U.S. patent application number 15/810073 was filed with the patent office on 2018-10-11 for polysilocarb materials and methods.
This patent application is currently assigned to Melior Innovations, Inc.. The applicant listed for this patent is Melior Innovations, Inc.. Invention is credited to Brian Benac, Douglas Dukes, George Keith, Mark Land, Michael Mueller, Walter Sherwood, Oliver Wilding, JR..
Application Number | 20180291155 15/810073 |
Document ID | / |
Family ID | 51529754 |
Filed Date | 2018-10-11 |
United States Patent
Application |
20180291155 |
Kind Code |
A1 |
Dukes; Douglas ; et
al. |
October 11, 2018 |
Polysilocarb Materials and Methods
Abstract
Silicon (Si) based materials and methods of making those
materials. More specifically, methods and materials having silicon,
oxygen and carbon that form filled and unfiled plastic materials
and filled and unfilled ceramics.
Inventors: |
Dukes; Douglas; (Troy,
NY) ; Land; Mark; (Houston, TX) ; Benac;
Brian; (Marble Falls, TX) ; Mueller; Michael;
(Cypress, TX) ; Keith; George; (Houston, TX)
; Wilding, JR.; Oliver; (Louisville, KY) ;
Sherwood; Walter; (Glenville, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Melior Innovations, Inc. |
Houston |
TX |
US |
|
|
Assignee: |
Melior Innovations, Inc.
Housto
TX
|
Family ID: |
51529754 |
Appl. No.: |
15/810073 |
Filed: |
November 12, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14268150 |
May 2, 2014 |
9815943 |
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15810073 |
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14212896 |
Mar 14, 2014 |
9815952 |
|
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14268150 |
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61818906 |
May 2, 2013 |
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61818981 |
May 3, 2013 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C04B 2235/5427 20130101;
C04B 2235/483 20130101; C04B 35/64 20130101; C04B 2235/528
20130101; C04B 2235/5436 20130101; C08L 83/04 20130101; C08G 77/50
20130101; C04B 2235/6581 20130101; C04B 35/806 20130101; C04B
2235/44 20130101; C08L 83/00 20130101; C04B 35/56 20130101; C04B
2235/3418 20130101; C09K 8/80 20130101; C04B 2235/48 20130101; C04B
35/571 20130101; C04B 2235/3826 20130101; C04B 2235/96 20130101;
C04B 2235/77 20130101; C08G 77/12 20130101; C08G 77/20 20130101;
C04B 35/515 20130101; C04B 35/5603 20130101; C08L 83/04 20130101;
C08L 83/00 20130101 |
International
Class: |
C08G 77/20 20060101
C08G077/20; C04B 35/515 20060101 C04B035/515; C04B 35/64 20060101
C04B035/64; C08L 83/04 20060101 C08L083/04; C08G 77/50 20060101
C08G077/50 |
Claims
1-68. (canceled)
69. A solvent free method for making a neat solid material, the
method comprising: a. preparing a mixture of a first liquid
polysilocarb precursor with a second liquid precursor in the
absence of a solvent to form a solvent free liquid polysilocarb
precursor formulation, whereby the first liquid polysilocarb
precursor is not chemically reacted with the second liquid
precursor; and, b. curing the polysilocarb precursor formulation to
form a neat sold material, whereby the first liquid polysilocarb
precursor and the second liquid precursor chemically react to form
the neat solid material.
70. A reaction free method for making a polysilocarb material, the
method comprising: a. obtaining a first liquid polysilocarb
precursor; b. obtaining a second liquid polysilocarb precursor
comprising a first reactive group; c. obtaining a third liquid
polysilocarb precursor comprising a second reactive group; and, d.
mixing the first liquid polysilocarb precursor, the second liquid
polysilocarb precursor and the third liquid polysilocarb precursor
to form a liquid polysilocarb precursor formulation, wherein the
first reactive group is unreacted; and the first liquid
polysilocarb precursor is not chemically reacted with the second
liquid precursor; and, e. curing the polysilocarb precursor
formulation to form a neat sold material, whereby the first liquid
polysilocarb precursor and the second liquid precursor chemically
react to form the neat solid material.
71. The method of claim 70, wherein the first reactive group
comprises a hydride, and the second reactive group comprises a
vinyl.
72. The method of claim 70, wherein the first reactive group
comprises a reactive group selected from the group consisting of
vinyl, allyl, hydroxy, hydride, phenyl, and phenylethyl.
73. The method of claim 70, wherein the second reactive group
comprises a reactive group selected from the group consisting of
vinyl, allyl, hydroxy, hydride, phenyl, and phenylethyl.
74. The method of claim 70, wherein the first reactive group and
the second reactive group comprises a reactive group selected from
the group consisting of vinyl, allyl, hydroxy, hydride, phenyl, and
phenylethyl.
75. (canceled)
76. A method for making a neat polysilocarb material, the method
comprising: a. obtaining a first liquid polysilocarb precursor; b.
obtaining a second liquid polysilocarb precursor comprising a first
reactive group; c. obtaining a third liquid polysilocarb precursor
comprising a second reactive group; d. mixing the first liquid
polysilocarb precursor, the second liquid polysilocarb precursor
and the third liquid polysilocarb precursor to form a liquid
polysilocarb precursor formulation, wherein the first reactive
group is unreacted; and, e. curing the polysilocarb precursor
formulation, whereby the first reactive group and the second
reactive group chemically react to form a neat sold material.
77. The method of claim 76, wherein the first reactive group
comprises a hydride, and the second reactive group comprises a
vinyl.
78. The method of claim 76, wherein the first reactive group
comprises a reactive group selected from the group consisting of
vinyl, allyl, hydroxy, hydride, phenyl, and phenylethyl.
79. The method of claim 76, wherein the second reactive group
comprises a reactive group selected from the group consisting of
vinyl, allyl, hydroxy, hydride, phenyl, and phenylethyl.
80. The method of claim 76, wherein the first reactive group and
the second reactive group comprises a reactive group selected from
the group consisting of vinyl, allyl, hydroxy, hydride, phenyl, and
phenylethyl.
81.-102. (canceled)
Description
[0001] This application: (i) claims, under 35 U.S.C. .sctn.
119(e)(1), the benefit of the filing date of May 2, 2013 of U.S.
provisional application Ser. No. 61/818,906; (ii) claims, under 35
U.S.C. .sctn. 119(e)(1), the benefit of the filing date of May 3,
2013 of U.S. provisional application Ser. No. 61/818,981; and,
(iii) is a continuation-in-part of U.S. patent application Ser. No.
14/212,896 filed Mar. 14, 2014, which claims under 35 U.S.C. .sctn.
119(e)(1) the benefit of the filing date of Mar. 15, 2013 of U.S.
provisional application Ser. No. 61/788,632, the entire disclosures
of each of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present inventions relate to polyorganic compositions,
structures and materials; polymer derived preceramic and ceramic
materials; and in particular polysilocarb compositions, structures
and materials. The present inventions further relate to methods for
making these compositions, structures and materials.
[0003] Materials made of, or derived from, carbosilane or
polycarbosilane (Si--C), silane or polysilane (Si--Si), silazane or
polysilazane (Si--N--Si), silicon carbide (SiC), carbosilazane or
polycarbosilazane (Si--N--Si--C--Si), siloxane or polysiloxanes
(Si--O) are known. These general types of materials have great, but
unrealized promise; and have failed to find large-scale
applications or market acceptance. Instead, their use has been
relegated to very narrow, limited, low volume, high priced and
highly specific applications, such as a ceramic component in a
rocket nozzle, or a patch for the space shuttle. Thus, they have
failed to obtain wide spread use as ceramics, and it is believed
they have obtained even less acceptance and use, if any, as a
plastic material, e.g., cured but not pyrolized.
[0004] To a greater or lesser extent all of these materials and the
process used to make them suffer from one or more failings,
including for example: they are exceptionally expensive and
difficult to make, having costs in the thousands and
tens-of-thousands of dollars per pound; they require high and very
high purity starting materials; the process requires hazardous
organic solvents such as toluene, tetrahydrofuran (THF), and
hexane; the materials are incapable of making non-reinforced
structures having any usable strength; the process produces
undesirable and hazardous byproducts, such as hydrochloric acid and
sludge, which may contain magnesium; the process requires multiple
solvent and reagent based reaction steps coupled with curing and
pyrolyzing steps; the materials are incapable of forming a useful
prepreg; and their overall physical properties are mixed, e.g.,
good temperature properties but highly brittle.
[0005] As a result, although believed to have great promise, these
types of materials have failed to find large-scale applications or
market acceptance and have remained essentially scientific
curiosities.
SUMMARY
[0006] Accordingly, there has been a long-standing and unfulfilled
need for new materials, and methods of making such materials, that
have the performance characteristic and features of high and higher
priced ceramics, but with lower costs and greater flexibility in
manufacturing and using the material, and further have performance
characteristic and features unobtainable with existing ceramics and
plastics. The present invention, among other things, solves these
needs by providing the materials, compositions, and methods taught
herein.
[0007] Thus, there is provided a solvent free method for making a
ceramic material, and the material made from this method, the
method involving: mixing a first liquid polysilocarb precursor with
a second liquid precursor in the absence of a solvent to form a
solvent free liquid polysilocarb precursor formulation, whereby the
first liquid polysilocarb precursor is not chemically reacted with
the second liquid precursor; curing the polysilocarb precursor
formulation to form a sold material, whereby the first liquid
polysilocarb precursor and the second liquid precursor chemically
react to form the solid material; and, pyrolyzing the sold material
to form a ceramic material.
[0008] Yet further there are provided methods and materials having
or involving one or more of the following features: wherein the
first liquid precursor is methyl hydrogen fluid; wherein the first
liquid precursor is a methyl terminated hydride substituted
polysiloxane; wherein the first liquid precursor is selected from
the group consisting of a methyl terminated vinyl polysiloxane, a
vinyl terminated vinyl polysiloxane, a hydride terminated vinyl
polysiloxane, and an allyl terminated dimethyl polysiloxane;
wherein the first liquid precursor is selected from the group
consisting of a vinyl terminated dimethyl polysiloxane, a hydroxy
terminated dimethyl polysiloxane, a hydride terminated dimethyl
polysiloxane, and a hydroxy terminated vinyl polysiloxane; wherein
the first liquid precursor is selected from the group consisting of
a phenyl terminated dimethyl polysiloxane, a phenyl and methyl
terminated dimethyl polysiloxane, a methyl terminated dimethyl
diphenyl polysiloxane, a vinyl terminated dimethyl diphenyl
polysiloxane, a hydroxy terminated dimethyl diphenyl polysiloxane,
and a hydride terminated dimethyl diphenyl polysiloxane; wherein
the second liquid precursor is selected from the group consisting
of a methyl terminated phenylethyl polysiloxane, a tetravinyl
cyclosiloxane, a trivinyl cyclosiloxane, and a divinyl
cyclosiloxane.
[0009] The method of claim 1, wherein the second liquid precursor
is selected from the group consisting of a trivinyl hydride
cyclosiloxane, a divinyl dihydride cyclosiloxane, and a dihydride
cyclosiloxane; wherein the second liquid precursor is a silane;
wherein the second liquid precursor is selected from the group
consisting of a methyl terminated dimethyl ethyl methyl phenyl
silyl silane, an ethyl methyl phenyl silyl-cyclosiloxane, a
cyclosiloxane and an orthosilicate; wherein the first liquid
precursor is methyl hydrogen fluid; and wherein the second liquid
precursor is selected from the group consisting of a methyl
terminated phenylethyl polysiloxane, a tetravinyl cyclosiloxane, a
trivinyl cyclosiloxane, and a divinyl cyclosiloxane; wherein the
first liquid precursor is a methyl terminated hydride substituted
polysiloxane; and wherein the second liquid precursor is selected
from the group consisting of a methyl terminated phenylethyl
polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane,
and a divinyl cyclosiloxane; wherein the first liquid precursor is
selected from the group consisting of a methyl terminated vinyl
polysiloxane, a vinyl terminated vinyl polysiloxane, a hydride
terminated vinyl polysiloxane, and an allyl terminated dimethyl
polysiloxane; and, wherein the second liquid precursor is selected
from the group consisting of a methyl terminated phenylethyl
polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane,
a divinyl cyclosiloxane, a trivinyl hydride cyclosiloxane, a
divinyl dihydride cyclosiloxane, a dihydride cyclosiloxane, a
silane, a methyl terminated dimethyl ethyl methyl phenyl silyl
silane, an ethyl methyl phenyl silyl-cyclosiloxane, a cyclosiloxane
and an orthosilicate; and wherein the first liquid precursor is
selected from the group consisting of a vinyl terminated dimethyl
polysiloxane, a hydroxy terminated dimethyl polysiloxane, a hydride
terminated dimethyl polysiloxane, and a hydroxy terminated vinyl
polysiloxane and, wherein the second liquid precursor is selected
from the group consisting of a methyl terminated phenylethyl
polysiloxane, a tetravinyl cyclosiloxane, a trivinyl cyclosiloxane,
a divinyl dihydride cyclosiloxane, a dihydride cyclosiloxane, a
silane, a methyl terminated dimethyl ethyl methyl phenyl silyl
silane, an ethyl methyl phenyl silyl-cyclosiloxane, a cyclosiloxane
and an orthosilicate.
[0010] Still further there is provided a solvent free method for
making a neat ceramic material, and a material made therefrom, the
method involving: preparing a mixture of a first liquid
polysilocarb precursor with a second liquid precursor in the
absence of a solvent to form a solvent free liquid polysilocarb
precursor formulation, whereby the first liquid polysilocarb
precursor is not chemically reacted with the second liquid
precursor; curing the polysilocarb precursor formulation to form a
neat sold material, whereby the first liquid polysilocarb precursor
and the second liquid precursor chemically react to form the neat
solid material; and, pyrolyzing the neat sold material to form a
neat ceramic material.
[0011] Moreover, there are provided methods and materials having or
involving one or more of the following features: wherein the
pyrolysis is conducted in an inert atmosphere; wherein the
pyrolysis is conducted under a reduced pressure atmosphere; wherein
the reduced pressure atmosphere is essentially a vacuum; and,
wherein the first liquid precursor is methyl hydrogen fluid;
wherein the first liquid precursor is a methyl terminated hydride
substituted polysiloxane.
[0012] Furthermore, there are provided methods and materials having
or involving one or more of the following features: wherein the
material is bead shaped; wherein the material is a neat material in
the shape of a bead; the material is a neat ceramic material in the
shape of a bead; the material is in the shape of a film; the
material is a net material in the shape of a film; the material is
a neat ceramic material in the shape of a film; the material is a
coating; the materials is a neat material and is a coating; and the
material is a neat ceramic material and is a coating.
[0013] Yet still further, there are provided methods and materials
having or involving one or more of the following features: wherein
the solvent free liquid polysilocarb precursor formulation contains
hydride groups; wherein the solvent free liquid polysilocarb
precursor formulation contains vinyl groups; wherein the solvent
free liquid polysilocarb precursor formulation contains vinyl
groups and hydride groups; wherein the molar ratio of hydride
groups to vinyl groups is about 1.50 to 1; wherein the molar ratio
of hydride groups to vinyl groups is about 3.93 to 1.
[0014] The method of claim 49, wherein the molar ratio of hydride
groups to vinyl groups is about 5.93 to 1; wherein the molar ratio
of hydride groups to vinyl groups is about 0.08 to 1 to about 24.00
to 1; wherein the molar ratio of hydride groups to vinyl groups is
about 2.03 to 1 to about 24.00 to 1; wherein the molar ratio of
hydride groups to vinyl groups is about 3.93 to 1 to about 24.00 to
1; wherein the molar ratio of hydride groups to vinyl groups is
about 0.08 to 1 to about 1.82 to 1; wherein the molar ratio of
hydride groups to vinyl groups is about 1.12 to 1 to about 2.36 to
1; wherein the molar ratio of hydride groups to vinyl groups is
about 1.75 to 1 to about 23.02 to 1; wherein the molar ratio of
hydride groups to vinyl groups is about 1.50 to 1 to about 3.93 to
1; wherein the molar ratio of hydride groups to vinyl groups is
about 1.26 to 1 to about 4.97 to 1; and, wherein the molar ratio of
hydride groups to vinyl groups is about 0.08 to 1 to about 1.50 to
1.
[0015] Still additionally there is provided a solvent free method
for making a neat solid material, and materials made therefrom, the
method involving: preparing a mixture of a first liquid
polysilocarb precursor with a second liquid precursor in the
absence of a solvent to form a solvent free liquid polysilocarb
precursor formulation, whereby the first liquid polysilocarb
precursor is not chemically reacted with the second liquid
precursor; and, curing the polysilocarb precursor formulation to
form a neat sold material, whereby the first liquid polysilocarb
precursor and the second liquid precursor chemically react to form
the neat solid material.
[0016] Yet moreover, there is provided a reaction free method for
making a polysilocarb material, and the material made therefrom,
the method involving: obtaining a first liquid polysilocarb
precursor; obtaining a second liquid polysilocarb precursor
comprising a first reactive group; obtaining a third liquid
polysilocarb precursor comprising a second reactive group; and,
mixing the first liquid polysilocarb precursor, the second liquid
polysilocarb precursor and the third liquid polysilocarb precursor
to form a liquid polysilocarb precursor formulation, wherein the
first reactive group is unreacted; and the first liquid
polysilocarb precursor is not chemically reacted with the second
liquid precursor; and, curing the polysilocarb precursor
formulation to form a neat sold material, whereby the first liquid
polysilocarb precursor and the second liquid precursor chemically
react to form the neat solid material.
[0017] Yet still further, there are provided methods and materials
having or involving one or more of the following features: wherein
the first reactive group comprises a hydride, and the second
reactive group comprises a vinyl; wherein the first reactive group
comprises a reactive group selected from the group consisting of
vinyl, allyl, hydroxy, hydride, phenyl, and phenylethyl; wherein
the second reactive group comprises a reactive group selected from
the group consisting of vinyl, allyl, hydroxy, hydride, phenyl, and
phenylethyl; wherein the first reactive group and the second
reactive group comprises a reactive group selected from the group
consisting of vinyl, allyl, hydroxy, hydride, phenyl, and
phenylethyl.
[0018] Still further there is provided a method for making a
polysilocarb material, and materials made therefrom, the method
involving: obtaining a first liquid polysilocarb precursor;
obtaining a second liquid polysilocarb precursor comprising a first
reactive group; obtaining a third liquid polysilocarb precursor
comprising a second reactive group; mixing the first liquid
polysilocarb precursor, the second liquid polysilocarb precursor
and the third liquid polysilocarb precursor to form a liquid
polysilocarb precursor formulation, wherein the first reactive
group is unreacted; and, curing the polysilocarb precursor
formulation, whereby the first reactive group and the second
reactive group chemically react to form a sold material.
[0019] Still additionally, there is provided a method for making a
neat polysilocarb material, and the materials made therefrom, the
method involving: obtaining a first liquid polysilocarb precursor;
obtaining a second liquid polysilocarb precursor comprising a first
reactive group; obtaining a third liquid polysilocarb precursor
comprising a second reactive group; mixing the first liquid
polysilocarb precursor, the second liquid polysilocarb precursor
and the third liquid polysilocarb precursor to form a liquid
polysilocarb precursor formulation, wherein the first reactive
group is unreacted; and, curing the polysilocarb precursor
formulation, whereby the first reactive group and the second
reactive group chemically react to form a neat sold material.
[0020] Furthermore, there are provided methods and materials having
or involving one or more of the following features: wherein the
first reactive group comprises a hydride, and the second reactive
group comprises a vinyl; wherein the first reactive group comprises
a reactive group selected from the group consisting of vinyl,
allyl, hydroxy, hydride, phenyl, and phenylethyl; wherein the
second reactive group comprises a reactive group selected from the
group consisting of vinyl, allyl, hydroxy, hydride, phenyl, and
phenylethyl; and, wherein the first reactive group and the second
reactive group comprises a reactive group selected from the group
consisting of vinyl, allyl, hydroxy, hydride, phenyl, and
phenylethyl.
[0021] Additionally, there is provided a method of making a
polysilocarb precursor formulation, and materials made from curing
and pyrolyzing that formulation, the method involving: providing an
amount of a first precursor to a reaction vessel, the first
precursor comprising silicon; providing an amount of a source of
thermal mass to the reaction vessel; providing an amount of water
to the reaction vessel; providing an amount of a proton source to
the reaction vessel; thereby forming a reaction mixture comprising
the first precursor, the source of thermal mass, water and the
proton source; heating the reaction mixture, whereby the activation
energy for the reaction mixture is reached, wherein an exothermic
reaction takes place in the reaction vessel; controlling the
exothermic reaction to form a polysilocarb precursor formulation;
separating the polysilocarb precursor formation.
[0022] Still moreover, there is provided a method of making a
polysilocarb precursor formulation, and materials made from curing
and pyrolyzing this formulation, the method involving: providing an
amount of a first precursor, the first precursor comprising silicon
and an ethoxy group, to a reaction vessel; providing a reactant to
the reaction vessel; thereby forming a reaction mixture comprising
the first precursor and the reactant; and, obtaining the activation
energy for the reaction mixture, wherein an exothermic reaction
takes place, the exothermic reaction comprising the formation of a
hydroxy group on the first precursor and the reaction of the
hydroxy group with an ethoxy group on the first precursor; thereby
forming a polysilocarb precursor.
[0023] Yet further there is provided a polysilocarb derived ceramic
material resulting from the pyrolysis of a polymeric precursor
comprising a backbone having the formula
--R.sub.1--Si--C--C--Si--O--Si--C--C--Si--R.sub.2--, where R.sub.1
and R.sub.2 comprise materials selected from the group consisting
of methyl, hydroxyl, vinyl and allyl.
[0024] Furthermore, there are provided methods and materials having
or involving one or more of the following features: wherein the
first precursor is selected from the group consisting of methyl
hydrogen, siloxane backbone additive, vinyl substituted and vinyl
terminated polydimethyl siloxane, vinyl substituted and hydrogen
terminated polydimethyl siloxane, allyl terminated polydimethyl
siloxane, silanol terminated polydimethyl siloxane, hydrogen
terminated polydimethyl siloxane, vinyl terminated diphenyl
dimethyl polysiloxane, hydroxyl terminated diphenyl dimethyl
polysiloxane, hydride terminated diphenyl dimethyl polysiloxane,
styrene vinyl benzene dimethyl polysiloxane, and
tetramethyltetravinylcyclotetrasiloxane; and.
[0025] Yet moreover there is provided a solid, solvent-free
composition comprising:.quadrature.a cross-linked polymer matrix
having a density of from 0.99 g/cc to 1.25 g/cc, a hardness from
Shore D35 to Shore D85, and a flexural strength of up to 3 ksi, the
composition being free of ester, carbonate, carbamate or urea
linkages.
[0026] Furthermore, there are provided methods and materials having
or involving one or more of the following features: wherein the
composition has a flame resistance of UL-V0 without any
fire-retardant additives; having fibers to form a composite 10
composition having a flexural strength of 40 ksi to 140 ksi; adding
a catalyst, light, heat, or a combination thereof to the
premixture; wherein the premixture includes between 5 and 20 40%
addition reaction cross-linkable groups; and wherein the addition
reaction cross-linkable groups are vinyl, allyl, propargyl or
ethynyl groups.
[0027] Additionally, there is provided a method of synthesizing a
solid material in the absence of solvent comprising: mixing liquid
components in the absence of a solvent to form a premixture, the
premixture including between 2 and 50% addition reaction
cross-linkable groups; and 15 crosslinking the premixture in the
absence of a solvent to form a solid structure free of ester,
carbonate, carbamate or urea linkages.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 is a chemical formula for an embodiment of a methyl
terminated hydride substituted polysiloxane precursor material in
accordance with the present inventions.
[0029] FIG. 2 is a chemical formula for an embodiment of a methyl
terminated vinyl polysiloxane precursor material in accordance with
the present inventions.
[0030] FIG. 3 is a chemical formula for an embodiment of a vinyl
terminated vinyl polysiloxane precursor material in accordance with
the present inventions.
[0031] FIG. 4 is a chemical formula for an embodiment of a hydride
terminated vinyl polysiloxane precursor material in accordance with
the present inventions.
[0032] FIG. 5 is a chemical formula for an embodiment of an allyl
terminated dimethyl polysiloxane precursor material in accordance
with the present inventions.
[0033] FIG. 6 is a chemical formula for an embodiment of a vinyl
terminated dimethyl polysiloxane precursor material in accordance
with the present inventions.
[0034] FIG. 7 is a chemical formula for an embodiment of a hydroxy
terminated dimethyl polysiloxane precursor material in accordance
with the present inventions.
[0035] FIG. 8 is a chemical formula for an embodiment of a hydride
terminated dimethyl polysiloxane precursor material in accordance
with the present inventions.
[0036] FIG. 9 is a chemical formula for an embodiment of a hydroxy
terminated vinyl polysiloxane precursor material in accordance with
the present inventions.
[0037] FIG. 10 is a chemical formula for an embodiment of a phenyl
terminated dimethyl polysiloxane precursor material in accordance
with the present inventions.
[0038] FIG. 11 is a chemical formula for an embodiment of a phenyl
and methyl terminated dimethyl polysiloxane precursor material in
accordance with the present inventions.
[0039] FIG. 12 is a chemical formula for an embodiment of a methyl
terminated dimethyl diphenyl polysiloxane precursor material in
accordance with the present inventions.
[0040] FIG. 13 is a chemical formula for an embodiment of a vinyl
terminated dimethyl diphenyl polysiloxane precursor material in
accordance with the present inventions.
[0041] FIG. 14 is a chemical formula for an embodiment of a hydroxy
terminated dimethyl diphenyl polysiloxane precursor material in
accordance with the present inventions.
[0042] FIG. 15 is a chemical formula for an embodiment of a hydride
terminated dimethyl diphenyl polysiloxane precursor material in
accordance with the present inventions.
[0043] FIG. 16 is a chemical formula for an embodiment of a methyl
terminated phenylethyl polysiloxane precursor material in
accordance with the present inventions.
[0044] FIG. 17 is a chemical formula for an embodiment of a
tetravinyl cyclosiloxane in accordance with the present
inventions.
[0045] FIG. 18 is chemical formula for an embodiment of a trivinyl
cyclosiloxane in accordance with the present inventions.
[0046] FIG. 19 is a chemical formula for an embodiment of a divinyl
cyclosiloxane in accordance with the present inventions.
[0047] FIG. 20 is a chemical formula for an embodiment of a
trivinyl hydride cyclosiloxane in accordance with the present
inventions.
[0048] FIG. 21 is a chemical formula for an embodiment of a divinyl
dihydride cyclosiloxane in accordance with the present
inventions.
[0049] FIG. 22 is a chemical formula for an embodiment of a
dihydride cyclosiloxane in accordance with the present
inventions.
[0050] FIG. 23 is a chemical formula for an embodiment of a
dihydride cyclosiloxane in accordance with the present
inventions.
[0051] FIG. 24 is a chemical formula for an embodiment of a silane
in accordance with the present inventions.
[0052] FIG. 25 is a chemical formula for an embodiment of a silane
in accordance with the present inventions.
[0053] FIG. 26 is a chemical formula for an embodiment of a silane
in accordance with the present inventions.
[0054] FIG. 27 is a chemical formula for an embodiment of a silane
in accordance with the present inventions.
[0055] FIG. 28 is a chemical formula for an embodiment of a methyl
terminated dimethyl ethyl methyl phenyl silyl silane polysiloxane
precursor material in accordance with the present inventions.
[0056] FIG. 29 is chemical formulas for an embodiment of a
polysiloxane precursor material in accordance with the present
inventions.
[0057] FIG. 30 is chemical formulas for an embodiment of a
polysiloxane precursor material in accordance with the present
inventions.
[0058] FIG. 31 is chemical formulas for an embodiment of a
polysiloxane precursor material in accordance with the present
inventions.
[0059] FIG. 32 is a chemical formula for an embodiment of an ethyl
methyl phenyl silyl-cyclosiloxane in accordance with the present
inventions.
[0060] FIG. 33 is a chemical formula for an embodiment of a
cyclosiloxane in accordance with the present inventions.
[0061] FIG. 34 is a chemical formula for an embodiment of a
siloxane precursor in accordance with the present inventions.
[0062] FIGS. 34A to 34D are chemical formula for embodiments of the
E.sub.1 and E.sub.2 groups in the formula of FIG. 34.
[0063] FIG. 35 is a chemical formula for an embodiment of an
orthosilicate in accordance with the present inventions.
[0064] FIG. 36 is a chemical formula for an embodiment of a
polysiloxane in accordance with the present inventions.
[0065] FIG. 37 is a chemical formula for an embodiment of a
triethoxy methyl silane in accordance with the present
inventions.
[0066] FIG. 38 is a chemical formula for an embodiment of a
diethoxy methyl phenyl silane in accordance with the present
inventions.
[0067] FIG. 39 is a chemical formula for an embodiment of a
diethoxy methyl hydride silane in accordance with the present
inventions.
[0068] FIG. 40 is a chemical formula for an embodiment of a
diethoxy methyl vinyl silane in accordance with the present
inventions.
[0069] FIG. 41 is a chemical formula for an embodiment of a
dimethyl ethoxy vinyl silane in accordance with the present
inventions.
[0070] FIG. 42 is a chemical formula for an embodiment of a
diethoxy dimethyl silane in accordance with the present
inventions.
[0071] FIG. 43 is a chemical formula for an embodiment of an ethoxy
dimethyl phenyl silane in accordance with the present
inventions.
[0072] FIG. 44 is a chemical formula for an embodiment of a
diethoxy dihydride silane in accordance with the present
inventions.
[0073] FIG. 45 is a chemical formula for an embodiment of a
triethoxy phenyl silane in accordance with the present
inventions.
[0074] FIG. 46 is a chemical formula for an embodiment of a
diethoxy hydride trimethyl siloxane in accordance with the present
inventions.
[0075] FIG. 47 is a chemical formula for an embodiment of a
diethoxy methyl trimethyl siloxane in accordance with the present
inventions.
[0076] FIG. 48 is a chemical formula for an embodiment of a
trimethyl ethoxy silane in accordance with the present
inventions.
[0077] FIG. 49 is a chemical formula for an embodiment of a
diphenyl diethoxy silane in accordance with the present
inventions.
[0078] FIG. 50 is a chemical formula for an embodiment of a
dimethyl ethoxy hydride siloxane in accordance with the present
invention.
[0079] FIGS. 51A to 51F are chemical formulas for starting
materials in accordance with the present inventions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0080] In general, the present inventions relate to unique and
novel silicon (Si) based materials that are easy to manufacture,
handle and have surprising and unexpected properties and
applications. These silicon based materials have applications and
utilizations as a liquid material, a cured material, e.g., a
plastic, a preceramic, and a pyrolized material, e.g., a
ceramic.
[0081] Further, and generally, the present inventions relate to the
precursors to preceramic materials, inorganic polymers, inorganic
semi-organic polymers, organosilcon materials and polymers,
mixtures of such precursors, preceramic materials, cured preceramic
materials, cured mixtures of precursors, cured inorganic polymers,
cured inorganic semi-organic polymers, ceramic materials, and
methods and processes for making these precursors, inorganic
polymers, inorganic semi-organic polymers, mixtures, preceramic
materials, cured materials and ceramic materials. In particular,
and preferably, the present inventions include polymer derived
ceramic materials, polymer derived cured preceramic materials,
polymer derived preceramic materials, precursors to polymer derived
preceramic and ceramic materials, mixtures of precursors to polymer
derived preceramic and ceramic materials, and methods and processes
relating to these materials.
[0082] The silicon based materials of the present inventions go
against the general trends of the art of silicon chemistry and
uses. Generally, the art of silicon chemistry, and in particular
organosilicon chemistry, has moved toward greater and greater
complexity in the functional groups that are appended to, and a
part of, a silicon based polymeric backbone. Similarly, in general,
the processes that are utilized to make these polymers have moved
toward greater and greater complexity. The present inventions move
away from this trend, by preferably functionalizing a silicon based
polymeric backbone with simpler structures, such as phenyl,
phenylethyl and smaller groups, and do so with processes that are
simplified, e.g., solvent free, reduced solvent, lower cost
starting materials, fewer steps, and reduction of reaction
intermediates.
[0083] Further, and generally, the art views silicones as tacky,
soft or liquid materials that are used with, on, or in conjunction
with, other materials to enhance or provide a performance feature
to those other materials. Silicon based materials generally are not
viewed as stand alone products, primary products, or structural
elements. The silicon based materials of the present inventions,
however, move away from this trend and understanding in the art.
The silicon based materials of the present inventions provide
materials that, among other things, can function as stand alone
products, primary products and structural elements. The silicon
based materials of the present invention can also function as
composites, coatings, components, additives, material performance
enhancers, and other applications and utilizations.
[0084] Thus, the present inventions, among other things, provide a
new material systems and platform having many varied formulations,
applications and uses, which could not generally have been obtained
with prior silicon based products, and in particular, could not
generally have been obtained with prior silicon based products at
acceptable costs, volumes, manufacturing conditions, handling
requirements, or processing conditions among other things.
[0085] Generally, the present inventions are directed toward
"polysilocarb" materials, e.g., material containing silicon (Si),
oxygen (O) and carbon (C), and materials that have been pyrolized
from such materials. Polysilocarb materials may also contain other
elements. Polysilocarb materials are made from one or more
polysilocarb precursor formulation or precursor formulation. The
polysilocarb precursor formulation contains one or more
functionalized silicon polymers, or monomers, as well as,
potentially other ingredients, such as for example, inhibitors,
catalysts, pore formers, fillers, reinforcers, fibers, particles,
colorants, pigments, dies, polymer derived ceramics ("PDC"),
ceramics, metals, metal complexes, and combinations and variations
of these and other materials and additives.
[0086] The polysilocarb precursor formulation is then cured to form
a solid or semi-sold material, e.g., a plastic. The polysilocarb
precursor formulation may be processed through an initial cure, to
provide a partially cured material, which may also be referred to,
for example, as a preform, green material, or green cure (not
implying anything about the material's color). The green material
may then be further cured. Thus, one or more curing steps may be
used. The material may be "end cured," i.e., being cured to that
point at which the material has the necessary physical strength and
other properties for its intended purpose. The amount of curing may
be to a final cure (or "hard cure"), i.e., that point at which all,
or essentially all, of the chemical reaction has stopped (as
measured, for example, by the absence of reactive groups in the
material, or the leveling off of the decrease in reactive groups
over time). Thus, the material may be cured to varying degrees,
depending upon it's intended use and purpose. For example, in some
situations the end cure and the hard cure may be the same.
[0087] The curing may be done at standard ambient temperature and
pressure ("SATP", 1 atmosphere, 25.degree. C.), at temperatures
above or below that temperature, at pressures above or below that
pressure, and over varying time periods (both continuous and
cycled, e.g., heating followed by cooling and reheating), from less
than a minute, to minutes, to hours, to days (or potentially
longer), and in air, in liquid, or in a preselected atmosphere,
e.g., Argon (Ar) or nitrogen (N.sub.2).
[0088] The polysilocarb precursor formulations can be made into
non-reinforced, non-filled, composite, reinforced, and filled
structures, intermediates and end products, and combinations and
variations of these and other types of materials. Further, these
structures, intermediates and end products can be cured (e.g.,
green cured, end cured, or hard cured), uncured, pyrolized to a
ceramic, and combinations and variations of these (e.g., a cured
material may be filled with pyrolized beads derived from the same
polysilocarb as the cured material).
[0089] The precursor formulations may be used to form a "neat"
material, (by "neat" material it is meant that all, and essentially
all of the structure is made from the precursor material or
unfilled formulation; and thus, there are no fillers or
reinforcements). They may be used to form composite materials,
e.g., reinforced products. They may be used to form non-reinforced
materials, which are materials that are made of primarily,
essentially, and preferably only from the precursor materials, for
example a pigmented polysiloxane structure having only precursor
material and a colorant would be considered non-reinforced
material.
[0090] In making the polysilocarb precursor formulation into a
structure, part, intermediate, or end product, the polysilocarb
formulation can be, for example, sprayed, flowed, thermal sprayed,
painted, molded, formed, extruded, spun, dropped, injected or
otherwise manipulated into essentially any volumetric shape,
including planer shape (which still has a volume, but is more akin
to a coating, skin, film, or even a counter top, where the
thickness is significantly smaller, if not orders of magnitude
smaller, than the other dimensions), and combinations and
variations of these. These volumetric shapes would include, for
example, spheres, pellets, rings, lenses, disks, panels, cones,
frustoconical shapes, squares, rectangles, trusses, angles,
channels, hollow sealed chambers, hollow spheres, blocks, sheets,
coatings, films, skins, particulates, beams, rods, angles, columns,
fibers, staple fibers, tubes, cups, pipes, and combinations and
various of these and other more complex shapes, both engineering
and architectural. Additionally, they may be shaped into preforms,
or preliminary shapes that correspond to, or with, a final product,
such as for example use in or with, a break pad, a clutch plate, a
break shoe, a motor, high temperature parts of a motor, a diesel
motor, rocket components, turbine components, air plane components,
space vehicle components, building materials, shipping container
components, and other structures or components.
[0091] The polysilocarb precursor formulations may be used with
reinforcing materials to form a composite material. Thus, for
example, the formulation may be flowed into, impregnated into,
absorbed by or otherwise combined with a reinforcing material, such
as carbon fibers, glass fiber, woven fabric, non-woven fabric,
copped fibers, fibers, rope, braided structures, ceramic powders,
glass powders, carbon powders, graphite powders, ceramic fibers,
metal powders, carbide pellets or components, staple fibers, tow,
nanostructures of the above, PDCs, any other material that meets
the temperature requirements of the process and end product, and
combinations and variations of these. Thus, for example, the
reinforcing materials may be any of the high temperature resistant
reinforcing materials currently used, or capable of being used
with, existing plastics and ceramic composite materials.
Additionally, because the polysilocarb precursor formulation may be
formulated for a lower temperature cure (e.g., SATP) or a cure
temperature of for example about 100.degree. F. to about
400.degree. F., the reinforcing material may be polymers, organic
polymers, such as nylons, polypropylene, and polyethylene, as well
as aramid fibers, such as NOMEX or KEVLAR.
[0092] The reinforcing material may also be made from, or derived
from the same material as the formulation that has been formed into
a fiber and pyrolized into a ceramic, or it may be made from a
different precursor formulation material, which has been formed
into a fiber and pyrolized into a ceramic. In addition to ceramic
fibers derived from the precursor formulation materials that may be
used as reinforcing material, other porous, substantially porous,
and non-porous ceramic structures derived from a precursor
formulation material may be used.
[0093] The polysilocarb precursor formulation may be used to form a
filled material. A filled material would be any material having
other solid, or semi-solid, materials added to the polysilocarb
precursor formulation. The filler material may be selected to
provide certain features to the cured product, the ceramic product
or both. These features may relate to or be aesthetic, tactile,
thermal, density, radiation, chemical, magnetic, electric, and
combinations and variations of these and other features. These
features may be in addition to strength. Thus, the filler material
may not affect the strength of the cured or ceramic material, it
may add strength, or could even reduce strength in some situations.
The filler material could impart color, magnetic capabilities, fire
resistances, flame retardance, heat resistance, electrical
conductivity, anti-static, optical properties (e.g., reflectivity,
refractivity and iridescence), aesthetic properties (such as stone
like appearance in building products), chemical resistivity,
corrosion resistance, wear resistance, abrasions resistance,
thermal insulation, UV stability, UV protective, and other features
that may be desirable, necessary, and both, in the end product or
material. Thus, filler materials could include copper lead wires,
thermal conductive fillers, electrically conductive fillers, lead,
optical fibers, ceramic colorants, pigments, oxides, dyes, powders,
ceramic fines, PDC particles, pore-formers, carbosilanes, silanes,
silazanes, silicon carbide, carbosilazanes, siloxane, powders,
ceramic powders, metals, metal complexes, carbon, tow, fibers,
staple fibers, boron containing materials, milled fibers, glass,
glass fiber, fiber glass, and nanostructures (including
nanostructures of the forgoing) to name a few. For example,
crushed, PDC particles, e.g., fines or beads, can be added to a
polysilocarb formulation and then cured to form a filled cured
plastic material, which has significant fire resistant properties
as a coating or structural material.
[0094] As used herein, unless specifically provided otherwise, the
terms flame retardant, fire retardant, flame resistant, fire
resistant, flame protection, fire protection, flame suppression,
fire suppression, and similar such terms are to be given their
broadest possible meanings, and would include all burning, fire,
combustion or flame related meanings that are found, described or
set forth in standards, codes, certifications, regulations, and
guidelines, and would include the lessening, reduction, and
avoidance of fire, combustion or smoke.
[0095] The fill material may also be made from, or derived from the
same material as the formulation that has been formed into a cured
or pyrolized solid, or it may be made from a different precursor
formulation material, which has been formed into a cured solid or
semi-solid, or pyrolized solid.
[0096] The polysilocarb formulation and products derived or made
from that formulation may have metals and metal complexes. Thus,
metals as oxides, carbides or silicides can be introduced into
precursor formulations, and thus into a silica matrix in a
controlled fashion. Thus, using organometallic, metal halide
(chloride, bromide, iodide), metal alkoxide and metal amide
compounds of transition metals and then copolymerizing in the
silica matrix, through incorporation into a precursor formulation
is contemplated.
[0097] For example, Cyclopentadienyl compounds of the transition
metals can be utilized. Cyclopentadienyl compounds of the
transition metals can be organized into two classes:
Bis-cyclopentadienyl complexes; and Monocyclopentadienyl complexes.
Cyclopentadienyl complexes can include C.sub.5H.sub.5,
C.sub.5Me.sub.5, C.sub.5H.sub.4Me, CH.sub.5R.sub.5 (where R=Me, Et,
Propyl, i-Propyl, butyl, Isobutyl, Sec-butyl). In either of these
cases Si can be directly bonded to the Cyclopentadienyl ligand or
the Si center can be attached to an alkyl chain, which in turn is
attached to the Cyclopentadienyl ligand.
[0098] Cyclopentadienyl complexes, that can be utilized with
precursor formulations and in products, can include:
bis-cyclopentadienyl metal complexes of first row transition metals
(Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel); second row
transition metals (Zirconium, Molybdenum, Ruthenium, Rhodium,
Palladium); third row transition metals (Hafnium, Tantalum,
Tungsten, Iridium, Osmium, Platinum); Lanthanide series (La, Ce,
Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho); Actinide series (Ac, Th, Pa,
U, Np).
[0099] Monocyclopentadienyl complexes may also be utilized to
provide metal functionality to precursor formulations and would
include monocyclopentadienyl complexes of: first row transition
metals (Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel); second
row transition metals (Zirconium, Molybdenum, Ruthenium, Rhodium,
Palladium); third row transition metals (Hafnium, Tantalum,
Tungsten, Iridium, Osmium, Platinum) when preferably stabilized
with proper ligands, (for instance Chloride or Carbonyl).
[0100] Alky complexes of metals may also be used to provide metal
functionality to precursor formulations and products. In these
alkyl complexes the Si center has an alkyl group (ethyl, propyl,
butyl, vinyl, propenyl, butenyl) which can bond to transition metal
direct through a sigma bond. Further, this would be more common
with later transition metals such as Pd, Rh, Pt, Ir.
[0101] Coordination complexes of metals may also be used to provide
metal functionality to precursor formulations and products. In
these coordination complexes the Si center has an unsaturated alkyl
group (vinyl, propenyl, butenyl, acetylene, butadienyl) which can
bond to carbonyl complexes or ene complexes of Cr, Mo, W, Mn, Re,
Fe, Ru, Os, Co, Rh, Ir, Ni. The Si center may also be attached to a
phenyl, substituted phenyl or other aryl compound (pyridine,
pyrimidine) and the phenyl or aryl group can displace carbonyls on
the metal centers.
[0102] Metal alkoxides may also be used to provide metal
functionality to precursor formulations and products. Metal
alkoxide compounds can be mixed with the Silicon precursor
compounds and then treated with water to form the oxides at the
same time as the polymer, copolymerize. This can also be done with
metal halides and metal amides. Preferably, this may be done using
early transition metals along with Aluminum, Gallium and Indium,
later transition metals: Fe, Mn, Cu, and alkaline earth metals: Ca,
Sr, Ba, Mg.
[0103] Compounds where Si is directly bonded to a metal center
which is stabilized by halide or organic groups may also be
utilized to provide metal functionality to precursor formulations
and products.
[0104] Additionally, it should be understood that the metal and
metal complexes may be the continuous phase after pyrolysis, or
subsequent heat treatment. Formulations can be specifically
designed to react with selected metals to in situ form metal
carbides, oxides and other metal compounds, generally known as
cermets (e.g., ceramic metallic compounds). The formulations can be
reacted with selected metals to form in situ compounds such as
mullite, alumino silicate, and others. The amount of metal relative
to the amount of silica in the formulation or end product can be
from about 0.1 mole % to 99.9 mole %, about 1 mole % or greater,
about 10 mole % or greater, about 20 mole percent or greater % and
greater. The forgoing use of metals with the present precursor
formulas can be used to control and provide predetermined
stoichiometries.
[0105] Filled materials would include reinforced materials. In many
cases, cured, as well as pyrolized polysilocarb filled materials
can be viewed as composite materials. Generally, under this view,
the polysilocarb would constitute the bulk or matrix phase, (e.g.,
a continuous, or substantially continuous phase), and the filler
would constitute the dispersed (e.g., non-continuous), phase.
[0106] It should be noted, however, that by referring to a material
as "filled" or "reinforced" it does not imply that the majority
(either by weight, volume, or both) of that material is the
polysilcocarb. Thus, generally, the ratio (either weight or volume)
of polysilocarb to filler material could be from about 0.1:99.9 to
99.9:0.1. Smaller amounts of filler material or polysilocarb could
also be present or utilized, but would more typically be viewed as
an additive or referred to in other manners. Thus, the terms
composite, filled material, polysilocarb filled materials,
reinforced materials, polysilocarb reinforced materials,
polysilocarb filled materials, polysilocarb reinforced materials
and similar such terms should be viewed as non-limiting as to
amounts and ratios of the material's constitutes, and thus in this
context, be given their broadest possible meaning.
[0107] The polysilocarb precursor formulation may be specifically
formulated to cure under conditions (e.g., temperature, and perhaps
time) that match, e.g., are predetermined to match, the properties
of the reinforcing material, filler material or substrate. These
materials may also be made from, or derived from, the same material
as the polysilocarb precursor formulation that is used as the
matrix, or it may be made from a different polysilocarb precursor
formulation. In addition to ceramic fibers derived from the
polysilocarb precursor formulation materials, porous, substantially
porous, and non-porous ceramic structures derived from a
polysilocarb precursor formulation material may be used as filler
or reinforcing material.
[0108] The polysilocarb precursor formulations may be used to coat
or impregnate a woven or non-woven fabric, made from for example
carbon fiber, glass fibers or fibers made from a polysilocarb
precursor formulation (the same or different formulation), to from
a prepreg material. Further, a polysilocarb precursor formulation
may be used as an interface coating on the reinforcing material,
for use either with a polysilocarb precursor formulation as the
matrix material. Further, carbon fiber may be heat treated to about
1,400.degree. to about 1,800.degree. or higher, which creates a
surface feature that eliminates the need for a separate interface
coating, for use with polysilocarb precursor formulations.
[0109] Fillers can reduce the amount of shrinkage that occurs
during the processing of the formulation into a ceramic, they can
be used to provide a predetermined density of the product, either
reducing or increasing density, and can be used to provide other
customized and predetermined product and processing features.
Fillers, at larger amounts, e.g., greater than 10%, can have the
effect of reducing shrinkage during cure.
[0110] Depending upon the particular application, product or end
use, the filler can be evenly distributed in the precursor
formulation, unevenly distributed, a predetermined rate of
settling, and can have different amounts in different formulations,
which can then be formed into a product having a predetermined
amounts of filler in predetermined areas, e.g., striated layers
having different filler concentration.
[0111] Preferably, for a typical filled product, the filler is
substantially evenly distributed and more preferably evenly
distributed within the end product. In this manner localize
stresses or weak points can be avoided. Generally, for a
non-reinforced material each filler particle may have a volume that
is less than about 0.3%, less than about 0.2%, less than about
0.1%, and less than about 0.05% of the volume of a product,
intermediate or part. For example if the product is spherical in
shape and the filler is spherical in shape the diameter of the
filler should preferable be about 1/10 to about 1/20 of the
diameter of the proppant particle, and more preferably the filler
diameter should be less than about 1/20 of the diameter of the
proppant particle. Generally, the relative amount of filler used in
a material should preferable be about 30% to about 65% of the
volume of the sphere, e.g., volume %.
[0112] Generally, when a small particulate filler, e.g., fines,
beads, pellets, is used for the purposes of increasing strength,
without the presence of fibers, fabric, etc., generally at least
about 2% to at least about 5 volume %, can show an increase in the
strength, although this may be greater or smaller depending upon
other factors, such as the shape and volume of the product, later
processing conditions, e.g., cure time, temperature, number of
pyrolysis reinfiltrations. Generally, as the filler level increases
from about above 5 volume % no further strength benefits may be
realized. Such small particulate filled products, in which
appreciable strength benefits are obtained from the filler, and in
particular an increase in strength of at least about 5%, at last
about 10% and preferably at least about 20% would be considered to
be reinforced products and materials.
[0113] As used herein, unless specified otherwise the terms %,
weight % and mass % are used interchangeably and refer to the
weight of a first component as a percentage of the weight of the
total, e.g., formulation, mixture, material or product. As used
herein, unless specified otherwise "volume %" and "% volume" and
similar such terms refer to the volume of a first component as a
percentage of the volume of the total, e.g., formulation, material
or product.
[0114] At various points during the manufacturing process, the
polysilocarb structures, intermediates and end products, and
combinations and variations of these, may be machined, milled,
molded, shaped, drilled or otherwise mechanically processed and
shaped.
[0115] Generally, the term "about" is meant to encompass a variance
or range of .+-.10%, the experimental or instrument error
associated with obtaining the stated value, and preferably the
larger of these.
[0116] The precursor formulations are preferably clear or are
essentially colorless and generally transmissive to light in the
visible wavelengths. They may, depending upon the formulation have
a turbid, milky or clouding appearance. They may also have color
bodies, pigments or colorants, as well as color filler (which can
survive pyrolysis, for ceramic end products, such as those used in
ceramic pottery glazes). The precursor may also have a yellow or
amber color or tint, without the need of the addition of a
colorant.
[0117] The precursor formulations may be packaged, shipped and
stored for later use in forming products, e.g., structures or
parts, or they may be used directly in these processes, e.g.,
continuous process to make a product. Thus, a precursor formulation
may be stored in 55 gallon drums, tank trucks, rail tack cars,
onsite storage tanks having the capable of holding hundreds of
gals, and shipping totes holding 1,000 liters, by way of example.
Additionally, in manufacturing process the formulations may be made
and used in a continuous, and semi-continuous processes.
[0118] The present inventions, among other things, provide
substantial flexibility in designing processes, systems, ceramics,
having processing properties and end product performance features
to meet predetermined and specific performance criteria. Thus, for
example the viscosity of the precursor formulation may me
predetermined by the formulation to match a particular morphology
of the reinforcing material, the cure temperature of the precursor
formulation may be predetermined by the formulation to enable a
prepreg to have an extended shelf life. The viscosity of the of the
precursor formulation may be established so that the precursor
readily flows into the reinforcing material of the prepreg while at
the same time being thick enough to prevent the precursor
formulation from draining or running off of the reinforcing
material. The formulation of the precursor formulation may also,
for example, be such that the strength of a cured preform is
sufficient to allow rough or initial machining of the preform,
prior to pyrolysis.
[0119] Custom and predetermined control of when chemical reactions
occur in the various stages of the process from raw material to
final end product can provide for reduced costs, increased process
control, increased reliability, increased efficiency, enhanced
product features, and combinations and variation of these and other
benefits. The sequencing of when chemical reactions take place can
be based primarily upon the processing or making of precursors, and
the processing or making of precursor formulations; and may also be
based upon cure and pyrolysis conditions. Further, the custom and
predetermined selection of these steps, formulations and
conditions, can provide enhanced product and processing features
through chemical reactions, molecular arrangements and
rearrangements, and microstructure arrangements and rearrangements,
that preferably have been predetermined and controlled.
[0120] It should be understood that the use of headings in this
specification is for the purpose of clarity, and are not limiting
in any way. Thus, the processes and disclosures described under a
heading should be read in context with the entirely of this
specification, including the various examples. The use of headings
in this specification should not limit the scope of protection
afford the present inventions.
[0121] Generally, the process form making the present polysilocarb
materials involves one or more steps. The starting materials are
obtained, made or derived. Precursors are obtained or can be made
from starting materials. The precursors are combined to form a
precursor formulation. The precursor formulation is then shaped,
formed, molded, etc. into a desired form, which form is then cured,
which among other things transforms the precursor formulation into
a plastic like material. This cured plastic like material can then
be pyrolized into a ceramic. It being understood, that these steps
may not all be used, that some of these steps may be repeated,
once, twice or several times, and that combinations and variations
of these general steps may be utilized to obtain a desired product
or result.
[0122] Processes for Obtaining a Polysilocarb Precursor
Formulation
[0123] Polysilocarb precursor formulations can generally be made
using two types of processes, although other processes and
variations of these types of processes may be utilized. These
processes generally involve combining precursors to form a
polysilocarb precursor formulation. One type of process generally
involves the mixing together of precursor materials in preferably a
solvent free process with essentially no chemical reactions taking
place, e.g., "the mixing process." The other type of process
generally involves chemical reactions to form specific, e.g.,
custom, polysilocarb precursor formulations, which could be
monomers, dimers, trimers and polymers. Generally, in the mixing
process essentially all, and preferably all, of the chemical
reactions take place during subsequent processing, such as during
curing, pyrolysis and both. It should be understood that these
terms--reaction type process and the mixing type process--are used
for convenience, e.g., a short hand reference, and should not be
viewed as limiting. Further, it should be understood that
combinations and variations of these two processes may be used in
reaching a precursor formulation, and in reaching intermediate, end
and final products. Depending upon the specific process and desired
features of the product the precursors and starting materials for
one process type can be used in the other. These processes provide
great flexibility to create custom features for intermediate, end
and final products, and thus, typically, either process type, and
combinations of them, can provide a specific predetermined product.
In selecting which type of process is preferable factors such as
cost, controllability, shelf life, scale up, manufacturing ease,
etc., can be considered.
[0124] The two process types are described in this specification,
among other places, under their respective headings. It should be
understood that the teachings for one process, under one heading,
and the teachings for the other process, under the other heading,
can be applicable to each other, as well as, being applicable to
other sections and teachings in this specification, and vice versa.
The starting or precursor materials for one type of process may be
used in the other type of process. Further, it should be understood
that the processes described under these heading should be read in
context with the entirely of this specification, including the
various examples. Thus, the use of headings in this specification
should not limit the scope of protection afford the present
inventions.
[0125] Additionally, the formulations from the mixing type process
may be used as a precursor, or component in the reaction type
process. Similarly, a formulation from the reaction type process
may be used in the mixing type process. Thus, and preferably, the
optimum performance and features from either process can be
combined and utilized to provide a cost effective and efficient
process and end product.
[0126] In addition to being commercially available the precursors
may be made by way of an ethoxylation type process. In this process
chlorosilanes are reacted with ethanol in the presences of a
catalysis, e.g., HCl, to provide the precursor materials, which
materials may further be reacted to provide longer chain
precursors. Other alcohols, e.g., Methanol may also be used. Thus,
the compounds the formulas of FIGS. 51A to 51F are reacted with
ethanol (C--C--OH) to form the precursors of FIGS. 37-50. In some
of these reactions phenols may be the source of the phenyl group,
which is substitute for a hydride group that has been placed on the
silicon. One, two or more step reaction may need to take place.
[0127] The Mixing Type Process
[0128] Precursor materials may be methyl hydrogen, and substituted
and modified methyl hydrogens, siloxane backbone additives,
reactive monomers, reaction products of a siloxane backbone
additive with a silane modifier or an organic modifier, and other
similar types of materials, such as silane based materials,
silazane based materials, carbosilane based materials,
phenol/formaldehyde based materials, and combinations and
variations of these. The precursors are preferably liquids at room
temperature, although they may be solids that are melted, or that
are soluble in one of the other precursors. (In this situation,
however, it should be understood that when one precursor dissolves
another, it is nevertheless not considered to be a "solvent" as
that term is used with respect to the prior art processes that
employ non-constituent solvents, e.g., solvents that do not form a
part or component of the end product, are treated as waste
products, and both.)
[0129] The precursors are mixed together in a vessel, preferably at
room temperature. Preferably, little, and more preferably no
solvents, e.g., water, organic solvents, polar solvents, non-polar
solvents, hexane, THF, toluene, are added to this mixture of
precursor materials. Preferably, each precursor material is
miscible with the others, e.g., they can be mixed at any relative
amounts, or in any proportions, and will not separate or
precipitate. At this point the "precursor mixture" or "polysilocarb
precursor formulation" is compete (noting that if only a single
precursor is used the material would simply be a "polysilocarb
precursor" or a "polysilocarb precursor formulation"). Although
complete, fillers and reinforcers may be added to the formulation.
In preferred embodiments of the formulation, essentially no, and
more preferably no chemical reactions, e.g., crosslinking or
polymerization, takes place within the formulation, when the
formulation is mixed, or when the formulation is being held in a
vessel, on a prepreg, or other time period, prior to being
cured.
[0130] Additionally, inhibitors such as cyclohexane,
1-Ethynyl-1-cyclohexanol (which may be obtained from ALDRICH),
Octamethylcyclotetrasiloxane,
tetramethyltetravinylcyclotetrasiloxane (which may act, depending
upon amount and temperature as a reactant or a reactant retardant
(i.e., slows down a reaction to increase pot life), e.g., at room
temperature it is a retardant and at elevated temperatures it is a
reactant), may be added to the polysilocarb precursor formulation,
e.g., an inhibited polysilocarb precursor formulation. Other
materials, as well, may be added to the polysilocarb precursor
formulation, e.g., a filled polysilocarb precursor formulation, at
this point in processing, including fillers such as SiC powder, PDC
particles, pigments, particles, nano-tubes, whiskers, or other
materials, discussed in this specification or otherwise known to
the arts. Further, a formulation with both inhibitors and fillers
would be considered an inhibited, filled polysilocarb precursor
formulation.
[0131] Depending upon the particular precursors and their relative
amounts in the polysilocarb precursor formulation, polysilocarb
precursor formulations may have shelf lives at room temperature of
greater than 12 hours, greater than 1 day, greater than 1 week,
greater than 1 month, and for years or more. These precursor
formulations may have shelf lives at high temperatures, for
example, at about 90.degree. F., of greater than 12 hours, greater
than 1 day, greater than 1 week, greater than 1 month, and for
years or more. The use of inhibitors may further extend the shelf
life in time, for higher temperatures, and combinations and
variations of these. As used herein the term "shelf life" should be
given its broadest possible meaning unless specified otherwise, and
would include the formulation being capable of being used for its
intended purpose, or performing, e.g., functioning, for its
intended use, at 100% percent as well as a freshly made
formulation, at least about 90% as well as a freshly made
formulation, at least about 80% as well as a freshly made
formulation, and at about 70% as well as a freshly made
formulation.
[0132] Precursors and precursor formulations are preferably
non-hazardous materials. They have flash points that are preferably
above about 70.degree. C., above about 80.degree. C., above about
100.degree. C. and above about 300.degree. C., and above. They may
be noncorrosive. They may have as low vapor pressure, may have low
or no odor, and may be non- or mildly irritating to the skin.
[0133] A catalyst may be used, and can be added at the time of,
prior to, shortly before, or at an earlier time before the
precursor formulation is formed or made into a structure, prior to
curing. The catalysis assists in, advances, promotes the curing of
the precursor formulation to form a preform.
[0134] The time period where the precursor formulation remains
useful for curing after the catalysis is added is referred to as
"pot life", e.g., how long can the catalyzed formulation remain in
its holding vessel before it should be used. Depending upon the
particular formulation, whether an inhibitor is being used, and if
so the amount being used, storage conditions, e.g., temperature,
and potentially other factors, precursor formulations can have pot
lives, for example of from about 5 minutes to about 10 days, about
1 day to about 6 days, about 4 to 5 days, about 1 hour to about 24
hours, and about 12 hours to about 24 hours.
[0135] The catalysis can be any platinum (Pt) based catalyst, which
can for example be diluted to a range from: 1 part per million Pt
to 200 parts per million (ppm) and preferably in the 5 ppm to 50
ppm range. It can be a peroxide based catalyst with a 10 hour half
life above 90 C at a concentration of between 0.5% and 2%. It can
be an organic based peroxide. It can be any organometallic catalyst
capable of reacting with Si--H bond, Si--OH bonds, or unsaturated
carbon bonds, these catalyst may include: dibutyltin dilaurate,
zinc octoate, and titanium organometallic compounds. Combinations
and variations of these and other catalysts may be used. Such
catalysts may be obtained from ARKEMA under the trade name LUPEROX,
e.g., LUPEROX 231.
[0136] Further, custom and specific combinations of these and other
catalysts may be used, such that they are matched to specific
formulation formulations, and in this way selectively and
specifically catalyze the reaction of specific constituents. Custom
and specific combinations of catalysts may be used, such that they
are matched to specific formulation formulations, and in this way
selectively and specifically catalyze the reaction of specific
constituents at specific temperatures. Moreover, the use of these
types of matched catalyst-formulations systems may be used to
provide predetermined product features, such as for example, pore
structures, porosity, densities, density profiles, and other
morphologies of cured structures and ceramics.
[0137] In this mixing type process for making a precursor
formulation, preferably chemical reactions or molecular
rearrangements only take place during the making of the precursors,
the curing process of the preform, and in the pyrolyzing process.
Thus, chemical reactions, e.g., polymerizations, reductions,
condensations, substitutions, take place or are utilized in the
making of a precursor. In making a polysilocarb precursor
formulation preferably no and essentially no, chemical reactions
and molecular rearrangements take place. These embodiments of the
present mixing type process, which avoid the need to, and do not,
utilize a polymerization or other reaction during the making of a
precursor formulation, provides significant advantages over prior
methods of making polymer derived ceramics. Preferably, in the
embodiments of these mixing type of formulations and processes,
polymerization, crosslinking or other chemical reactions take place
primarily, preferably essentially, and more preferably solely in
the preform during the curing process.
[0138] The precursor may be methyl hydrogen (MH), which formula is
shown in FIG. 1. The MH may have a molecular weight (mw) may be
from about 400 mw to about 10,000 mw, from about 600 mw to about
1,000 mw, and may have a viscosity preferably from about 20 cps to
about 40 cps. The percentage of methylsiloxane units "X" may be
from 1% to 100%. The percentage of the dimethylsiloxane units "Y"
may be from 0% to 99%. This precursor may be used to provide the
backbone of the cross-linked structures, as well as, other features
and characteristics to the cured preform and ceramic material.
Typically, methyl hydrogen fluid (MHF) has minimal amounts of "Y",
and more preferably "Y" is for all practical purposes zero.
[0139] The precursor may be a siloxane backbone additive, such as
vinyl substituted polydimethyl siloxane, which formula is shown in
FIG. 2. This precursor may have a molecular weight (mw) may be from
about 400 mw to about 10,000 mw, and may have a viscosity
preferably from about 50 cps to about 2,000 cps. The percentage of
methylvinylsiloxane units "X" may be from 1% to 100%. The
percentage of the dimethylsiloxane units "Y" may be from 0% to 99%.
Preferably, X is 100%. This precursor may be used to decrease
cross-link density and improve toughness, as well as, other
features and characteristics to the cured preform and ceramic
material.
[0140] The precursor may be a siloxane backbone additive, such as
vinyl substituted and vinyl terminated polydimethyl siloxane, which
formula is shown in FIG. 3. This precursor may have a molecular
weight (mw) may be from about 500 mw to about 15,000 mw, and may
preferably have a molecular weight from about 500 mw to 1,000 mw,
and may have a viscosity preferably from about 10 cps to about 200
cps. The percentage of methylvinylsiloxane units "X" may be from 1%
to 100%. The percentage of the dimethylsiloxane units "Y" may be
from 0% to 99%. This precursor may be used to provide branching and
decrease the cure temperature, as well as, other features and
characteristics to the cured preform and ceramic material.
[0141] The precursor may be a siloxane backbone additive, such as
vinyl substituted and hydrogen terminated polydimethyl siloxane,
which formula is shown in FIG. 4. This precursor may have a
molecular weight (mw) may be from about 300 mw to about 10,000 mw,
and may preferably have a molecular weight from about 400 mw to 800
mw, and may have a viscosity preferably from about 20 cps to about
300 cps. The percentage of methylvinylsiloxane units "X" may be
from 1% to 100%. The percentage of the dimethylsiloxane units "Y"
may be from 0% to 99%. This precursor may be used to provide
branching and decrease the cure temperature, as well as, other
features and characteristics to the cured preform and ceramic
material.
[0142] The precursor may be a siloxane backbone additive, such as
allyl terminated polydimethyl siloxane, which formula is shown in
FIG. 5. This precursor may have a molecular weight (mw) may be from
about 400 mw to about 10,000 mw, and may have a viscosity
preferably from about 40 cps to about 400 cps. The repeating units
are the same. This precursor may be used to provide UV curability
and to extend the polymeric chain, as well as, other features and
characteristics to the cured preform and ceramic material.
[0143] The precursor may be a siloxane backbone additive, such as
vinyl terminated polydimethyl siloxane ("VT"), which formula is
shown in FIG. 6. This precursor may have a molecular weight (mw)
may be from about 200 mw to about 5,000 mw, and may preferably have
a molecular weight from about 400 mw to 1,500 mw, and may have a
viscosity preferably from about 10 cps to about 400 cps. The
repeating units are the same. This precursor may be used to provide
a polymeric chain extender, improve toughness and to lower cure
temperature down to for example room temperature curing, as well
as, other features and characteristics to the cured preform and
ceramic material.
[0144] The precursor may be a siloxane backbone additive, such as
silanol (hydroxy) terminated polydimethyl siloxane, which formula
is shown in FIG. 7. This precursor may have a molecular weight (mw)
may be from about 400 mw to about 10,000 mw, and may preferably
have a molecular weight from about 600 mw to 1,000 mw, and may have
a viscosity preferably from about 30 cps to about 400 cps. The
repeating units are the same. This precursor may be used to provide
a polymeric chain extender, a toughening mechanism, can generate
nano- and micro-scale porosity, and allows curing at room
temperature, as well as other features and characteristics to the
cured preform and ceramic material.
[0145] The precursor may be a siloxane backbone additive, such as
silanol (hydroxy) terminated vinyl substituted dimethyl siloxane,
which formula is shown in FIG. 9. This precursor may have a
molecular weight (mw) may be from about 400 mw to about 10,000 mw,
and may preferably have a molecular weight from about 600 mw to
1,000 mw, and may have a viscosity preferably from about 30 cps to
about 400 cps. The percentage of methylvinylsiloxane units "X" may
be from 1% to 100%. The percentage of the dimethylsiloxane units
"Y" may be from 0% to 99%.
[0146] The precursor may be a siloxane backbone additive, such as
hydrogen (hydride) terminated polydimethyl siloxane, which formula
is shown in FIG. 8. This precursor may have a molecular weight (mw)
may be from about 200 mw to about 10,000 mw, and may preferably
have a molecular weight from about 500 mw to 1,500 mw, and may have
a viscosity preferably from about 20 cps to about 400 cps. The
repeating units are the same. This precursor may be used to provide
a polymeric chain extender, as a toughening agent, and it allows
lower temperature curing, e.g., room temperature, as well as, other
features and characteristics to the cured preform and ceramic
material.
[0147] The precursor may be a siloxane backbone additive, such as
phenyl terminated polydimethyl siloxane, which formula is shown in
FIG. 10. This precursor may have a molecular weight (mw) may be
from about 500 mw to about 2,000 mw, and may have a viscosity
preferably from about 80 cps to about 300 cps. The repeating units
are the same. This precursor may be used to provide a toughening
agent, and to adjust the refractive index of the polymer to match
the refractive index of various types of glass, to provide for
example transparent fiberglass, as well as, other features and
characteristics to the cured preform and ceramic material.
[0148] The precursor may be a siloxane backbone additive, such as
methyl-phenyl terminated polydimethyl siloxane, which formula is
shown in 11. This precursor may have a molecular weight (mw) may be
from about 500 mw to about 2,000 mw, and may have a viscosity
preferably from about 80 cps to about 300 cps. The repeating units
are the same. This precursor may be used to provide a toughening
agent and to adjust the refractive index of the polymer to match
the refractive index of various types of glass, to provide for
example transparent fiberglass, as well as, other features and
characteristics to the cured preform and ceramic material.
[0149] The precursor may be a siloxane backbone additive, such as
diphenyl dimethyl polysiloxane, which formula is shown in FIG. 12.
This precursor may have a molecular weight (mw) may be from about
500 mw to about 20,000 mw, and may have a molecular weight from
about 800 to about 4,000, and may have a viscosity preferably from
about 100 cps to about 800 cps. The percentage of dimethylsiloxane
units "X" may be from 25% to 95%. The percentage of the diphenyl
siloxane units "Y" may be from 5% to 75%. This precursor may be
used to provide similar characteristics to the precursor of 11, as
well as, other features and characteristics to the cured preform
and ceramic material.
[0150] The precursor may be a siloxane backbone additive, such as
vinyl terminated diphenyl dimethyl polysiloxane, which formula is
shown in FIG. 13. This precursor may have a molecular weight (mw)
may be from about 400 mw to about 20,000 mw, and may have a
molecular weight from about 800 to about 2,000, and may have a
viscosity preferably from about 80 cps to about 600 cps. The
percentage of dimethylsiloxane units "X" may be from 25% to 95%.
The percentage of the diphenyl siloxane units "Y" may be from 5% to
75%. This precursor may be used to provide chain extension,
toughening agent, changed or altered refractive index, and
improvements to high temperature thermal stability of the cured
material, as well as, other features and characteristics to the
cured preform and ceramic material.
[0151] The precursor may be a siloxane backbone additive, such as
hydroxy terminated diphenyl dimethyl polysiloxane, which formula is
shown in FIG. 14. This precursor may have a molecular weight (mw)
may be from about 400 mw to about 20,000 mw, and may have a
molecular weight from about 800 to about 2,000, and may have a
viscosity preferably from about 80 cps to about 400 cps. The
percentage of dimethylsiloxane units "X" may be from 25% to 95%.
The percentage of the diphenyl siloxane units "Y" may be from 5% to
75%. This precursor may be used to provide chain extension,
toughening agent, changed or altered refractive index, and
improvements to high temperature thermal stability of the cured
material, can generate nano- and micro-scale porosity, as well as
other features and characteristics to the cured preform and ceramic
material.
[0152] The precursor may be a siloxane backbone additive, such as
hydride terminated diphenyl dimethyl polysiloxane, which formula is
shown in FIG. 15. This precursor may have a molecular weight (mw)
may be from about 400 mw to about 20,000 mw, and may have a
molecular weight from about 800 to about 2,000, and may have a
viscosity preferably from about 60 cps to about 300 cps. The
percentage of dimethylsiloxane units "X" may be from 25% to 95%.
The percentage of the diphenyl siloxane units "Y" may be from 5% to
75%. This precursor may be used to provide chain extension,
toughening agent, changed or altered refractive index, and
improvements to high temperature thermal stability of the cured
material, as well as, other features and characteristics to the
cured preform and ceramic material.
[0153] The precursor may be a siloxane backbone additive, such as
styrene vinyl benzene dimethyl polysiloxane, which formula is shown
in FIG. 16. This precursor may have a molecular weight (mw) may be
from about 800 mw to at least about 10,000 mw to at least about
20,000 mw, and may have a viscosity preferably from about 50 cps to
about 350 cps. The percentage of styrene vinyl benzene siloxane
units "X" may be from 1% to 60%. The percentage of the
dimethylsiloxane units "Y" may be from 40% to 99%. This precursor
may be used to provide improved toughness, decreases reaction cure
exotherm, may change or alter the refractive index, adjust the
refractive index of the polymer to match the refractive index of
various types of glass, to provide for example transparent
fiberglass, as well as, other features and characteristics to the
cured preform and ceramic material.
[0154] The precursor may be a reactive monomer, such as
tetramethyltetravinylcyclotetrasiloxane ("TV"), which formula is
shown in FIG. 17. This precursor may be used to provide a branching
agent, a three-dimensional cross-linking agent, (and in certain
formulations, e.g., above 2%, and certain temperatures (e.g., about
from about room temperature to about 60.degree. C., it acts as an
inhibitor to cross-linking, e.g., in may inhibit the cross-linking
of hydride and vinyl groups), as well as, other features and
characteristics to the cured preform and ceramic material.
[0155] The precursor may be a reactive monomer, such as trivinyl
cyclotetrasiloxane, which formula is shown in FIG. 18. The
precursor may be a reactive monomer, such as divinyl
cyclotetrasiloxane, which formula is shown in FIG. 19. The
precursor may be a reactive monomer, such as monohydride
cyclotetrasiloxane, which formula is shown in FIG. 20. The
precursor may be a reactive monomer, such as dihydride
cyclotetrasiloxane, which formula is shown in FIG. 21. The
precursor may be a reactive monomer, such as hexamethyl
cyclotetrasiloxane, which formula is shown in FIG. 22 and FIG.
23.
[0156] The precursor may be a silane modifier, such as vinyl phenyl
methyl silane, which formula is shown in FIG. 24. The precursor may
be a silane modifier, such as diphenyl silane, which formula is
shown in FIG. 25. The precursor may be a silane modifier, such as
diphenyl methyl silane, which formula is shown in FIG. 26 (which
may be used as an end capper or end termination group). The
precursor may be a silane modifier, such as phenyl methyl silane,
which formula is shown in FIG. 27 (which may be used as an end
capper or end termination group).
[0157] The precursors of FIGS. 24, 25 and 27 can provide chain
extenders and branching agents. They also improve toughness, alter
refractive index, and improve high temperature cure stability of
the cured material, as well as improving the strength of the cured
material, among other things. The precursor of FIG. 26 may function
as an end capping agent, that may also improve toughness, alter
refractive index, and improve high temperature cure stability of
the cured material, as well as improving the strength of the cured
material, among other things.
[0158] The precursor may be a reaction product of a silane modifier
with a siloxane backbone additive, such as phenyl methyl silane
substituted MH, which formula is shown in FIG. 26.
[0159] The precursor may be a reaction product of a silane modifier
(e.g., FIGS. 24 to 27) with a vinyl terminated siloxane backbone
additive (e.g., FIG. 6), which formula is shown in FIG. 29, where R
may be the silane modifiers having the structures of FIGS. 24 to
27.
[0160] The precursor may be a reaction product of a silane modifier
(e.g., FIGS. 24 to 27) with a hydroxy terminated siloxane backbone
additive (e.g., FIG. 7), which formula is shown in FIG. 30, where R
may be the silane modifiers having the structures of FIGS. 24 to
27.
[0161] The precursor may be a reaction product of a silane modifier
(e.g., FIGS. 24 to 27) with a hydride terminated siloxane backbone
additive (e.g., FIG. 8), which formula is shown in FIG. 31, where R
may be the silane modifiers having the structures of FIGS. 24 to
27.
[0162] The precursor may be a reaction product of a silane modifier
(e.g., FIGS. 24 to 27) with TV (e.g., FIG. 17), which formula is
shown in FIG. 30.
[0163] The precursor may be a reaction product of a silane modifier
(e.g., FIGS. 24 to 27) with a cyclosiloxane, examples of which
formulas are shown in FIG. 17 (TV), FIG. 32, and in FIG. 33, where
R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may be a methyl or the
silane modifiers having the structures of FIGS. 24 to 27, taking
into consideration steric hindrances.
[0164] The precursor may be a partially hydrolyzed tertraethyl
orthosilicate, which formula is shown in FIG. 35, such as TES 40 or
Silbond 40.
[0165] The precursor may also be a methylsesquisiloxane such as
SR-350 available from General Electric Company, Wilton, Conn. The
precursor may also be a phenyl methyl siloxane such as 604 from
Wacker Chemie AG. The precursor may also be a
methylphenylvinylsiloxane, such as H62 C from Wacker Chemie AG.
[0166] The precursors may also be selected from the following:
TABLE-US-00001 SiSiB .RTM. TRIMETHYLSILYL TERMINATED METHYL 63148-
HF2020 HYDROGEN SILICONE FLUID 57-2
This is a type of material commonly called methylhydrogen fluid,
and has the formula below:
##STR00001##
[0167] Trimethylsilyl Terminated
TABLE-US-00002 SiSiB .RTM. METHYLHYDROSILOXANE 68037- HF2050
DIMETHYLSILOXANE COPOLYMER 59-2
This may be called methyl terminated with dimethyl groups and has
the formula below.
##STR00002##
In some embodiments this precursor can decrease the exotherm and
decrease shrinkage
TABLE-US-00003 SiSiB .RTM. HYDRIDE TERMINATED 69013- HF2060
METHYLHYDROSILOXANE 23-6 DIMETHYLSILOXANE COPOLYMER
This may be called hydride terminated with dimethyl groups and has
the formula below.
##STR00003##
In some embodiments this precursor can decrease the exotherm and
decrease shrinkage and provide branch points
SISIB.RTM. HF2038 Hydrogen Terminated Polydiphenyl Siloxane
##STR00004##
[0168] In some embodiments this precursor can improve as-cured
toughness and decrease shrinkage and improve thermal stability of
as-cured material
TABLE-US-00004 SiSiB .RTM. HYDRIDE TERMINATED 115487- HF2068
METHYLHYDROSILOXANE 49-5 DIMETHYLSILOXANE COPOLYMER
##STR00005##
In some embodiments this precursor can improve as-cured toughness
and decrease shrinkage and improve thermal stability of as-cured
material; but, may allow for higher cross-link density
TABLE-US-00005 iSiB .RTM. HYDRIDE TERMINATED POLY(PHENYL- 68952-
HF2078 DIMETHYLSILOXY) SILOXANE 30-7
[0169] Phenyl Silsesquioxane, Hydrogen-Terminated
##STR00006##
In some embodiments this precursor's tri-functionality can be used
for controlled branching, as well as in some embodiments to reduced
shrinkage.
TABLE-US-00006 SiSiB .RTM. VINYLDIMETHYL TERMINATED 68083- VF6060
VINYLMETHYL-DIMETHYL 18-1 POLYSILOXANE COPOLYMERS
##STR00007##
In some embodiments this precursor's tri-functionality can be used
for controlled branching, as well as in some embodiments to reduced
shrinkage.
TABLE-US-00007 SiSiB .RTM. VINYLDIMETHYL TERMINATED DIMETHYL-
68951- VF6862 DIPHENYL POLYSILOXANE COPOLYMER 96-2
##STR00008##
In some embodiments this precursor can be used to improve as cured
toughness and decreased shrinkage
TABLE-US-00008 SiSiB .RTM. VINYLDIMETHYL TERMINATED DIMETHYL- --
VF6872 METHYLVINYL-DIPHENYL POLYSILOXANE COPOLYMER
##STR00009##
In some embodiments this precursor can be used to improve as cured
toughness and decreased shrinkage; as well as providing the ability
to improve crosslink density through branching if needed.
TABLE-US-00009 SiSiB .RTM. PC9401 1,1,3,3-TETRAMETHYL-1,3-
2627-95-4 DIVINYLDISILOXANE
##STR00010##
In some embodiments this precursor may provided for less shrinkage
than the tetravinyl; but still can provide for high crosslink
density due to high vinyl percentage, but primarily through
2-dimensional crosslinking, without any branching
TABLE-US-00010 SiSiB .RTM. SILANOL TERMINATED 70131- PF1070
POLYDIMETHYLSILOXANE (OF1070) 67-8
##STR00011##
In some embodiments this precursor may assist in decreasing the
density by in-situ nano/micro pore formation.
TABLE-US-00011 SiSiB .RTM. SILANOL TERMINATED 70131-67-8 OF1070
POLYDIMETHYSILOXANE 73138-87-1 OH-ENDCAPPED POLYDIMETHYLSILOXANE
HYDROXY TERMINATED POLYDIMETHYLSILOXANE
##STR00012##
In some embodiments this precursor may assist in decreasing the
density by in-situ nano/micro pore formation.
TABLE-US-00012 SiSiB .RTM. VINYL TERMINATED POLYDIMETHYL 68083-19-2
VF6030 SILOXANE
##STR00013##
In some embodiments this precursor can increase cure speed,
decrease shrinkage slightly, and improves thermal/structural
stability of cured and pyrolized material
TABLE-US-00013 SiSiB .RTM. HYDROGEN TERMINATED 70900- HF2030
POLYDIMETHYLSILOXANE FLUID 21-9
##STR00014##
[0170] Thus, in additional to the forgoing specific precursors, it
is contemplated that a precursor may be compound of the general
formula of FIG. 34, wherein end cappers E.sub.1 and E.sub.2 are
chosen from groups such as trimethyl silicon (SiC.sub.3H.sub.9)
FIG. 34A, dimethyl silicon hydroxy (SiC.sub.2OH.sub.7) FIG. 34C,
dimethyl silicon hydride (SiC.sub.2H.sub.7) FIG. 34B and dimethyl
vinyl silicon (SiC.sub.4H.sub.9) FIG. 34D. The R groups R.sub.1,
R.sub.2, R.sub.3, and R.sub.4 may all be different, or one or more
may be the same, thus R2 is the same as R3 is the same as R.sub.4,
R.sub.1 and R2 are different with R.sub.3 and R.sub.4 being the
same, etc. The R groups are chosen from groups such as phenyl,
vinyl, hydride, methyl, ethyl, allyl, phenylethyl, methoxy, and
alkxoy.
[0171] In general, embodiments of formulations for polysilocarb
formulations may for example have from about 20% to about 99% MH,
about 0% to about 30% siloxane backbone additives, about 1% to
about 60% reactive monomers, and, about 0% to about 90% reaction
products of a siloxane backbone additives with a silane modifier or
an organic modifier reaction products.
[0172] Further, and in general, embodiments of formulations for
batches may for example have from about 5% to about 80% MHF, about
100% 604, about 10% to about 100% H62 C, about 20% to about 60% TV,
about 10% to about 64% styrene substituted MHF (FIG. 16), about 5%
vinyl terminated (FIG. 5), about 85% to 100% SR 350, about 10-15%
TES (FIG. 35), about 2% to 10% of OH terminated MHF (FIG. 7).
[0173] In further embodiments there is in general, a solid,
solvent-free composition prepared by mixing liquid components in
the absence of a solvent to form a premixture, the premixture
including addition reaction cross-linkable groups, and crosslinking
the premixture in the absence of a solvent to form a solid
structure free of ester, carbonate, carbamate or urea linkages. The
content of addition reaction cross-linkable groups can be between 2
and 50%, or between 5 and 40%. The addition reaction cross-linkable
groups can include vinyl, allyl, propargyl, or ethynyl groups, or
combinations thereof. The curing or crosslinking method can include
adding a catalyst, the use of light, heat, or a combination thereof
to the premixture. The catalyst can be a transition metal catalyst,
a peroxide catalyst, an acid, a base, or a combination thereof.
[0174] In another aspect of this embodiment, the resulting solid
can be a cross-linked polymer matrix of controllable cross-link
density having a density of from 0.99 g/cc to 1.25 g/cc, a hardness
from Shore D35 to Shore D85, and a flexural strength of up to 3
ksi. In certain circumstances, the composition can have a flame
resistance of UL-V0. A composite composition can be made by forming
the cross-linked polymer matrix in the presence of fibers, such as
glass fibers, basalt fibers or carbon fibers. The fibers can be
glass fibers or carbon fibers or combinations thereof. The
composite composition can have a flexural strength of 40 ksi to 140
ksi, or 60 ksi to 120 ksi.
[0175] In other embodiments a solvent free premixture of components
can be prepared from a first component and a second component. The
first component has an addition reaction cross-linkable group
including at least one carbon-carbon double bond. The second
component includes an addition reaction cross-linkable group
including at least one reactive moiety capable for addition over
the carbon-carbon bond. For example, the first component can
include one or more vinyl, alpha-beta unsaturated ketone group, or
aryl group. The second component can include one or more radical or
anion creation sites. For example, the second component can have an
alpha-ketone group, a benzyl group or a hydrosilyl group.
[0176] In mixing the formulations a sufficient time to permit the
precursors to become effectively mixed and dispersed. Generally,
mixing of about 15 minutes to an hour is sufficient. Typically, the
precursor formulations are relatively, and essentially, shear
insensitive, and thus the type of pumps or mixing are not critical.
It is further noted that in higher viscosity formulations
additional mixing time may be required. The temperature of the
formulations, during mixing should be kept below about 45 degrees
C., and preferably about about 10 degrees C. (It is noted that
these mixing conditions are for the pre-catalyzed formulations)
[0177] The Reaction Type Process
[0178] In the reaction type process, in general, a chemical
reaction is used to combine one, two or more precursors, typically
in the presence of a solvent, to form a precursor formulation that
is essentially made up of a single polymer that can then be cured
and if need be pyrolized. This process provides the ability to
build custom precursor formulations that when cured can provide
plastics having unique and desirable features such as high
temperature, flame resistance and retardation, strength and other
features. The cured materials can also be pyrolized to form
ceramics having unique features. The reaction type process allows
for the predetermined balancing of different types of functionality
in the end product by selecting function groups for incorporation
into the polymer that makes up the precursor formulation, e.g.,
phenyls which typically are not used for ceramics but have benefits
for providing high temperature capabilities for plastics, and
styrene which typically does not provide high temperature features
for plastics but provides benefits for ceramics.
[0179] In general a custom polymer for use as a precursor
formulation is made by reacting precursors in a condensation
reaction to form the polymer precursor formulation. This precursor
formulation is then cured into a preform through a hydrolysis
reaction. The condensation reaction forms a polymer of the type
shown in FIG. 36, where R.sub.1 and R.sub.2 in the polymeric units
can be a H, a Methyl (Me)(--C), a vinyl (--C.dbd.C), alkyl (--R), a
phenyl (Ph)(--C.sub.6H.sub.5), an ethoxy (--O--C--C), a siloxy,
methoxy (--O--C), alkoxy, (--O--R), hydroxy, (--O--H), and
phenylethyll (--C--C--C.sub.6H.sub.5). R.sub.1 and R.sub.2 may be
the same or different. The custom precursor polymers can have
several different polymeric units, e.g., A.sub.1, A.sub.2, A.sub.n,
and may include as many as 10, 20 or more units, or it may contain
only a single unit. (For example, if methyl hydrogen fluid is made
by the reaction process). The end units, Si End 1 and Si End 2, can
come from the precursors of FIGS. 41, 43, 48, and 50. Additionally,
if the polymerization process is properly controlled a hydroxy end
cap can be obtained from the precursors used to provide the
repeating units of the polymer.
[0180] In general, the precursors, e.g., FIGS. 37 to 50 are added
to a vessel with ethanol (or other material to absorb heat, e.g.,
to provide thermal mass), an excess of water, and hydrochloric acid
(or other proton source). This mixture is heated until it reaches
its activation energy, after which the reaction is exothermic. In
this reaction the water reacts with an ethoxy group of the silicon
of the precursor monomer, forming a hydroxy (with ethanol as the
byproduct). Once formed this hydroxy becomes subject to reaction
with an ethoxy group on the silicon of another precursor monomer,
resulting in a polymerization reaction. This polymerization
reaction is continued until the desired chain length(s) is
built.
[0181] Control factors for determining chain length are: the
monomers chosen (generally, the smaller the monomers the more that
can be added before they begin to coil around and bond to
themselves); the amount and point in the reaction where end cappers
are introduced; and the amount of water and the rate of addition.
Thus, the chain lengths can be from about 180 mw (viscosity about 5
cps) to about 65,000 mw (viscosity of about 10,000 cps), greater
than about 1000 mw, greater than about 10,000 mw, greater than
about 50,000 mw and greater. Further, the polymerized precursor
formulation may, and typically does, have polymers of different
molecular weights, which can be predetermined to provide
formulation, cured, and ceramic product performance features.
[0182] Upon completion of the polymerization reaction the material
is transferred into a separation apparatus, e.g., a separation
funnel, which has an amount of deionized water that is from about
1.2.times. to about 1.5.times. the mass of the material. This
mixture is vigorously stirred for about less than 1 minute and
preferably from about 5 to 30 sections. Once stirred the material
is allowed to settle and separate, which may take from about 1 to 2
hours. The polymer is the higher density material and is removed
from the vessel. This removed polymer is then dried by either
warming in a shallow tray at 90 C for about two hours; or,
preferably, is passed through a wiped film distillation apparatus,
to remove any residual water and ethanol. Alternatively, sodium
bicarbonate sufficient to buffer the aqueous layer to a pH of about
4 to about 7 is added. It is further understood that other, and
commercial, manners of separating the polymer from the material may
be employed.
[0183] Preferably a catalyst is used in the curing process of the
polymer pressure formulations from the reaction type process. The
same polymers as used for curing the formulation from the mixing
type process can be used. It is noted that unlike the mixing type
formulations, a catalyst is not necessarily required. However, if
not used, reaction time and rates will be slower. The pyrolysis of
the cured material is essentially the same as the cured material
from the mixing process.
[0184] Curing and Pyrolysis
[0185] The preform can be cured in a controlled atmosphere, such as
an inert gas, or it can be cured in the atmosphere. The cure
conditions, e.g., temperature, time, rate, can be predetermined by
the formulation to match, for example the size of the preform, the
shape of the preform, or the mold holding the preform to prevent
stress cracking, off gassing, or other problems associated with the
curing process. Further, the curing conditions may be such as to
take advantage of, in a controlled manner, what may have been
previously perceived as problems associated with the curing
process. Thus, for example, off gassing may be used to create a
foam material having either open or closed structure. Further, the
porosity of the material may be predetermined such that, for
example, a particular pore size may be obtained, and in this manner
a filter or ceramic screen having predetermined pore sizes, flow
characteristic may be made.
[0186] The preforms, either unreinforced, neat, or reinforced, may
be used as a stand alone product, an end product, a final product,
or a preliminary product for which later machining or processing
may be performed on. The preforms may also be subject to pyrolysis,
which converts the preform material into a ceramic.
[0187] During the curing process some formulations may exhibit an
exotherm, i.e., a self heating reaction, that can produce a small
amount of heat to assist or drive the curing reaction, or they may
produce a large amount of heat that may need to be managed and
removed in order to avoid problems, such as stress fractures.
During the cure off gassing typically occurs and results in a loss
of material, which loss is defined generally by the amount of
material remaining, e.g., cure yield. The formulations and
polysilocarb precursor formulations of embodiments of the present
inventions can have cure yields of at least about 90%, about 92%,
about 100%. In fact, with air cures the materials may have cure
yields above 100%, e.g., about 101-105%, as a result of oxygen
being absorbed from the air. Additionally, during curing the
material shrinks, this shrinkage may be, depending upon the
formulation and the nature of the preform shape, and whether the
preform is reinforce, neat or unreinforced, from about 20%, less
than 20%, less than about 15%, less than about 5%, less than about
1%, less than about 0.5%, less than about 0.25% and smaller.
[0188] In pyrolyzing the preform, or cured structure or cured
material, it is heated to above about 650.degree. C. to about
1,200.degree. C. At these temperatures typically all organic
structures are either removed or combined with the inorganic
constituents to form a ceramic. Typically at temperatures in the
650.degree. C. to 1,200.degree. C. range the material is an
amorphous glassy ceramic. When heated above 1,200.degree. C. the
material may from nano crystalline structures, or micro crystalline
structures, such as SiC, Si3N.sub.4, SiCN, .beta. SiC, and above
1,900.degree. C. an a SiC structure may form.
[0189] During pyrolysis material is loss through off gassing. The
amount of material remaining at the end of a pyrolysis set is
referred to as char yield (or pyrolysis yield). The formulations
and polysilocarb precursor formulations of embodiments of the
present inventions can have char yields of at least about 60%,
about 70%, about 80%, and at least about 90%, at least about 91%
and greater. In fact, with air pyrolysis the materials may have
cure yields well above 91%, which can approach 100%. In order to
avoid the degradation of the material in an air pyrolysis (noting
that typically pyrolysis is conducted in an inert atmospheres)
specifically tailored formulations must be used, such as for
example, formulations high in phenyl content (at least about 11%,
and preferably at least about 20% by weight phenyls), formulations
high in allyl content (at least about 15% to about 60%). Thus,
there is provided formulations and polysilocarb precursor
formulations that are capable of being air pyrolized to form a
ceramic and to preferably do so at char yield in excess of at least
about 80% and above 88%.
[0190] The initial or first pyrolysis step generally yields a
structure that is not very dense, and for example, has not reached
the density required for its intended use. However, in some
examples, such as the use of light weight spheres, the first
pyrolysis may be sufficient. Thus, typically a reinfiltration
process may be performed on the pyrolized material, to add in
additional polysilocarb precursor formulation material, to fill in,
or fill the voids and spaces in the structure. This reinfiltrated
material is they repyrolized. This process of pyrolization,
reinfiltration may be repeated, through one, two, three, and up to
10 or more times to obtain the desired density of the final
product. Additionally, with formulations of embodiments of the
present inventions, the viscosity of the formulation may be
tailored to provide more efficient reinfiltrations, and thus, a
different formulation may be used at later reinfiltration steps, as
the voids or pores become smaller and more difficult to get the
formulation material into it. The high char yields, and other
features of embodiments of the present invention, enable the
manufacture of completely closed structures, e.g., "helium tight"
materials, with less than twelve reinfiltration steps, less than
about 10 reinfiltrations steps and less than five reinfiltrations
steps. Thus, by way of example, an initial inert gas pyrolysis may
be performed with a high char yield formulation followed by four
reinfiltration air pyrolysis steps.
[0191] Upon curing the polysilocarb precursor formulation a cross
linking reaction takes place that provides a cross linked structure
having, among other things, an
--R.sub.1--Si--C--C--Si--O--Si--C--C--Si--R.sub.2-- where R.sub.1
and R.sub.2 vary depending upon, and are based upon, the precursors
used in the formulation. The cured structure may also have a
structure comprising --Si--O--Si--O--Si--O--Si-- with carbon groups
appended from that back bone, which carbon groups may not be a part
of that back bone.
[0192] Embodiments of the present inventions have the ability to
utilize precursors that have impurities, high-level impurities and
significant impurities. Thus, the precursors may have more than
about 0.1% impurities, more than about 0.5%, more than about 1%
impurities, more than about 5% impurities, more than about 10%
impurities, and more than about 50% impurities. In using materials
with impurities, the amounts of these impurities, or at least the
relative amounts, so that the amount of actual precursor is known,
should preferably be determined by for example GPC (Gel Permeation
Chromatography) or other methods of analysis. In this manner the
formulation of the polysilocarb precursor formulation may be
adjusted for the amount of impurities present. The ability of
embodiments of the present invention to utilize lower level
impurity materials, and essentially impure materials, and highly
impure materials, provides significant advantages over other method
of making polymer derived ceramics. This provides two significant
advantages, among other things. First, the ability to use impure,
lower purity, materials in embodiments of the present inventions,
provides the ability to greatly reduce the cost of the formulations
and end products, e.g., cured preforms, cured parts, and ceramic
parts or structures. Second, the ability to use impure, lower
purity, materials in embodiments of the present inventions,
provides the ability to have end products, e.g., cured preforms,
cured parts, and ceramic parts or structures, that have a
substantially greater consistence from part to part, because
variations in starting materials can be adjusted for during the
formulation of each polysilocarb precursor formulation.
EXAMPLES
[0193] The following examples are provided to illustrate various
embodiments of processes, precursors, polysilocarb formulations,
prepregs, cured preforms, and ceramics of the present inventions.
These examples are for illustrative purposes, and should not be
viewed as, and do not otherwise limit the scope of the present
inventions. The percentages used in the examples, unless specified
otherwise, are weight percents of the total formulation, preform or
structure.
Example 1
[0194] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together at room
temperature 70% of the MHF precursor of the formula of FIG. 1 and a
molecular weight of about 800 and 30% of the allyl terminated
precursor of the formula of FIG. 5 having a molecular weight of
about 500 are mixed together in a vessel and put in storage for
later use. The polysilocarb formulation has good shelf life and
room temperature and the precursors have not, and do not react with
each other. The polysilocarb formulation has a viscosity of about
12 cps.
Example 2
[0195] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together at room
temperature 60% of the MHF precursor of the formula of FIG. 1 and a
molecular weight of about 800 and 40% of the vinyl terminated
precursor of the formula of FIG. 6 having a molecular weight of
about 9,400 are mixed together in a vessel and put in storage for
later use. The polysilocarb formulation has good shelf life and
room temperature and the precursors have not, and do not react with
each other. The polysilocarb formulation has a viscosity of about
200 cps.
Example 3
[0196] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together 50% of the
MH precursor of the formula of FIG. 1 and a molecular weight of
about 800 and 50% of the vinyl terminated precursor of the formula
of FIG. 6 having a molecular weight of about 800 are mixed together
in a vessel and put in storage for later use. The polysilocarb
formulation has good shelf life and room temperature and the
precursors have not, and do not react with each other. The
polysilocarb formulation has a viscosity of about 55 cps.
Example 4
[0197] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together 40% of the
MH precursor of the formula of FIG. 1 and a molecular weight of
about 1,000 and 60% of the vinyl terminated precursor of the
formula of FIG. 6 having a molecular weight of about 500 are mixed
together in a vessel and put in storage for later use. The
polysilocarb formulation has good shelf life and room temperature
and the precursors have not, and do not react with each other. The
polysilocarb formulation has a viscosity of about 25 cps.
Example 5
[0198] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together 30% of the
MHF precursor of the formula of FIG. 1 and a molecular weight of
about 800 and 70% of the vinyl terminated precursor of the formula
of FIG. 6 having a molecular weight of about 500 are mixed together
in a vessel and put in storage for later use. The polysilocarb
formulation has good shelf life and room temperature and the
precursors have not, and do not react with each other. The
polysilocarb formulation has a viscosity of about 10 cps.
Example 6
[0199] The polysilocarb formulation of Example 1 has 40% of an
about 80 micron to about 325 mesh SiC filler added to the
formulation to make a filled polysilocarb formulation, which can be
kept for later use.
Example 7
[0200] The polysilocarb formulation of Example 2 has 30% of an
about 80 micron to about 325 mesh SiC filler added to the
formulation to make a filled polysilocarb formulation, which can be
kept for later use.
Example 7a
[0201] The polysilocarb batch of Example 3 has 50% of an about 80
micron to about 325 mesh SiC filler added to the batch to make a
filled polysilocarb batch, which can be kept for later use.
Example 7b
[0202] The polysilocarb batch of Example 4 has 28% of an about 80
micron to about 325 mesh SiC filler added to the batch to make a
filled polysilocarb batch, which can be kept for later use.
Example 7c
[0203] The polysilocarb batch of Example 5 has 42% of an about 80
micron to about 325 mesh SiC filler added to the batch to make a
filled polysilocarb batch, which can be kept for later use.
Example 8
[0204] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together 10% of the
MHF precursor of the formula of FIG. 1 and a molecular weight of
about 800 and 73% of the styrene (phenylethyl) precursor of the
formula of FIG. 16 (having 10% X) and a molecular weight of about
1,000, and 16% of the TV precursor of the formula of FIG. 17, and
1% of the OH terminated precursor of the formula of FIG. 7, having
a molecular weight of about 1,000 are mixed together in a vessel
and put in storage for later use. The polysilocarb formulation has
good shelf life and room temperature and the precursors have not,
and do not react with each other. The polysilocarb formulation has
a viscosity of about 72 cps.
Example 9
[0205] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together 0-90% of the
MH precursor of the formula of FIG. 1 and a molecular weight of
about 800, and 0-90% of the styrene precursor of the formula of
FIG. 16 (having 10% X) and a molecular weight of about 1000, and
0-30% of the TV precursor of the formula of FIG. 17, and 0-30% of
the vinyl terminated precursor of the formula of FIG. 6 having a
molecular weight of about 9400 and 0-20% of the OH terminated
precursor of the formula of FIG. 7, having a molecular weight of
about 800 are mixed together in a vessel and put in storage for
later use. The polysilocarb formulation has good shelf life and
room temperature and the precursors have not, and do not react with
each other. The polysilocarb formulation has a viscosity of about
100 cps.
Example 10
[0206] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together 70% of the
MHF precursor of the formula of FIG. 1 and 30% of the vinyl
terminated precursor of the formula of FIG. 6 having a molecular
weight of about 500 and about 42% of a submicron and a 325 mesh
silica are mixed together in a vessel and put in storage for later
use. The polysilocarb formulation has good shelf life and room
temperature and the precursors have not, and do not react with each
other. The polysilocarb formulation has a viscosity of about 300
cps.
Example 11
[0207] A polysilocarb formulation using the mixing type method is
formulated. The formulation is made by mixing together 20-80% of
the MH precursor of the formula of FIG. 1 and a molecular weight of
about 800, and 0-10% of the TV precursor of the formula of FIG. 17,
and 5-80% of the vinyl terminated precursor of the formula of FIG.
6 having a molecular weight of about and about 500 of submicron,
325 mesh, and 8 micron SiC are mixed together in a vessel and put
in storage for later use. The polysilocarb formulation has good
shelf life and room temperature and the precursors have not, and do
not react with each other. The polysilocarb formulation has a
viscosity of about 300 cps.
Example 12
[0208] 40 ppm of a platinum catalyst is added to the polysilocarb
formulation of Examples 6, 7, 7a, 7b, and 7c and these catalyzed
formulations are added drop wise (e.g., drops of the formulation
are dropped into) to a 50-120.degree. C. hot water bath to cure the
formulation. The time in the hot water bath was about 1-2 minutes.
The cured drop structures were then pyrolized at 950.degree. C. for
about 60 minutes. The pyrolized structures were hollow spheres with
densities of less than about 1 g/cc, diameters of about 60 microns
to about 2 mm, and crush strengths of about 0.5-2 ksi.
Example 13
[0209] A precursor formulation of having 75% MHF, 15% TV, and 10%
VT is formed using the mixing type process and stored.
Example 14a
[0210] 1% catalyst (10 ppm platinum and 0.5% LUPEROX 231 peroxide)
is added to the precursor formulation of Example 13. The catalyzed
precursor is then impregnated into a reinforcing material and cured
to form a composite.
Example 14b
[0211] The cured material of Example 14a is pyrolized to form a
polysilocarb derived ceramic composite material.
Example 14c
[0212] 1% catalyst (10 ppm platinum and 0.5% LUPEROX 231 peroxide)
is added to the precursor formulation of Example 13. Using a tower
forming and cure system, the catalyzed polysilocarb formulation is
formed from a sonic nozzle having an internal diameter of 0.180
inches into droplets that fall from the nozzle into and through an
8 foot curing tower. The temperature at the top of the tower is
from 495-505.degree. C. the temperature at the bottom of the tower
is 650.degree. C. There are no discrete temperature zones in the
tower. Airflow up the tower is by convection. The collection pan is
maintained at 110.degree. C. The forming and curing are done in
air. The preform beads are removed from the pan and post (hard)
cured at 200.degree. C. in air for 2 hours. The hard cured preform
proppants are pyrolized at 1000.degree. C. in an argon atmosphere
for 2 hours. The cure yield is from 99% to 101%. The char yield is
86%.
Example 14d
[0213] 1% catalyst (10 ppm platinum and 0.5% LUPEROX 231 peroxide)
is added to the formulation of Example 13, and the polysilocarb
formulation is formed into a prepreg having carbon fiber
reinforcement. The prepreg curing is done in Argon and at
200.degree. C. for 2 hours. The hard cured preform are pyrolized at
1000.degree. C. under vacuum for 5 hours.
Example 15
[0214] A polysilocarb precursor formulation having 70% MHF, 20% TV,
and 10% VT is formed using the mixing type process and placed in a
container.
Example 16a
[0215] 1% catalyst (10 ppm platinum and 0.5% LUPEROX 231 peroxide)
is added to the precursor formulation of Example 15. The catalyzed
precursor is then impregnated into a reinforcing material and cured
to form a composite.
Example 16b
[0216] The cured material of Example 16a is pyrolized to form a
polysilocarb derived ceramic composite material.
Example 16c
[0217] 1% catalyst (10 ppm platinum and 0.5% LUPEROX 231 peroxide)
is added to the formulation of Example 15, and the polysilocarb
formulation is formed into a prepreg having carbon fiber
reinforcement. The prepreg curing is done in Argon and at
200.degree. C. for 2 hours. The hard cured preform are pyrolized at
1000.degree. C. under vacuum for 5 hours.
Example 17
[0218] Using a tower forming and cure system, a polysilocarb
formulation from the mixing type process and having 70% MHF, 20%
TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% LUPEROX 231
peroxide) is formed from a sonic nozzle having an internal diameter
of 0.180 inches into droplets that fall from the nozzle into and
through an 8 foot curing tower. The temperature at the top of the
tower is from 495-505.degree. C. the temperature at the bottom of
the tower is 650.degree. C. There are no discrete temperature zones
in the tower. Airflow up the tower is by convection. The collection
pan is maintained at 110.degree. C. The forming and curing are done
in air. The preform proppants are removed from the pan and post
(hard) cured at 200.degree. C. in air for 2 hours. The hard cured
preform beads are pyrolized at 1000.degree. C. under vacuum for 2
hours. The cure yield is from 99% to 101%. The char yield is
86%.
Example 18a
[0219] The pyrolized preform of Example 16c, is infused with a
polysiloxane precursor formulation and pyrolized.
Example 18b
[0220] The pyrolized preform of Example 18a, is infused with a
polysiloxane precursor formulation and pyrolized.
Example 19
[0221] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00014 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Methyltriethoxysilane (FIG. 120.00 19.5% 178.30 0.67 47.43%
0.67 2.02 37) Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00%
-- -- (FIG. 38) Dimethyldiethoxysilane (FIG. 70.00 11.4% 148.28
0.47 33.27% 0.47 0.94 42) Methyldiethoxysilane (FIG. 39) 20.00 3.3%
134.25 0.15 10.50% 0.15 0.30 Vinylmethyldiethoxysilane 20.00 3.3%
160.29 0.12 8.79% 0.12 0.25 (FIG. 40) Trimethyethoxysilane (FIG.
48) 0.00 0.0% 118.25 -- 0.00% -- -- Hexane in hydrolyzer 0.00 0.0%
86.18 -- Acetone in hydrolyzer 320.00 52.0% 58.08 5.51 Ethanol in
hydrolyzer 0.00 0.0% 46.07 -- Water in hydrolyzer 64.00 10.4% 18.00
3.56 HCl 0.36 0.1% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00
0.01
Example 20
[0222] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 72.degree. C. for 21 hours.
TABLE-US-00015 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 234.00 32.0% 240.37 0.97
54.34% 0.97 2.92 Phenylmethyldiethoxysilane 90.00 12.3% 210.35 0.43
23.88% 0.43 0.86 (FIG. 38) Dimethyldiethoxysilane (FIG. 0.00 0.0%
148.28 -- 0.00% -- -- 42) Methyldiethoxysilane (FIG. 39) 28.50 3.9%
134.25 0.21 11.85% 0.21 0.42 Vinylmethyldiethoxysilane (FIG. 28.50
3.9% 160.29 0.18 9.93% 0.18 0.36 40) Trimethyethoxysilane (FIG. 48)
0.00 0.0% 118.25 -- 0.00% -- -- Acetone in hydrolyzer 0.00 0.0%
58.08 -- Ethanol in hydrolyzer 265.00 36.3% 46.07 5.75 Water in
hydrolyzer 83.00 11.4% 18.00 4.61 HCl 0.36 0.0% 36.00 0.01 Sodium
bicarbonate 0.84 0.1% 84.00 0.01
Example 21
[0223] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00016 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 142.00 21.1% 240.37 0.59
37.84% 0.59 1.77 Phenylmethyldiethoxysilane 135.00 20.1% 210.35
0.64 41.11% 0.64 1.28 (FIG. 38) Dimethyldiethoxysilane (FIG. 0.00
0.0% 148.28 -- 0.00% -- -- 42) Methyldiethoxysilane (FIG. 39) 24.00
3.6% 134.25 0.18 11.45% 0.18 0.36 Vinylmethyldiethoxysilane 24.00
3.6% 160.29 0.15 9.59% 0.15 0.30 (FIG. 40) Trimethyethoxysilane
(FIG. 48) 0.00 0.0% 118.25 -- 0.00% -- -- Acetone in hydrolyzer
278.00 41.3% 58.08 4.79 Ethanol in hydrolyzer 0.00 0.0% 46.07 --
Water in hydrolyzer 69.00 10.2% 18.00 3.83 HCl 0.36 0.1% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 22
[0224] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 72.degree. C. for 21 hours.
TABLE-US-00017 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Methyltriethoxysilane (FIG. 0.00 0.0% 178.30 -- 0.00% -- --
37) Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- --
(FIG. 38) Dimethyldiethoxysilane (FIG. 56 7.2% 148.28 0.38 17.71%
0.38 0.76 42) Methyldiethoxysilane (FIG. 39) 182 23.2% 134.25 1.36
63.57% 1.36 2.71 Vinylmethyldiethoxysilane 64 8.2% 160.29 0.40
18.72% 0.40 0.80 (FIG. 40) Triethoxysilane (FIG. 44) 0.00 0.0%
164.27 -- 0.00% -- -- Hexane in hydrolyzer 0.00 0.0% 86.18 --
Acetone in hydrolyzer 0.00 0.0% 58.08 -- Ethanol in hydrolyzer
400.00 51.1% 46.07 8.68 Water in hydrolyzer 80.00 10.2% 18.00 4.44
HCl 0.36 0.0% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00
0.01
Example 23
[0225] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00018 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 198.00 26.6% 240.37 0.82
52.84% 0.82 2.47 Phenylmethyldiethoxysilane 0.00 0.0% 210.35 --
0.00% -- -- (FIG. 38) Dimethyldiethoxysilane (FIG. 109.00 14.6%
148.28 0.74 47.16% 0.74 1.47 42) Methyldiethoxysilane (FIG. 39)
0.00 0.0% 134.25 -- 0.00% -- -- Vinylmethyldiethoxysilane 0.00 0.0%
160.29 -- 0.00% -- -- (FIG. 40) Trimethyethoxysilane (FIG. 48) 0.00
0.0% 118.25 -- 0.00% -- -- Acetone in hydrolyzer 365.00 49.0% 58.08
6.28 Ethanol in hydrolyzer 0.00 0.0% 46.07 -- Water in hydrolyzer
72.00 9.7% 18.00 4.00 HCl 0.36 0.0% 36.00 0.01 Sodium bicarbonate
0.84 0.1% 84.00 0.01
Example 24
[0226] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 72.degree. C. for 21 hours.
TABLE-US-00019 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 180.00 22.7% 240.37 0.75
44.10% 0.75 2.25 Phenylmethyldiethoxysilane 50.00 6.3% 210.35 0.24
14.00% 0.24 0.48 (FIG. 38) Dimethyldiethoxysilane (FIG. 40.00 5.0%
148.28 0.27 15.89% 0.27 0.54 42) Methyldiethoxysilane (FIG. 39)
30.00 3.8% 134.25 0.22 13.16% 0.22 0.45 Vinylmethyldiethoxysilane
35.00 4.4% 160.29 0.22 12.86% 0.22 0.44 (FIG. 40)
Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 -- 0.00% -- --
Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in hydrolyzer 0.00
0.0% 58.08 -- Ethanol in hydrolyzer 380.00 48.0% 46.07 8.25 Water
in hydrolyzer 76.00 9.6% 18.00 4.22 HCl 0.36 0.0% 36.00 0.01 Sodium
bicarbonate 0.84 0.1% 84.00 0.01
Example 25
[0227] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 72.degree. C. for 21 hours.
TABLE-US-00020 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 190.00 23.8% 240.37 0.79
47.22% 0.79 2.37 Phenylmethyldiethoxysilane 75.00 9.4% 210.35 0.36
21.30% 0.36 0.71 (FIG. 38) Dimethyldiethoxysilane 45.00 5.6% 148.28
0.30 18.13% 0.30 0.61 (FIG. 42) Methyldiethoxysilane (FIG. 30.00
3.8% 134.25 0.22 13.35% 0.22 0.45 39) Vinylmethyldiethoxysilane
0.00 0.0% 160.29 -- 0.00% -- -- (FIG. 40) Trimethyethoxysilane
(FIG. 0.00 0.0% 118.25 -- 0.00% -- -- 48) Hexane in hydrolyzer 0.00
0.0% 86.18 -- Acetone in hydrolyzer 0.00 0.0% 58.08 -- Ethanol in
hydrolyzer 380.00 47.7% 46.07 8.25 Water in hydrolyzer 76.00 9.5%
18.00 4.22 HCl 0.36 0.0% 36.00 0.01 Sodium bicarbonate 0.84 0.1%
84.00 0.01
Example 26
[0228] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00021 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 0.00 0.0% 240.37 -- 0.00% --
-- Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- -- (FIG.
38) Dimethyldiethoxysilane (FIG. 235.00 31.5% 148.28 1.58 83.32%
1.58 3.17 42) Methyldiethoxysilane (FIG. 39) 0.00 0.0% 134.25 --
0.00% -- -- Vinylmethyldiethoxysilane 0.00 0.0% 160.29 -- 0.00% --
-- (FIG. 40) TES 40 (FIG. 35) 66.00 8.8% 208.00 0.32 16.68% 0.32
1.27 Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in hydrolyzer
370.00 49.6% 58.08 6.37 Ethanol in hydrolyzer 0.00 0.0% 46.07 --
Water in hydrolyzer 74.00 9.9% 18.00 4.11 HCl 0.36 0.0% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 27
[0229] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00022 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 0.00 0.0% 240.37 -- 0.00% --
-- Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- -- (FIG.
38) Dimethyldiethoxysilane (FIG. 95.00 11.8% 148.28 0.64 34.95%
0.64 1.28 42) Methyldiethoxysilane (FIG. 39) 60.80 7.6% 134.25 0.45
24.71% 0.45 0.91 Vinylmethyldiethoxysilane 73.15 9.1% 160.29 0.46
24.90% 0.46 0.91 (FIG. 40) TES 40 (FIG. 35) 58.90 7.3% 208.00 0.28
15.45% 0.28 1.13 Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in
hydrolyzer 430.00 53.4% 58.08 7.40 Ethanol in hydrolyzer 0.00 0.0%
46.07 -- Water in hydrolyzer 86.00 10.7% 18.00 4.78 HCl 0.36 0.0%
36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 28
[0230] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00023 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 0.00 0.0% 240.37 -- 0.00% --
-- Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- -- (FIG.
38) Dimethyldiethoxysilane (FIG. 140.00 17.9% 148.28 0.94 58.38%
0.94 1.89 42) Methyldiethoxysilane (FIG. 39) 0.00 0.0% 134.25 --
0.00% -- -- Vinylmethyldiethoxysilane 0.00 0.0% 160.29 -- 0.00% --
-- (FIG. 40) TES 40 (F(G. 35) 140.00 17.9% 208.00 0.67 41.62% 0.67
2.69 Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in hydrolyzer
420.00 53.6% 58.08 7.23 Ethanol in hydrolyzer 0.00 0.0% 46.07 --
Water in hydrolyzer 84.00 10.7% 18.00 4.67
Example 29
[0231] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00024 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 0.00 0.0% 240.37 -- 0.00% --
-- Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- -- (FIG.
38) Dimethyldiethoxysilane (FIG. 20.00 2.6% 148.28 0.13 10.67% 0.13
0.27 42) Methyldiethoxysilane (FIG. 39) 0.00 0.0% 134.25 -- 0.00%
-- -- Vinylmethyldiethoxysilane 0.00 0.0% 160.29 -- 0.00% -- --
(FIG. 40) TES 40 (FIG. 35) 235.00 30.0% 208.00 1.13 89.33% 1.13
4.52 Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in hydrolyzer
440.00 56.2% 58.08 7.58 Ethanol in hydrolyzer 0.00 0.0% 46.07 --
Water in hydrolyzer 88.00 11.2% 18.00 4.89
Example 30
[0232] The polysilocarb formulation is 60% MHF, 20% TV, 5% Vt and
10% MVF (a reacted formulation of all vinylmethyldiethoxysilane,
e.g., the formulations of Examples 38-40)
Example 31
[0233] The polysilocarb formulation has 41% MHF and 59% TV.
Example 32
[0234] The polysilocarb formulation has from about 40% MHF to about
55% MHF and from about 60% MVF to about 55% MVF.
Example 33
[0235] The polysilocarb formulation has 70% MHF, 20% TV, and 10%
VT.
Example 34
[0236] The polysilocarb formulation has 95% MHF and 5% TV.
Example 35
[0237] The polysilocarb formulations are made using
phenyltriethoxysilane (FIG. 45), phenylmethyldiethoxysilane (FIG.
38), methyldiethoxysilane (FIG. 39) and Vinylmethyldiethoxysilane
(FIG. 40), as well as, dimethyldiethoxysilane and
methytriethoxysilane. The mass percentages of the
phenyltriethoxysilane and phenylmethyldiethoxysilane (or
dimethyldiethoxysilane and methytriethoxysilane) would likely range
from 10% to 80%, with the preferred range around 40-60% (of either,
or total of both).
Example 36
[0238] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00025 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 145.00 18.5% 240.37 0.60
34.58% 0.60 1.81 Phenylmethyldiethoxysilane 0.00 0.0% 210.35 --
0.00% -- -- (FIG. 38) Dimethyldiethoxysilane (FIG. 0.00 0.0% 148.28
0.57 32.88% 0.57 1.55 42) Methyldiethoxysilane (FIG. 39) 77.00 9.8%
134.25 -- 0.00% -- -- Vinylmethyldiethoxysilane 91.00 11.6% 160.29
0.57 32.54% 0.57 1.14 (FIG. 40) Trimethyethoxysilane (FIG. 48) 0.00
0.0% 118.25 -- 0.00% -- -- Acetone in hydrolyzer 395.00 50.3% 58.08
6.80 Ethanol in hydrolyzer 0.00 0.0% 46.07 -- Water in hydrolyzer
76.00 9.7% 18.00 4.22 HCl 0.36 0.0% 36.00 0.01 Sodium bicarbonate
0.84 0.1% 84.00 0.01
Example 37
[0239] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00026 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 0.00 0.00% 240.37 -- 0.0% --
-- Phenylmethyldiethoxysilane 145.00 18.4% 210.35 0.69 34.47% 0.69
1.38 (FIG. 38) Dimethyldiethoxysilane (FIG. 0.00 0.00% 148.28 --
0.00% -- -- 42) Methyldiethoxysilane (FIG. 39) 88.00 11.2% 134.25
0.66 32.78% 0.66 1.31 Vinylmethyldiethoxysilane 105.00 13.3% 160.29
0.66 32.76% 0.66 1.31 (FIG. 40) Trimethyethoxysilane (FIG. 48) 0.00
0.0% 118.25 -- 0.00% -- -- Acetone in hydrolyzer 375.00 47.5% 58.08
6.46 Ethanol in hydrolyzer 0.00 0.0% 46.07 -- Water in hydrolyzer
75.00 9.5% 18.00 4.17 HCl 0.36 0.0% 36.00 0.01 Sodium bicarbonate
0.84 0.1% 84.00 0.01
Example 38
[0240] Using the reaction type process an MVF precursor formulation
was made using the following formulation. The temperature of the
reaction was maintained at 72.degree. C. for 21 hours.
TABLE-US-00027 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 0.00 0.0% 240.37 -- 0.00% --
-- Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- -- (FIG.
38) Dimethyldiethoxysilane (FIG. 0.00 0.0% 148.28 -- 0.00% -- --
42) Methyldiethoxysilane (FIG. 39) 0.00 0.0% 134.25 -- 0.00% -- --
Vinylmethyldiethoxysilane 1584.00 41.1% 160.29 9.88 100.00% 9.88
19.76 (FIG. 40) Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in
hydrolyzer 0.00 0.0% 58.08 -- Ethanol in hydrolyzer 1875.00 49.0%
46.07 40.70 Water in hydrolyzer 370.00 9.7% 18.00 20.56 HCl (pH 2,
36 g/100 g water) 0.36 36.00 0.01 Sodium bicarbonate 0.84 84.00
0.01
Example 39
[0241] Using the reaction type process an MVF precursor formulation
was made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00028 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 0.00 0.0% 240.37 -- 0.00% --
-- Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- -- (FIG.
38) Dimethyldiethoxysilane (FIG. 0.00 0.0% 148.28 -- 0.00% -- --
42) Methyldiethoxysilane (FIG. 39) 0.00 0.0% 134.25 -- 0.00% -- --
Vinylmethyldiethoxysilane 1584.00 42.0% 160.29 9.88 100.00% 9.88
19.76 (FIG. 40) Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in
hydrolyzer 1825.00 48.3% 58.08 31.42 Ethanol in hydrolyzer 0.00
0.0% 46.07 -- Water in hydrolyzer 365.00 9.7% 18.00 20.28 HCl (pH
2, 36 g/100 g water) 0.36 36.00 0.01 Sodium bicarbonate 0.84 84.00
0.01
Example 40
[0242] Using the reaction type process an MVF precursor formulation
was made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00029 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 0.00 0.0% 240.37 -- 0.00% --
-- Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- -- (FIG.
38) Dimethyldiethoxysilane (FIG. 0.00 0.0% 148.28 -- 0.00% -- --
42) Methyldiethoxysilane (FIG. 39) 0.00 0.0% 134.25 -- 0.00% -- --
Vinylmethyldiethoxysilane 33.00 41.9% 160.29 2.06 100.00% 2.06 4.12
(FIG. 40) Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in
hydrolyzer 380.00 48.3% 58.08 6.54 Ethanol in hydrolyzer 0.00 0.0%
46.07 -- Water in hydrolyzer 76.00 9.7% 18.00 4.22 HCl (pH 2, 36
g/100 g water) 0.36 36.00 0.01 Sodium bicarbonate 0.84 84.00
0.01
Example 41
[0243] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 72.degree. C. for 21 hours.
TABLE-US-00030 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Methyltriethoxysilane (FIG. 0.00 0.0% 178.30 -- 0.00% -- --
37) Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- --
(FIG. 38) Dimethyldiethoxysilane (FIG. 56 7.2% 148.28 0.38 17.71%
0.38 0.76 42) Methyldiethoxysilane (FIG. 39) 182 23.2% 134.25 1.36
63.57% 1.36 2.71 Vinylmethyldiethoxysilane 64 8.2% 160.29 0.40
18.72% 0.40 0.80 (FIG. 40) Triethoxysilane 0.00 0.0% 164.27 --
0.00% -- -- Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in
hydrolyzer 0.00 0.0% 58.08 -- Ethanol in hydrolyzer 400.00 51.1%
46.07 8.68 Water in hydrolyzer 80.00 10.2% 18.00 4.44 HCl 0.36 0.0%
36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 42
[0244] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the
reaction was maintained at 61.degree. C. for 21 hours.
TABLE-US-00031 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Methyltriethoxysilane (FIG. 0.00 0.0% 178.30 -- 0.00% -- --
37) Phenylmethyldiethoxysilane 0.00 0.0% 210.35 -- 0.00% -- --
(FIG. 38) Dimethyldiethoxysilane (FIG. 56 7.2% 148.28 0.38 17.71%
0.38 0.76 42) Methyldiethoxysilane (FIG. 39) 182 23.2% 134.25 1.36
63.57% 1.36 2.71 Vinylmethyldiethoxysilane 64 8.2% 160.29 0.40
18.72% 0.40 0.80 (FIG. 40) Triethoxysilane 0.00 0.0% 164.27 --
0.00% -- -- Hexane in hydrolyzer 0.00 0.0% 86.18 -- Acetone in
hydrolyzer 400.00 51.1% 58.08 6.89 Ethanol in hydrolyzer 0.00 0.0%
46.07 -- Water in hydrolyzer 80.00 10.2% 18.00 4.44 HCl 0.36 0.0%
36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 43
[0245] A polysilocarb formulation has 80% MHF, 15% TV, and 5%
VT.
Example 73
[0246] A polysilocarb formulation has 95% MHF and 5% TV.
Example 74
[0247] A polysilocarb formulation has 90% MHF, 5% TV, and 5%
VT.
Example 76A
[0248] Using the reaction type process a polysilocarb precursor
formulation was made using the following formulation. The
temperature of the reaction was maintained at 72.degree. C. for 21
hours.
TABLE-US-00032 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 180.00 22.7% 240.37 0.75
44.10% 0.75 2.25 Phenylmethyldiethoxysilane 50.00 6.3% 210.35 0.24
14.00% 0.24 0.48 (FIG. 38) Dimethyldiethoxysilane (FIG. 40.00 5.0%
148.28 0.27 15.89% 0.27 0.54 42) Methyldiethoxysilane (FIG. 39)
30.00 3.8% 134.25 0.22 13.16% 0.22 0.45 Vinylmethyldiethoxysilane
35.00 4.4% 160.29 0.22 12.86% 0.22 0.44 (FIG. 40)
Trimethyethoxysilane (FIG. 0.00 0.0% 118.25 0.00% -- -- 48) Hexane
in hydrolyzer 0.00 0.0% 86.18 -- Acetone in hydrolyzer 0.00 0.0%
58.08 Ethanol in hydrolyzer 380.00 48.0% 46.07 8.25 Water in
hydrolyzer 76.00 10.9% 18.00 4.22 HCl (pH 2, 36 g/100 g water) 0.36
0% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 76B
[0249] Using the reaction type process a polysilocarb precursor
formulation was made using the following formulation. The
temperature of the reaction was maintained at 61.degree. C. for 21
hours.
TABLE-US-00033 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 180.00 22.7% 240.37 0.75
44.10% 0.75 2.25 Phenylmethyldiethoxysilane 50.00 6.3% 210.35 0.24
14.00% 0.24 0.48 (FIG. 38) Dimethyldiethoxysilane (FIG. 10.00 1.3%
148.28 0.07 3.95% 0.07 0.13 42) Methyldiethoxysilane (FIG. 39)
45.00 5.7% 134.25 0.34 19.63% 0.34 0.67 Vinylmethyldiethoxysilane
51.00 6.4% 160.29 0.32 18.64% 0.32 0.64 (FIG. 40)
Trimethyethoxysilane (FIG. 0.00 0.0% 118.25 0.00% -- -- 48) Hexane
in hydrolyzer 0.00 0.0% 86.18 -- Acetone in hydrolyzer 380.00 47.9%
58.08 6.54 Ethanol in hydrolyzer 0.00 0.0% 46.07 0.00 Water in
hydrolyzer 76.00 9.6% 18.00 4.22 HCl (pH 2, 36 g/100 g water) 0.36
0% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 76C
[0250] Using the reaction type process a polysilocarb precursor
formulation was made using the following formulation. The
temperature of the reaction was maintained at 61.degree. C. for 21
hours.
TABLE-US-00034 Moles of % of Total % of Reactant/ Moles of Moles
Moles Reactant or Solvent Mass Total MW solvent Silane of Si of
EtOH Phenyltriethoxysilane (FIG. 45) 170.00 21.4% 240.37 0.71
40.76% 0.71 2.12 Phenylmethyldiethoxysilane 3200 4.0% 210.35 0.15
8.77% 0.15 0.30 (FIG. 38) Dimethyldiethoxysilane (FIG. 9.00 1.1%
148.28 0.06 3.50% 0.06 0.12 42) Methyldiethoxysilane (FIG. 39)
55.00 6.9% 134.25 0.41 23.61% 0.41 0.82 Vinylmethyldiethoxysilane
65.00 8.2% 160.29 0.41 23.37% 0.41 0.81 (FIG. 40)
Trimethyethoxysilane (FIG. 0.00 0.0% 118.25 0.00% -- -- 48) Hexane
in hydrolyzer 0.00 0.0% 86.18 -- Acetone in hydrolyzer 385.00 48.5%
58.08 6.63 Ethanol in hydrolyzer 0.00 0.0% 46.07 0.00 Water in
hydrolyzer 77.00 9.7% 18.00 4.28 HCl (pH 2, 36 g/100 g water) 0.36
0% 36.00 0.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01
Example 77
[0251] A polysilocarb liquid formulation has 40% MHF and 60%
TV.
Example 78
[0252] A polysilocarb formulation has 60% MHF and 40% TV may be
used as an infiltrant for a pyrolysis process.
Example 79
[0253] A polysilocarb formulation has 60% MHF, 30% TV, and 10% a
hydroxy terminated dimethyl polysiloxane.
Example 80
[0254] A polysilocarb formulation has 64% methyl terminated
phenylethyl polysiloxane of FIG. 16 (where group "X" makes up 10%
of the material), 26% TV, and 5% a hydroxy terminated dimethyl
polysiloxane.
Example 81
[0255] A polysilocarb formulation has 58% MHF, 26% TV, 5% VT and 5%
a hydroxy terminated dimethyl polysiloxane.
Example 82
[0256] A polysilocarb formulation has 0-20% MHF, 0-30% TV, 50-100%
H62 C and 0-5% a hydroxy terminated dimethyl polysiloxane.
Example 83
[0257] A polysilocarb formulation has 25% methyl terminated
phenylethyl polysiloxane of FIG. 16 (where group "X" makes up 10%
of the material), 20% TV, 50% MHF and 5% VT.
Example 84
[0258] A polysilocarb formulation has from 20-80% MHF and 20-80%
TV.
Example 85
[0259] A polysilocarb formulation has from 70% MHF and 30% TV may
be used as an infiltrant for a pyrolysis process.
Example 86
[0260] A polysilocarb formulation has from 80% MHF and 20% TV may
be used as an infiltrant for a pyrolysis process.
Example 87
[0261] A polysilocarb formulation has 20% methyl terminated
phenylethyl polysiloxane of FIG. 16 (where group "X" makes up 10%
of the material), 30% TV, and 50% MHF.
Example 88
[0262] A polysilocarb formulation has 40% methyl terminated
phenylethyl polysiloxane of FIG. 16 (where group "X" makes up 10%
of the material), 30% TV, and 10% MHF.
Example 89
[0263] A polysilocarb formulation has 80% methyl terminated
phenylethyl polysiloxane of FIG. 16 (where group "X" makes up 10%
of the material) and 20% TV.
Example 90
[0264] A polysilocarb formulation has 100% H62 C and may be used as
an infiltrant for a pyrolysis process.
Example 100
[0265] A polysilocarb formulation has 10% methyl terminated
phenylethyl polysiloxane of FIG. 16 (where group "X" makes up 10%
of the material), 20% TV, and 70% MHF.
Example 101
[0266] A polysilocarb formulation has 5% MHF, 10% TV, and 85% H62 C
and may be used as an infiltrant for a pyrolysis process.
Example 102
[0267] A polysilocarb formulation has 55% MHF, 35% TV, and 10% H62
C and may be used as an infiltrant for a pyrolysis process.
Example 103
[0268] A polysilocarb formulation has 40% MHF, 40% TV, and 20% VT
and has a hydride to vinyl molar ratio of 1.12:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 104
[0269] A polysilocarb formulation has 42% MHF, 38% TV, and 20% VT
and has a hydride to vinyl molar ratio of 1.26:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 105
[0270] A polysilocarb formulation has 46% MHF, 34% TV, and 20% VT
and has a hydride to vinyl molar ratio of 1.50:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 106
[0271] A polysilocarb formulation has 49% MHF, 31% TV, and 30% VT
and has a hydride to vinyl molar ratio of 1.75:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 107
[0272] A polysilocarb formulation has 51% MHF, 49% TV, and 0% VT
and has a hydride to vinyl molar ratio of 1.26:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 108
[0273] A polysilocarb formulation has 55% MHF, 35% TV, and 10% VT
and has a hydride to vinyl molar ratio of 1.82:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 109
[0274] A polysilocarb formulation has 52% MHF, 28% TV, and 20% VT
and has a hydride to vinyl molar ratio of 2.02:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 110
[0275] A polysilocarb formulation has 55% MHF, 25% TV, and 20% VT
and has a hydride to vinyl molar ratio of 2.36:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 111
[0276] A polysilocarb formulation has 65% MHF, 25% TV, and 10% VT
and has a hydride to vinyl molar ratio of 2.96:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 112
[0277] A polysilocarb formulation has 70% MHF, 20% TV, and 10% VT
and has a hydride to vinyl molar ratio of 3:93:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 113
[0278] A polysilocarb formulation has 72% MHF, 18% TV, and 10% VT
and has a hydride to vinyl molar ratio of 4.45:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 114
[0279] A polysilocarb formulation has 75% MHF, 17% TV, and 8% VT
and has a hydride to vinyl molar ratio of 4.97:1, and may be used
as to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 115
[0280] A polysilocarb formulation has 95% MHF, 5% TV, and 0% VT and
has a hydride to vinyl molar ratio of 23.02:1, and may be used as
to form strong ceramic beads, e.g., proppants for use in
hydraulically fracturing hydrocarbon producing formations.
Example 116
[0281] A polysilocarb batch having 70% of the MH precursor of the
formula of FIG. 1 and a molecular weight of about 800 and 30% of
the TV precursor of the formula of FIG. 17 are mixed together in a
vessel and put in storage for later use. The polysilocarb batch has
good shelf life and room temperature and the precursors have not,
and do not react with each other. The polysilocarb batch has a
viscosity of about 15 cps.
Example 117
[0282] A polysilocarb batch having 75% of the MH precursor of the
formula of FIG. 1 and a molecular weight of about 800 and 25% of
the TV precursor of the formula of FIG. 17 are mixed together in a
vessel and put in storage for later use. The polysilocarb batch has
good shelf life and room temperature and the precursors have not,
and do not react with each other. The polysilocarb batch has a
viscosity of about 18 cps.
Example 118
[0283] The polysilocarb batch of Example 11 has 28% of an about 80
micron to about 325 mesh SiC filler added to the batch to make a
filled polysilocarb batch, which can be kept for later use.
Example 119
[0284] The polysilocarb batch of Example 116 has 21% of a silica
fume to about 325 mesh silica filler added to the batch to make a
filled polysilocarb batch, which can be kept for later use.
Example 120
[0285] The polysilocarb batch of Example 12 has 40% of a silica
fume to about 325 mesh silica filler added to the batch to make a
filled polysilocarb batch, which can be kept for later use.
Example 121
[0286] A polysilocarb batch having 10% of the MH precursor of the
formula of FIG. 1 and a molecular weight of about 800 and 73% of
the styrene precursor of the formula of FIG. 16 (having 10% X) and
a molecular weight of about 1,000, and 16% of the TV precursor of
the formula of FIGS. 17, and 1% of the OH terminated precursor of
the formula of FIG. 7, having a molecular weight of about 1,000 are
mixed together in a vessel and put in storage for later use. The
polysilocarb batch has good shelf life and room temperature and the
precursors have not, and do not react with each other. The
polysilocarb batch has a viscosity of about 72 cps.
Example 122
[0287] A polysilocarb batch having about 70% of the MH precursor of
the formula of FIG. 1 and a molecular weight of about 800, and
about 20% of the TV precursor of the formula of FIGS. 17, and 10%
of the vinyl terminated precursor of the formula of FIG. 6 having a
molecular weight of about 6000 are mixed together in a vessel and
put in storage for later use. The polysilocarb batch has good shelf
life and room temperature and the precursors have not, and do not
react with each other. The polysilocarb batch has a viscosity of
about 55 cps.
Example 123
[0288] A polysilocarb batch having 0-90% of the MH precursor of the
formula of FIG. 1 and a molecular weight of about 800, and 0-90% of
the styrene precursor of the formula of FIG. 16 (having 10% X) and
a molecular weight of about 1000, and 0-30% of the TV precursor of
the formula of FIG. 17, and 0-30% of the vinyl terminated precursor
of the formula of FIG. 6 having a molecular weight of about 9400
and 0-20% of the OH terminated precursor of the formula of FIG. 7,
having a molecular weight of about 800 are mixed together in a
vessel and put in storage for later use. The polysilocarb batch has
good shelf life and room temperature and the precursors have not,
and do not react with each other. The polysilocarb batch has a
viscosity of about 100 cps.
Example 124
[0289] A polysilocarb batch having 70% of the MH precursor of the
formula of FIGS. 1 and 30% of the vinyl terminated precursor of the
formula of FIG. 6 having a molecular weight of about 500 and about
42% of a submicron and a 325 mesh silica are mixed together in a
vessel and put in storage for later use. The polysilocarb batch has
good shelf life and room temperature and the precursors have not,
and do not react with each other. The polysilocarb batch has a
viscosity of about 300 cps.
Example 125
[0290] 10 ppm of a platinum catalyst is added to each of the
polysilocarb batches of Examples 118-120 and these catalyzed
batches are dropped on a tray to form droplets and are cured in an
air oven at about 125.degree. C. for about 30 minutes. The cured
drop structures were slightly non-round beads with densities of
about 1.1-1.7 g/cc, diameters of about 200 microns to about 2 mm,
and crush strengths of about 3-7 ksi.
Example 126
[0291] 10 ppm of a platinum catalyst is added to the polysilocarb
batch of Example 121. Drops of the catalyzed batch are dripped into
a hot air column having a temperature of about 375.degree. C. and
fall by gravity for about a distance of 8 ft in the air column. The
cured spheres from the bottom of the air column are pyrolized in an
inert atmosphere at 1,000.degree. C. for about 120 minutes. The
pyrolized round spheres have a very uniform size (e.g., monosize
distribution), density of about 1.9-2.0 g/cc, a diameter of about
400-800 microns, and a crush strength of about 5.5-7 ksi.
Example 127
[0292] 10 ppm of a platinum and peroxide catalyst mixture is added
to the polysilocarb batch of Example 122. Drops of the catalyzed
batch are dripped into a hot air column having a temperature of
about 375.degree. C. and fall by gravity for about a distance of 8
ft in the air column. The cured spheres from the bottom of the air
column are pyrolized in an inert atmosphere at 1,000.degree. C. for
about 120 minutes. The pyrolized round spheres have a very uniform
size (e.g., monosize distribution), density of about 2.0-2.1 g/cc,
a diameter of about 400-800 microns, and a crush strength of about
4-5.5 ksi.
Example 128
[0293] A condensation cure reaction is performed in reinforced
preform in the shape of a diesel engine block, made from a batch
having 15% TES (FIG. 35) and 85% 350 and carbon fiber
reinforcement. The curing reaction produces water as a result of
the cross linking process. To manage the produced water the preform
is placed under vacuum and heated slowly through the cure
temperature, e.g., hrs at 120 C, followed by 4 hrs at 160 C,
followed by 4 hrs at 180 C. The cured preform is then pyrolized and
machined to provide a diesel engine block, which can be
subsequently assembled into a diesel engine.
Example 129
[0294] A condensation cure reaction is performed in reinforced
preform in the shape of a diesel engine block, made from a batch
having 10% TES (FIG. 35) and 90% 350 and ceramic fiber
reinforcement, e.g., NEXTEL 312. The curing reaction produces water
as a result of the cross linking process. To manage the produced
water the preform is placed under vacuum and heated slowly through
the cure temperature, e.g., 4 hrs at 140 C, followed by 4 hrs at
160 C, followed by 2 hrs at 180 C. The cured preform is then
pyrolized and machined to provide a diesel engine block, which can
be subsequently assembled into a diesel engine.
Example 130
[0295] A condensation cure reaction is performed in reinforced
preform in the shape of a oil field down hole casing pipe, made
from a batch having 15% TES (FIG. 25) and 85% 350 and fiberglass
reinforcement. The curing reaction produces water as a result of
the cross linking process. To manage the produced water the preform
is placed under vacuum and heated slowly through the cure
temperature, e.g., 4 hrs at 140 C, followed by 4 hrs at 160 C,
followed by 2 hrs at 180 C.
Example 131
[0296] A condensation cure reaction is performed in reinforced
preform in the shape of a oil field down hole tool, made from a
batch having 15% TES (FIG. 35) and 85% 350 and carbon fiber
reinforcement. The curing reaction produces water as a result of
the cross linking process. To manage the produced water the preform
is placed under vacuum and heated slowly through the cure
temperature, e.g., 4 hrs at 140 C, followed by 4 hrs at 160 C,
followed by 2 hrs at 180 C. The cured preform is then pyrolized and
machined to provide a down hole tool.
Example 132
[0297] A condensation cure reaction is performed in reinforced
preform in the shape of a cutter for use in a cutting tool from a
batch having 10% TES (FIG. 6) and 90% 350 and ceramic powder and
diamond powder. The curing reaction produces water as a result of
the cross linking process. To manage the produced water the preform
is placed under vacuum and heated slowly through the cure
temperature, e.g., 4 hrs at 140 C, followed by 4 hrs at 160 C,
followed by 2 hrs at 180 C. The cured preform is then pyrolized and
machined to provide cutters for use in, or with, cutting tools,
such as down hole drill bits.
[0298] The various embodiments of formulations, plastics, articles,
components, parts, uses, applications, methods, activities and
operations set forth in this specification may be used for various
other fields and for various other activities, uses and
embodiments. Additionally, these embodiments, for example, may be
used with: existing systems, articles, components, operations or
activities; may be used with systems, articles, components,
operations or activities that may be developed in the future; and
with such systems, articles, components, operations or activities
that may be modified, in-part, based on the teachings of this
specification. Further, the various embodiments and examples set
forth in this specification may be used with each other, in whole
or in part, and in different and various combinations. Thus, for
example, the configurations provided in the various embodiments and
examples of this specification may be used with each other; and the
scope of protection afforded the present inventions should not be
limited to a particular embodiment, example, configuration or
arrangement that is set forth in a particular embodiment, example,
or in an embodiment in a particular Figure.
[0299] The invention may be embodied in other forms than those
specifically disclosed herein without departing from its spirit or
essential characteristics. The described embodiments are to be
considered in all respects only as illustrative and not
restrictive.
* * * * *