limited to,
1,3,5,7-tetramethyltetrahydrocyclotetrasiloxane,
1,3,5,7-tetravinyltetrahydrocyclotetrasiloxane,
1,3,5,7~tetravinyltetraethylcyclotetrasiloxan~,
1,3,5,7-tetravinyltetramethylcyclotetra~iloxane,
1,3,5-trimethyltrivi~ylcyclotrisiloxane,
1,3,5-trivinyltrihydrocyclotrisiloxane,
1,3,5-trimethyltrihydrocyclotrisiloxane,
1,3,5,7,9-pe~t~vinylpentahydrocy~lopentasiloxa~e,
1,3,5,7,9-penta~lnylpentamethylcyclopentasiloxane,
1,1,3,3,5,5,7,7-octavinylcyclotetrasiloxane,
1,1,3,3,5,5,7,7-octahydrocyclotetrasiloxane,
1,3,5,7,9~ hexavinylhexamethylcyclohexasiloxane,
1,3,5,7,9,11-haxame~hylhexahydrocyelohexa~iloxane,
1,3,5,7,9,11,13,15,17,19-
dec~vinyld~aahydro~yclodecasiloxan~,
1,3,5,7,9,11,13,15~17,19,21,23,25,27,29~p~ntadecavinyl-
pentadecahydrocyclopentad~ca~iloxan~,
1,3,5,7-t~rapropenyltetrahydrocyclotetra~iloxane,
1~3,5~,7-t~txap~ntenyltetrapentylcyclotetrasiloxan~ and
1,3,5,7,9-pentadecenylpen~apropylcyclopentasiloxa~eO
The monomeric mixture can include a ~iller such as
cubic or hexago~al silicoD carbide, silicon nitrid~, silica,
alumina, hafnia, titania, and zirconia ko ~treng~hen the
re ulting monolith. Such a filler in the form o~ a powder,
whisker, or fib~r can be mixed into the monom~r using
conventional me~nsO The fllled product produced by the
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process of this invention shows not only increased strength
but also exhibits controlled shrinkage upon the pyroly~is
step. Pyroly~is of the precursor polymer~ change~ these
polymers into very hard ceramic bodie~ that can fi~d
application in high temperature, oxidation-resis~ant, high
strength compo~ite matrice~ and castabl~ cerami~s.
It has been discovered that applica~ion of
pressure to the monomer mixture during the pol~mer :Eorming
opera~ion will prevent nucleate bubbling o~ the reactants
and decrease reaction time in that higher temperatures can
be employed. Buhbling i~ to be avoided since it causes
void~ and cracks to form in the incipient polymer and
thereby weakening the fini~hed product. In the reaction o~
thls invention bubbling occurs whenever the filler content
of the monomer mixture is in excess of about 20% by weight.
Therefore, it is preferred to perform the polymeri~ation of
this inVentiQn under a pres~ure in the range of from 14 psi
to about 30,000 p~i ~o as to produce cra~k-free nearly
voidles~ polymer~0 The application of increased pressure
will also ha~ten the reaction time for unfilled polymer
fo~mation. For the purpose~ of thi~ application and~
appended claim~, the term "crack-free~ will be read ~o mean
fre~ o~ vi~ibl~ crack~.
Harada and Tanaka have shown in ~heir con~rol
experiment that ~he cured product obtained from a mixture o~
175 par~s of cyc:lote~ra~iloxane~ and 200 parts of quartz
f lour wa~ ound to have crack3 and to be urlu3able . xn their
invention, 100 part~ of an organopo~ysilo~ane ~ompo~ed of
~he ~rîorgano~iloxy and ~licon dioxide groups wa~ added to
the cyclotetrasiloxanes sol, resulting in a cured produc~
fr~e from crack defect~. Their monomer compu~ition thus
prepared i5 curable a~ a ~emperature in ~hE3 range from room
temp~rature ~o 100C. Our invention of high pre~sure
polymerization of cyclosiloxane~ by hydro~ilylation reaction
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2~23378
not only can produce cured thick-walled products without
cracking and gas pocke~s, but also allows the use of
polymerization temperatures higher than lO0C and higher
platinum concentr~tion, thus shortening the reaction tima
for polymerization.
Th~ black glass composition of ma~ter has an
empirical formula SiCXOy wherein x range~ from about 0.5 ~o
about 2.0, and y ranges from about 0.5 to about 3.0, whereby
the carbon co~tent ranges from abo~t 10% to about 40%. Mo
other method known in the art can achieve ~uch a high carbon
content black gla s wherein the car~on is r~sistant to
oxidation at high temperatures.
As di~cuss~d hereinbefore, January and Monomann
were able to produce high carbon black gla~s from
precur~ors diff~rent from this invention but their glass
contained low densities around 1.6 and the carbon was easily
oxidized at low temperature. Using the proce~s of our
inYentiOn~ the carbon contained iD the black glass is
resistant to oxidatian and our den~i~ies are abou~ 2.1 grams
per millilit~r., In addition, ~he prlor work utilizing
silicon hydroly~is had ex~.remely slow fabrication times for
monolith~ on the order of week~ ~ wherea3 our invention can
form th~ polym0r monolith~ in the order of minutes with
higher yield ~han those made from hydrolyRi~ reaction~ of
s~llcon. Our monoll~h~ czln be ~ormed in~o larger shapes
than the hydrolysl~ blac:k glas~
Our invention can be used to manufacture non-
porous a~ well as porous blaclc glass. For most purpose~ it
is preferred to u~ neat cyrlosiloxane~ ~o form non-porous
black gla~s, but porou black qlass can ~e fo~ned if so
de~ired by starting with solvent based cyclosiloxan~
monc1mer~. This inven~ion provide~ crack-free po:lymers when
run in the pre~n~ of pressure while the same reaction
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~2337~
mixture when run at atmospheric mixture provides a polvmer
containing cracks.
The ollowing examples are yiven for purpo~es of
illustration. E~owever, it i5 to be under~tood tha~ these
examples are only illustrative in nature and tha~ this
invention i~ not nec~ssarily limited thereto.
EXAMPI.E I
Ten milliliters of
tetravinyltetramethylcyclotetra~iloxane was mixed with 7~2
millilitexs of a mixture of cyclo~iloxane~ co~taining from 3
to about 6 ~i}icon atom~ and called m~thylhydrocyclosiloxane
and 0~05 milliliters of platinum-
divinyltetramethyldisiloxane complex containing 3~ platinum
in xylene was added to th~ above mixture. After heating to
about 60C for on~ hour a toluene in~olu~le gel polymer was
formed. The re~ul~ant poly~er wa~ then pyrolyzed in
nitrogen at a heating rate of 200C per hour to about 120UC
re~ulting in forma~ion Qf a carbon containing black ~lass.
The weight lo~ wa~ about 17% for the overall procass and
the skeleton density for the ground black glas~ powder was
about 2.10 gra~ per millillter. The carbon-containing
black gl~ lo~t les~ than 0.6~ by weight when heat~d in
flowing air ~o about 11$0C at a heatl~g rate of 10C p~r
minute in a thermogravime~r~c analysi~. X-ray analysls of
this black gla~ indicate~ that thi~ material is largely
amorphou~ and that ~he sample had a few sma~l diffrac~ion
peaks, whic~ wa~ diff2ren~ from crystalline silicon carbide.
Elemental compo-~ition gave the formula
~; iC 1 3 7 1 n 0 3
-
`
, ' ' :
~2337~
for the black glass and the black glass contained <n . l
weigh~ ~ hydrogen and <0.3 weight ~ nitrogen.
EXAMPLES II - VI T T
These examples were all parformed as deseribad in
Example I with the excsption that differen~ volume amounts
of tetravinvltetr~methylcyclotetrasiloxane (T) and
methylhydrocyclosiloxane ~M) were utilized ~o make the black
glass. The results of these experiments are presented in
Table 1 below where T/~ is a volume ratio. The data shows
that the silicon bonded carbon content can be varied and
this ~ariation is controllabl0 within + 1~.
Thermogra~imetric analysis in flowlng air showed that powder
samples from Examples II-VIII had less than 0.~% wei~ht loss
when hea~ed to 1150~.
:
"~:
:
.:
; .
~233'~8
TARLE 1
o~ ~ ti~ ~b ~
Pyrolysis Carbon wt. 9~ Empirical
T/~ _ Yieldin bla~k qlas~ Formulae
II 8/2 67%29.8# ~iCl 450.89
III 7/3 7g%28.0~ SiCl 511.17
IV 6/4 829~27~2~ SiCl 360.~8
.,
V 5/5 839~24,6P6 Si~1.300.95
VI 4/6 84~24.1% SiC1 231.16
,~:
~ VII 3/7 77%21.7% ~iCl 081.17
-
~; VIII 2/8 57%~9-4~ SiCl.01O1.39
.
.,
EXAMPLE IX
The pyrolysis mechani~m wa~ vestigated by
:her~nogr2~rime~rlc analysi~ ~T~,A). ~9.93 mg of the gel
polymer obtained from Exa~nple I was heated under flowing
nitrogen at a heating rate oiE 10C per mlnute ~o 1100 C.
The to~al weight los~ wa~ 17~ Re~ul~!3 for ~he controlled
pyroly~i. are ~u~ arized in Table II below.
,
' . .; :',~
. .
.~ , . ..
3378
Table_II
TGA Results fo~ rolvsls of Pol~mer ~.el
Temperature Range '~'eight TJOSS
8nc - 430C ;-
430C - 605~ 5.0%
605~ - 690C 5.n~
; 6gO~ - 745C
745C - 785C ~.0
~ 785C - g50C ?.5~ :
Total l6.8~
The ceramic conver~ion occurred in the 430~-~nC
temperature range. The derivatives of th~ T~.A curve
indica~ed three major pyrolysis mechanism~ at 430-7~0C,
650-800C and 780-900C. The third pyrolvsis step ac~ounted
for ca. 15~ of ~he total weight lo~s.
,
~; EX~UPLE X
~:~ 10 ~l of phenyltriethoxysilane was mixed with 10
ml o tetraethoxysilane in a beaker, 2~8 ml of l.0 ~ acetic
acid wa~ added, and ~he solutlon wa3 ad~usted to about p~ 1
by adding ~evexal drop~ of concentrated hydrochloric acid.
The gel Produ~e~ by this m~thod was pvrolvzed in nitro~en to
1200 & at a hea~ing rat~ o~ ~0~ per hour to qive ~6~l~ o~
a foam material with a 2~.6~ carbon oontent hy weight.
Thermossavimetric analysi~ o~ ~he b1ack glas~ ~oam ~a~
p~rformed in flowing air at a hea~ing ra~e of 20C per
. minute to 1150~C and show~d a loss in weight of 2n.~ which
began at around 550C. The ~olor of th~ sampl~ turned
whi~e, indica~ing that the rasidue is silica and the car~on
is not oxidation resi~tan~ as would he expected i~ the
.
~p
~2~78
carbon wa~ bound to the silicon structure rather than ~eing
present as a mixture of graphi~e in silica~
A second example using 20 ml of phenyl
triethoxysilane was reacted with 4 ml of tetraethoxysilane
as in the fir~t ~xample repor~ed above ~o give a 66% yiel~
of a porous product containing 35.0~ carbon by weight.
Thermogravime~ric analysis of this product showed a weight
loss Qf ~4.05%, again demonstratin~ ~hat the carbon presen~
is not resistant to oxidation at high ~emperatures as is the
carbon present in the black glass made in Example~ I~VTII.
EXAMPLE XI
A sol mixture was prepared as des~ribed in Example
I and silicon carbide whis~ex~ ~Tat~ho3 werP su~pended in
said mixture by ultrasonic agitation for from 15 to abou~ 30
seconds re.~ulting in a stable ~uspension of tha whiskers.
Polyme~ization of the sl~spension occurr~d after l20 minutes
heating at 50C affordin~ a rigid 3.5 centlmeter diameter
compo~ite cylind~r with about 13~ ~y weight whicXer content.
Pyroly~i~ of ~hi5 ~ylinder a~ 200C per hour up ~o
te~perature of about 1200C gave a cylinder who~e di~meter
had contracted by about 20%.
:
EX~PLE XII
In like manner a~ de cribed in Example I, a
mixture was prepared and then polymerized at about 90C in
about 10-15 minute~ under a pres~ur~ of 70 psi. Gelation
took abou~ 90 minutes if the tempera~ure i~ lowexed ~o 5~C
and th~ pre~sure ls atmospheric. An increa~ in pressure
then allow~ higher temperatur~ pol~merizatlo~ and affords
much ~horter polym~riæa~ion time~. Under a~mo~pheric
pres~ure, he sol liquid with 90 ppm P~ started ~o foam when
,
19
~23~78
gelation temperature was over 65C.
E ~ MP~E XIII
A mixture was prepared in like manner as described
in Example I and 50 w~ight percant of sili~on carbide powder
was added to said mixture. Polymerization oc~urred at 85C
and 70 p~i in 15 minutes wi~hout bubble formation. In
a~mospheric pressure operation it i~ not po~sible to obtain
bubblo-free sample~ for filler loadings exceeding about 20
by weight ~iller since the filler acts to produce nucleate
bubbling as ~he ~emperature is raised.
EXAMPLE XIV
For purpo~es of this example and for u~e in the
following Example~ ~V and XX, a standard mixture of
cyclosiloxane monomer~ wa.~ prepared from T,
tetravinyltetramethylcyclotetra~iloxane, and ~, a commercial
mixture of methylhydrocyclo~iloxane3 when the ~ilicon atoms
number fro~ 4-6, in the ratlo of S.7 T to 4~3 M in ~he
presence of 90 ppm platinum.
In this example 4 milliliter~ of the s~andard
mixtur~ wa~ plaG~d in a po}ypropylene ~ube and heat~d at
55C in an oven for 90 minu~e~ to form a polym~r which was
sub~eguen~ly hardened a~ 80C for 30 ml~u~e~O The polymer
exhibited a ~mooth ~ura~e and no cxac~s a~ter removal from
~he ~lypropylena kub~. Pyroly~is of th~ polymer in
nitrogen to 1200C at the ratQ o 200C per minu~e a~forded
a black gla~s ~th a bulk density of 2.05 g/ml exhibiting a
diamet~r shrinkag~ of about 21~ and a reduction in volume to
about 49~ of initial volume.
?O
2~2337~
EX~U~T E XV
Twelve milliliters of ~he mixture o~ ~xam~le XIV
wa~ mixed with 3 grams of alpha silicon carbide powder with
ultrasonic agi~ation and heated to 40C~ for 15 minutes. The
resultant mixtura wa~ poured into an 1lm~ x 1lmm x 55mm
copper case and placed in a pressure ves~el under ~0 p~iq.
The pressurized container waq placed in a 60C water bath
for 60 minutes to polymerize the monomers. ~he polrmsr was
heated in a 90C oven for one hour, and then taken out of
the copper case. The filled polvmer had dimension~ of 1.44
cm x 1.44 cm x 4.60 cm and exhibited a smooth surface and no
crack~. Pyrolysis under nitrogen at 200C per hour up to
12~0C produced a 1.14 cm x 1.t4 cm x ~.60 cm bla~k glass
obiect with uniform ~hrinkaye, as to height and width, of
19.0% and a final volume of ~2.9~ 0~ the initlal ~olume.
The black ~lass was ~hen impregna~ed under vacuum
with the starting mixture, polymerized at 55C ~or 80
minutes, cured at 90~ for 60 minutes, and pyrolvzed to
1200C as before. The pyrolyzed black glass ~xhi~ited no
change in d~mensions and weigh~d 10~28 gram~ wi~h a den~ity
of 2~3 g/ml. The ~ilicon carbide wa~ present in the~ black
glass ~t 23~ by weight.
RX~MPL~ XVI
A comparison experlment w~ run a~ de~cri~ed in
Exampl~ XIV but without a pressurlzed ves~ The resultant
polym~r exhibitPd gas poc~ets and cr~c~ af~er curing at
55~C for 90 minutes. A similar non-pre~surized sampl0 was
cured a~ 35C for 1fi hours and ~xhibi~ed crackq and ~a~
pock2ts. rAh~n a similar ~ixtur~ w~ cured at ~C for 48
hour~ t the polymer did not exhibit cracks and ~as pockets
but sedimen~atlon of the alpha silicon carbide pGwder
occurred and r~sulted i~ a clearlv defined boundary laver in
.
~ . ~
21 2~3378
the polymer.
EXAMPLE XVI I
l~leverl grams of a starting mix~ure as describ~d in
Example XIV was mixed with 7 grams of .alpha ~;ilicon carbide
powder ~39.3% by weight) by ultra~onic dispersion, plac~d in
a cylindrical alumi~sum cas~ with an int~xior diam~ r of 18
mm and a height of 74 mm, pres~uri~ed to 1~0 p ig, immersed
in an 85C water bath for 15 minutes, heated in a 105C ov~n
for one hour, and the filled polymer was then removed from
the case and ~xh~bited a smooth surface having no cracks
with a diameter of 18 mm and h~ight of 4 8 nun . Upon
pyrolysis 1:o 1200C at 200C per hour und~r ni~rogen, th~
filled black gla~ exhi}~ited a lS mm diameter with a height
of 41 m~, A weight of 16.34 gram~, a density of 2.2 g/ml~
and contained 43S by weight o~ ilicon caxbid~ powd~r.
EX~PI.IS XVIII
In lilc~ manner a~ in Example XVII, a 61~ alpha
silicon carbids f~ d monomer m:lxture!! ~as pr~pared from 16
grams of alph~ 8ilicon s~arhide powd~r and 10 ml of monomer
mixtur~. Thi~ ~alxtuxe wa~ heated at 40C for 20 minut~s,
the ~lurry w~ th~n poured into an 11 mm interlor diam~er
pe~lypropyl6~n~ ttlb~, th~ tube wa~ pre~3uri~d to 110 E~iy and
heated for 8 m~nut~ at 80C and aged a~ 8SC ~or 30
minu~ës, and the polym~r wa~ r~moved an~ exh~b~ ~ed a smoo~h
sur:Lacs and no cra~k~. Pyroly~is to 1200~C und~r nitrogen
at 200C per hour gave a f~lled bla~:lc glass wl~h a dlameter
of 8.7 mm arld a hei~ht of 45O7 mm, ~ weight of 6 gxam~, a
denslty of 2O23 g/ml, and contained 66% by weight: of silicon
carbide .
. - : ~ ..~ ,:,:
: ,:
.: . .
22 2~2~'37~
FXAMPLE XIX
;
In like mann~r as in Xxample ~VITI, 14.5 ml of
monomer mixture was combined with 5. 5 grams of ~i].icon
carbide whiskers and the whisker~ were dispersed
ultrasonically. The slurry was then poured in~o a ~ mm x
l8 mm x 12 mm rectangular aluminum mold and polymeri~ed at
50C for 3 hours when the polvmer was separated from the
mold and exhibited cracks and ga~ pockets. Pyrolysi~ was
performed at ~00C per hour under ni~rogen to 1~0~C
resulting in a black glas~ with a 1708 gm (86.6~ vield)
having dimensions of 50 mm x 15 mm x ll mm and a final
volume of 67~ of the initial volume. The density was ~.l6
g/ml and 32~ by weight of the fill~d black glas~ was silicon
carbide whisker.
EXAMPLF, XX
As described in Example XIX, the s~andard monom~r
mixture was heated at 40C for 30 minutes and then lO
millilit~rs wa~ mixed with 2.99 grams of silicon carbide
whiskers. This mixture wa~ di~ided into twc parts. ~One
part wa~ polymexized at 55C at atmos~heric pressure for 90
minut~ and produced a polymer exhibiting ga~ pocke~s and
surfac~ cracks. The second p~rt wa~ polYmerized under 7n
psig at 85C for 15 minutes givinq a polymer exhibitin~ a
smooth surfa~e and no cracks~ This experiment show~ the
impor~ance of pre sur~ in s~ortening the r~ac~ion time and
in produ~ing a crack-fre2 product.
~233~
XAMPLE XXI
A sol ~olutlon, prepared as de~cribed in ~xamplP
II was mixed wsth silicon carbid~ fibers (Nicalon - ~
manufactured by Nippon~ in a 1.9 millimeter glass vial. The
mi~ture was polymeri2ed at 52C for about two hour~
resulting in a crack-free fiber-reinfoxced polymer monolith.
Co~trolled pyrolysis, wherein the temperature wa~ raised
20nc per hour until a final temperature of 1200C wa~
reached, resulted in th~ formation of a black gla~s monolith
with the same diameter as the pre-fired polymer monolith, a
result that wa3 not ~hown by the unr~ orced polymer of
~xample II. The black gla~ fiber-reinforced monolith had a
density of 1.0 grams per milliliter and contained about 9.7
by weight silicon ~arbide flberO
The black glass monolith wa~ impre~nated, under
vacuum~ with monomer mixtur~ and pyroly~ed in nitrogen to
1200C at 200C per hour to give a monolith with a density
of 1.4 grams p~r milliliter. A second impregnation with
monomer mixtur~ followed by further pyroly~is gave a bla~k
glas~ monolith w~th a density of 1.6 gram~ per milliliter.