BORON, HIGH SILICA, QUARTZ 8

AND CERAMIC FIBERS

Anthony Marzullo

8.1 INTRODUCTION tinuous. Continuous fiber or whisker is capa-

ble of being manufactured to an indefinite
Boron, high silica, fused quartz and ceramic
length. Discontinuous fiber can be chopped
fibers are used in demanding industrial, auto-
continuous fiber, or a short fiber called staple.
motive, electronic, aircraft and aerospace
Discontinuous whisker is manufactured to a
environments. Boards made of ceramic fibers
definite length in batch type processing, while
such as alumina, alumina-silica or zirconia are
continuous whisker is produced by melt
used as supplemental linings to insulate high
processes such as the laser-heated floating-
temperature furnaces. Ceramic tiles contain-
zone process.
ing alumina and silica fibers protect the
Summarizing, there is continuous fiber
aluminum skin of USA's space shuttle orbiter
(indefinite length), continuous whisker (single
during re-entry, where the tile's surface may
crystal, indefinite length), discontinuous fiber
be aerodynamically heated to 1260°C (Banas,
(chopped continuous fiber or staple fiber) and
McCormick and Creedon, 1991). Other appli-
discontinuous whisker (single crystal, definite
cations of these fibers involve reinforcing
length).
polymer-, glass-, ceramic-, or metal-matrix
composites. If the composite is well designed,
it will be tougher than the matrix material by 8.2 MANUFACTURE
itself. As an example, the fracture toughness of
Sic is 1.5 MPa m-2,but 8-15 for Sic reinforced Melt, vapor deposition and chemical processes
with Sic fibers (Richerson, 1992). are used to manufacture fibers and whiskers.
Fibers and whiskers that are made by melt
Fibers can be classified according to struc-
processing include continuous quartz fibers
ture, diameter (or cross sectional width) and
by drawing from a fused quartz rod, alu-
length. In general, a material is classified as a
mina-silica staple by atomizing a molten
fiber if its diameter or cross sectional width is
ceramic stream and continuous alumina
less than 0.0254 m (0.010 in) and 1ength:diam-
whiskers by drawing from a melt. Vapor depo-
eter ratio is greater than 1O:l.Most commercial
sition processes include chemical vapor
fibers meet these requirements easily. A fiber is
deposition of silicon carbide or boron onto a
called a whisker if its microstructure is pre-
dominantly single crystal. Fibers or whiskers tungsten core to make continuous fibers and
can be subclassified as continuous or discon- the vapor-liquid-solid (VLS) process to make
discontinuous whiskers. Chemical processing
called sol-gel technology is used to create alu-
mina-based continuous fiber. Other chemical
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 processes include the creation of polymer
 Continuous fibers 157

precursor fiber that is later pyrolyzed into sili- fibers with a minimum of surface flaws, the
con, carbon and nitrogen-based continuous rod’s surface should be flame polished with an
fiber and the reaction between silica and car- oxy-hydrogen flame, as is done in optical fiber
bon to make discontinuous whiskers. manufacturing (Blyler and DiMarcello, 1991).
The manufacturing processes are summa-
rized in Table 8.1.
8.3.3 CONTINUOUS FIBERS BY CHEMICAL
VAPOR DEPOSITION
8.3 CONTINUOUS FIBERS Producing silicon carbide fibers by chemical
8.3.1 HIGH SILICA FIBERS vapor deposition (CVD) begins by pulling a
melt-spun carbon fiber through a mercury seal
Amorphous high silica fibers can be manufac- and into a tubular reactor. The carbon fiber is
tured by leaching sodium oxide from sodium heated by coupling the mercury seals on the
silicate glass fibers. The glass fibers, made by top and bottom of the reactor to a source of
using conventional glass fiber production tech- electricity. The melt-spun carbon fiber is called
niques, are composed primarily of 74.5%)silica a substrate or a core because silicon carbide is
and 24.2% sodium oxide. The fibers are held in vapor deposited onto it. The deposited silicon
a perforated basket, which is suspended within carbide is produced by the reaction of a gas
a cylindrical tank. A solution of HC1 and water mixture of silanes and hydrogen that enters
is pumped from the bottom of the tank up to the reactor through a port. Details of produc-
and over the glass fibers for several hours. The ing silicon fibers by CVD are found in
HCl/water/fiber mixture is stirred periodi- Wawner, Jr. (1988) and Textron Specialty
cally. The HCl and water are drained away, the Materials (1993b). Producing boron fibers by
fibers rinsed and a second leaching and rinsing CVD is a similar process (Tsirlin, 1985;
cycle is performed. The fibers are dried at a low Wawner, Jr., 1988; DeBolt, 1982).
temperature (Price and Kielmeyer, 1980).Other
techniques used to make high silica fibers
include spinning from solutions and spinning 8.3.4 PYROLYSIS OF POLYMERIC PRECURSOR
from a gel (Cooke, 1991). FIBER
Several ceramic fibers composed of various
combinations of silicon, carbon, nitrogen,
8.3.2 DRAWING CONTINUOUS FUSED
boron and titanium have been produced by
QUARTZ FIBERS
the pyrolysis of polymeric precursor fiber. The
Amorphous fused quartz fibers are made from process consists of four major steps: synthesize
preforms of fused quartz rods. The end of a a spinnable polymer, spin the polymer into
fused quartz rod is heated with an oxy-hydro- precursor fiber, cross-link (cure) the precursor
gen flame and the fiber is drawn, sized and fiber and pyrolyze the cured precursor fiber
either taken up on a spool or combined with into ceramic fiber.
other simultaneously drawn fibers to form a The synthesis of a polymeric precursor is
strand. Fused quartz rods are made by fusing known as Preceramic Polymer Chemistry.
chemically purified ground quartz crystal or Many spinnable polymers have been synthe-
quartz sand. Fused quartz rods are classified sized, including polycarbosilane as a
as Type I or Type I1 vitreous silica depending precursor for silicon carbide fiber (Yajima,
on the fusion technique. Type I signifies that 1985),polytitanocarbosilane as a precursor for
fusing was done in an electrically heated cru- Si-Ti-C-0 fiber (Yamamura et al., 1988) and
cible, while Type I1 implies fusing with an hydridopolysilazane as a precursor for silicon
oxy-hydrogen flame. To obtain fused quartz carbonitride fiber (LeGrow et al., 1987). In
158 Boron, high silica, quartz and ceramicfibers
a, 8
e
e
m irl
N
m
2 5
%
3
2-
I
0
a ti
Y
. 3
F;
3 2
s:
3
%
W W
0 0
8
a,
2 =
.3
m
Fi
Y
. 3 mI
e .I
8
0 8 .3
e
3
.3
m
d
T I
.2 2
C E;
'23
a!3
2 8
.e
3
0 3
m 5 d
0
3
3

X
2
W W
Y
8
2z x
z" rf!
F4
h
3
v1
m
5a
.e
b
m
Y
g
U
$ bD
$
U
.$ 30
s3 e
6
a"
 Staple 159

general, the polymeric precursor is melt spun. operation. They claimed that the fiber proper-
But other spinning methods, such as dry spin- ties were improved due to uniform heating and
ning, have been used. even fiber tensioning (Koba et al., 1989).
The spun precursor fiber is cross-linked to Sumitomo Chemical Co invented a fiber
prevent melting during the subsequent pyroly- with 85% gamma or delta-alumina and 15%sil-
sis step. Yajima cross-linked his polycarbosilane ica by calcining dry-spun fibers. The spinnable
precursor fiber by heating it in air to 200°C. mixture was formed by mixing an aluminum
Later research showed that silicon carbide fiber compound in a solvent and adding water to
properties were improved after curing the poly- get polyaluminoxane. A silica containing com-
carbosilane precursor fiber with electron beam pound, an organic polymer to improve
radiation (Takeda et al., 1992). spinnability and a compound such as lithium
The pyrolysis step consists of heating the to improve fiber properties were added. The
cured precursor fiber to a temperature gener- solvent was removed by distillation. The mix-
ally above 800°C in order to create a ceramic ture is spun into fiber and the fiber is calcined
fiber. (Kadokura, Harakawa and Matumoto, 1991).
Minnesota Mining and Mfg. Co. (3M)
makes fibers composed of alumina, boria and
8.3.5 ALUMINA BASED FIBER
silica by drying and sintering fiber that is spun
E.I. du Pont de Nemours patented a process to from concentrated aqueous solutions. The
make continuous alumina fibers that involved aqueous solution can be composed of an alu-
spinning a viscous slurry. One slurry composi- mina and boria precursor such as a basic
tion was prepared by dissolving an alumina aluminum acetate, silica sol and water. The
precursor such as aluminum chlorohydroxide 14%boria in 3M’s Nextel 312 fiber mhibits the
in water and then adding solid alumina parti- formation of alumina crystals and aluminum
cles. An organic polymer might be added to borosilicate is the predominant crystalline
the slurry to aid its spinnability by modifying species. The 2% boria in Nextel 440, however,
its viscosity. The viscous slurry was extruded is not enough to inhibit alumina, with eta-
through a spinneret and the green (unfired) alumina being the predominant crystalline
fibers were wound onto a bobbin. The fibers species (Sowman, 1988).
were fired at a temperature below the sinter-
ing temperature (calcining) to remove water
8.4 STAPLE
and volatile material. The calcined fibers were
sintered (densified) to remove porosity and The process to make alumina staple is similar
convert the alumina precursor to the stable to the processes that are used in making alu-
alpha-alumina structure. mina-based continuous fibers. An aqueous
This slurry-spinning process was advanced and viscous solution of an alumina precursor,
by Mitsui Mining Co. where the fiber was spun, silica and an organic polymer is extruded
dried, calcined and sintered in a continuous through apertures into a high velocity gas
stream, creating green (unfired) staple. The
green staple is sintered. The silica is added to
toughen the resultant staple by inhibiting alu-
Footnotes for Table 8.1
mina crystal growth while the green staple is
a Most of the trade names are registered trademarks. Each

trademark belongs to the manufacturer listed to its left.

being sintered (Bunsell et al., 1988).
All data on composition for the continuous and staple Imperial Chemical Industries (ICI) has a
fibers, except for Tyranno Fiber, are from the commercial alumina staple called Saffil. Saffil
manufacturers’ product literature. Tyranno Fiber is 3 ym in diameter and its length is 1-5 cm in
composition is from Weddell (1990). the mat form. Saffil comes in six grades ranging
160 Boron, high silica, quartz and ceramicfibers

from the catalytic grade with an eta-alumina the end of a polycrystalline feed rod is melted
structure, to an aerospace grade with a delta + with a CO, laser, a grain free seed crystal is
alpha-alumina or an alpha + delta-alumina + brought in contact with the melt and a whisker
mullite structure. is drawn. The LHFZ process can be used to
Alumina-silica staple, also called alumi- produce whiskers with diameters as low as
nosilicate staple, is made by atomizing a 10 pm or as high as 10 pm (Haggerty,Wills and
molten ceramic stream. The raw material for Sheehan, 1991).
the melt is a clay mineral or a blend of alumina
and silica. The melt is atomized by pouring it 8.5.2 DISCONTINUOUS WHISKERS BY THE VLS
into the path of a high velocity air stream or by PROCESS
feeding it onto a rotating wheel that throws
out the melt by centrifugal force. The former is VLS stands for vapor feed gases-liquid cata-
called the blowing process, while the latter is lyst-solid crystalline whisker growth. In a
called centrifugal spinning. One commercial particular VLS process to make single crystal
alumina-silica staple called Fiberfrax ranges Sic whiskers, uniformly sized catalyst particles
in length from 70-1000 pm and is made by The are applied to carbon substrates. The carbon
Carborundum Co. substrates and catalyst are placed within a
growth chamber. Also within the chambers are
Si0 generators, made by impregnating porous
8.5 WHISKERS brick with carbon and SiO,. The chamber is
placed within a furnace and heated to a growth
8.5.1 CONTINUOUS WHISKERS
temperature of 1300-1450°C. During t h s time,
Single crystal continuous alumina whiskers can gases such as CO, CH,, N, and H, are fed into
be grown from a pure melt by using a modifi- the chamber. The catalyst particles melt and
cation of the Czochralski method. The modified become supersaturated with material supplied
method is still classified as a moving crystal from the vapor and carbon from the substrate.
techruque, but, unlike Czochralslu’s technique, Solid Sic precipitates from the liquid catalyst
uses a die to shape the growing whisker. A cap- onto the growth substrate. As precipitation con-
illary tube draws the melt up to and over a die. tinues, the whisker grows, lifting the catalyst
The melt flows to the die’s vertical edges and ball from the substrate (Petrovic and Hurley
stops; so the die’s vertical edges control the 1990; Milewski et al., 1985).
shape of the subsequently drawn whisker. A The time necessary to produce Sic whiskers
grain free seed crystal is brought in contact with by the VLS process can be reduced by under-
the melt surface and a whisker is drawn. A lin- cooling or pre-alloying the catalyst balls. After
ear temperature distribution is maintained reaching the growth temperature, the catalyst
along the axis of the growing crystal to avoid balls are undercooled by 150”C,initiating pre-
defects by lowering thermal stresses (LaBelle, cipitation. The chamber is brought back up to
Jr, 1980; Antonov, 1990). Saphikon Inc. grows the growth temperature and held there until
whiskers in many shapes using a similar whisker growth is completed. Another tech-
process that they call EFG (edge-defined,film- nique to reduce the growth time is to pre-alloy
fed growth). One of the shapes is a hollow tube the catalyst particles with carbon and silicon
that may be used as a waveguide (Harrington so that whisker growth occurs immediately
and Gregory 1990). upon reaching the growth temperature
Another moving crystal technique to make (Shalek, 1987; Shalek, Katz and Hurley, 1988).
continuous alumina whiskers is called the Other whiskers produced by the VLS
laser heated floating zone directional solidifi- process include A1,0,, boron, MgO and Si
cation process (LHFZ). In the LHFZ process,

(Wagner, 1970); Tic by using TiC1, and CH, as
the primary feed gases and a nickel catalyst
(Pearson and Easley, 1992; Narasimhan and
Bhat, 1992);Si,N, by using Si,Cl, and NH, as the
primary feed gases and an iron catalyst
(Motojima et al., 1989);and TiB, by using TiC1,
and BC1, as the primary feed gases and Au or Si
as the catalyst (Withers, Loutfy and Lee, 1988).
8.5.3 OTHER DISCONTINUOUS WHISKER
GROWTH PROCESSES
An early vapor phase growth process to make
alumina whiskers involved hydrogen reduc-
tion. Wet hydrogen was passed over heated
aluminum powder. Whisker lengths and
diameters were from 1-30 mm and 3-50 pm,
respectively. Hydrogen reduction of methyl-
trichlorosilane was used to produce p-Sic
whiskers (Milewski, 1991).Other vapor phase
growth techniques are evaporation-condensa-
tion and vapor phase reaction. These and
other growth techniques, are discussed in
Bracke, Schurmans and Verhoest (1984).
Some commercial processes to make Sic
whiskers use a chemical reaction between silica
and carbon powders. Tokai Carbon manufac-
tures p-Sic whiskers by heating a mix of
pulverized silica gel, carbon black and a metal
catalyst. The mix is heated in a nonoxidizing
atmosphere at 1300-1700°C and the whiskers
grow within the pores of the mix (Yamamoto,
1985).The whiskers are under 1.0 pm in diame-
ter and under 300 pm in length.
Other companies have produced Sic
whiskers by chemical reactions: the J.M.
Huber Corp. passed perforated trays filled
with ground rice hulls over heated carbon pel-
lets and through a horizontal furnace. Ground
rice hulls were used as the reactant material
because they contain both silica and carbon
(Tanaka, Kawabe and Kobune, 1986).
Silicon nitride whiskers have been pro-
duced by heating a silica and carbon mix or
rice hulls in a nitrogen atmosphere (nitriding),
or by heating silica powder in a gas mixture of
ammonia gas and hydrocarbon gas.
Forms 161
8.6 PROPERTIES
Boron, h g h silica, quartz and ceramic fibers
have a high thermal and chemical stability rela-
tive to organic fibers. Maximum use
temperatures of boron, h g h silica, quartz and
ceramic fibers, except for boron fiber in an oxi-
dizing atmosphere, all are over 1000°C. These
fibers have a good balance of specific strength
(tensile strength/density ratio) and specific
modulus (elastic modulus/density ratio) com-
pared with other materials. Tsirlin’s (1985)
graphs of specific strength against specific
modulus for boron or Sic fibers with cores
illustrate this point. In Table 8.2 note the low
coefficient of thermal expansion for quartz
fibers, which allows them to be used in parts
that are subjected to high temperatures, such as
in high speed printed circuit boards.
8.7 FORMS
The form that a fiber can take depends on its
length, diameter and mechanical properties,
such as elastic modulus and tensile strength.
In general, discontinuous whiskers are too
short to be spun into yarn, however, VLS
whiskers about 75-100 mm long might be
spun into staple yarn (KO, 1989).A fiber’s flex-
ibility is related to its diameter, elastic
modulus and tensile strength. A measure of
flexibility is l / [ d ( E / o- l)]where d = diameter,
E = elastic (Young’s)modulus and cs = tensile
strength. A greater value indicates a greater
flexibility. Obviously, the greater a fiber’s flex-
ibility, the easier it is to twist, braid and weave
into complex shapes without breakage.
As an example, l / [ d ( E / o - l)]is about 126
for continuous Sic fiber with a core (d =
80 pm), 533 for continuous alumina fiber, 1298
for continuous Sic fiber (d = 12 pm) and 10 101
for continuous fused quartz fiber. The Sic
fiber with a core, having a lower flexibility rel-
ative to other fibers, is generally used for
unidirectional reinforcement. The fiber might
also be used in a material-geometric hybrid to
axially reinforce a woven preform of finer
162 Boron, high silica, quartz and ceramic fibers
V
\
f
0
r(
X 4 4
9
d. E E
x
0
+
x I
0
0
0
a
d m m
& h
o!
N
b
d z
0
L?
N
8
m
CYYZ?h x
LD
L?
N 2
2
E m
I
2 N m
a, d
e2mu
.3
3
.3
m
I
F.
2 8
8 '2 '2
3 3
.A
3
3
3
d a
a
6

diameter Sic fiber (KO, 1989). Fine diameter
(less than 20 pm) continuous ceramic fiber is
more flexible, can be formed into nontwisted
strands (sometimes called nontwisted yarn)
and braided or woven into two- or three-
dimensional shapes. The quartz fibers, being
the most flexible, can be twisted into filament
yarn and braided or woven into two- or three-
dimensional shapes.
Figure 8.1 shows some of the many forms
that fibers can take. Each strand of the fine
diameter ceramic fibers can contain anywhere
from 250 to 1000 filaments per strand, depend-
ing on the product. The strands may be
bundled to form roving. Fused quartz
untwisted strands are formed into roving that
contains either 2880 or 4800 filaments per rov-
ing. As mentioned earlier, fused quartz fibers
may be twisted into yarn at 4 turns per inch,
with 120, 240, 480, 960, or 1920 filaments per
yarn and in a variety of yarn constructions.
Fine diameter ceramic and fused quartz fibers
can be formed into many multidimensional
structures, such as orthogonal nonwoven fab-
rics (Fiber Materials, Inc., 1993; KO, 1989).
Orthogonal nonwoven fabrics are so-called
because there is no interlacing of fibers. Other
names for these fabrics are xyz fabrics, multi-
directional preforms and 3D, 4D, 5D, 7D or
11D woven blocks. The 5D, 7D and 11D blocks
have strands going in the three orthogonal
directions and in diagonal directions. The 4D
blocks have strands going in two orthogonal
Footnotes for Table 8.2
aAll values, except those for silicon carbide whiskers, are
from the manufacturers’ product literature.
Test methods may varv between manufacturers.
i ,
All values are averages, are for reference only and are
not to be taken as a specification.
Most fibers are under continual development. Contact
the manufacturers for the most up to date property values.
DNA = Data Not Available.
The silicon carbide whisker values are from Petrovic and
Hurley (1990).
This value in metric units was converted from a value
that was given in English units.
Most of the tradenames are registered trademarks. Each
trademark belongs to the manufacturer listed to its left
Applications 163
and two diagonal directions. Figure 8.1 shows
the 3D and 5D fabrics. See Ngai (1990) for dia-
grams of 4D, 7D and 11D fabrics.
Continuous boron fibers are supplied in the
form of borodepoxy prepreg tape and
boron/aluminum preform sheets. The
boron/aluminum preform sheets are made by
resin bonding the boron fibers to the side of
aluminum foil. The fibers can be aligned in
any direction. These preform sheets are used
in solid state (low temperature, high pressure)
diffusion bonding processes (TextronSpecialty
Materials, 1993a).
Continuous Sic fibers with a core are
formed into plasma-sprayed aluminum or
titanium preform sheets for hot molding (a
low pressure, hot pressing process) and into
’woven fabric’ for investment casting or diffu-
sion bonding. In diffusion bonding, the fabric
is placed between two metal foils prior to con-
solidation. The ’woven fabric’ is similar to
nonwoven roving because the fibers are
aligned in one direction and held together by a
cross-weave of metallic ribbons (Textron
Specialty Materials, 199313; Mittnick 1990).
Continuous high silica fibers are processed
into a variety of forms such as cloth, tape,
sleeving, yarn, cordage, rope, nonwoven mat,
blanket, felt, rigid tile and sewing thread.
Alumina-silica staple fibers are made into
paper, rigid board and cylinders, other rigid
three-dimensional shapes and into most of the
high silica fiber forms. Alumina staple fibers
are processed into paper, mat, felt, blanket,
rigid board and cylinders and other rigid
three-dimensional shapes.
8.8 APPLICATIONS
Table 8.3 provides a sampling of the many
applications for boron, high silica, fused
quartz and ceramic fibers. For other applica-
tions, see Bracke, Schurmans and Verhoest
(1984), Mortensen and Koczak (1993),
Schwartz (1992) and the other chapters within
this handbook.
164 Boron, high silica, quartz and ceramicfibers
0
U
0
mI
U
0
0-
I N
$3
mz
2
m
z
0
B

Fig. 8.1 Schematic of some fiber forms.

ui
Y
O
h z
W
3
Fig. 8.1 Schematic of some fiber forms.
Applications 165
166 Boron, high silica, quartz and ceramic fibers
8.8.1 NONCOMPOSITES
Alumina and alumina-silica staple fibers and
the continuous high silica fibers are used in
high temperature applications in many indus-
tries. Forms of these fibers are used for
thermal insulation, personnel protection and
gasketing. See Carborundum (1991) for the
many applications of high silica fibers and
Carborundum (1989) for the many applica-
tions of alumina-silica fibers.
8.8.2 COMPOSITES
Fibers and whiskers have been used to rein-
force polymers, epoxies, glasses, metals, or
ceramics. The reinforced materials are called
composites in general and, more specifically,
polymer, epoxy, glass, metal, or ceramic
matrix composites. The reinforcements are
either discontinuous whiskers or continuous
fibers for the applications in Table 8.3, but sta-
ple fiber and continuous whisker may be used
as a reinforcement material as well. Usually
the fiber or whisker is coated to cover its sur-
face flaws, provide a diffusional barrier
between it and the matrix material and protect
the fiber or whisker from oxidation. In addi-
tion, the coating provides a weak interface that
deflects cracks propagating through the
matrix in ceramic matrix composites
REFERENCES
Antonov, P.l. 1990. Review of Factors Controlling
the Growth of Shaped Crystals. J. Crysf. Growth
104: 3946.
Banas, R., McCormick, M. and Creedon, J. 1991.
HTP-6.5-22 and HTP-1-22, Reusable Rigid
Fibrous Ceramic Materials for Heat Shields on
Future Reentry Vehicles. In Ceramics Today -
Tomorrow’s Ceramics, ed. P. Vincenzini, pp.
2889-98. Amsterdam: Elsevier Science
Publishers B.V.
Blyler, Jr., L.L. and DiMarcello, F.V. 1991. Optical
Fibers, Drawing and Coating. In Encyclopedia of
Lasers and Optical Technology, ed. Robert A.
Meyers, pp. 457-67. New York: Academic Press
Bracke, I?, Schurmans, H. and Verhoest, J. 3984.
Inorganic Fibres and Composite Materials. New
York: Pergamon Press.
Brown, A.S. 1993. High-temperature materials
warm up for debut. Aerospace America 31 (3):
18-27.
Buljan, S.T., et al. 1992. ’Development of Ceramic
Matrix Composites for Application in Ceramic
Technology for Advanced Heat Engine
Program’, Contract DE-AC05-840R21400, U.S.
Department of Energy, April 1992.
Bunsell, A.R. ef al. 1988. Ceramic fibers. In Fibre
Reinforcenien ts for Composite Materials, ed. A.R.
Bunsell, pp. 427-78. Vol. 2 of Composite
Materials Series, Series ed. R.B. Pipes.
Amsterdam: Elsevier Science Publishers B.V.
Carborundum 1989. ‘Fiberfrax Ceramic Fiber’. The
Carborundum Company. Niagara Falls, NU,
USA.
Carborundum 1991. ’Refrasil Products. Product
Specifications’. The Carborundum Company.
Niagara Falls, NY, USA.
Cooke, T.F. 1991. Inorganic Fibers - A Literature
Review. I. A m Cernm. Soc. 74 (12): 2959-78.
Covington, M.A. and Sawko, P.M. 1986. Optical
Properties of Woven Ceramic Fabrics for
Flexible Heat Shields. AIAA/ASME 4th Joint
Thermophysics and Heat Transfer Conference,
2 4 June 1986, Boston, Mass.
DeBolt, H.E. 1982. Boron and Other High-Strength,
High Modulus, Low Density Filamentary
Reinforcing Agents. In Handbook of Composites,
ed. George Lubin, pp. 171-95. New York: Van
Nostrand Reinhold.
Fiber Materials, Inc. 1993. ’3-D Orthogonal Woven
Blocks’ and ’Multi-Directional Woven
Preforms’. Fiber Materials, Inc. Biddeford,
Maine, USA.
Haggerty, J.S., Wills, K.C. and Sheehan, J.E. 1991.
Growth and Properties of Single Crystal Oxide
Fibers. Ceram. Eng. Sci. Proc. 12 (9-10):
1785-1801.
Harrington, J.A. and Gregory, Christopher C. 1990.
Hollow sapphire fibers for delivery of CO, laser
energy. Optics Letters 15 (10): 54103.
Kadokura, H., Harakawa, M. and Matumoto, T. 1991.
Process for Producing Alumina-Based Fiber. US
Patent 5002 750. Mar. 26, 1991. Assigned to
Sumitomo Chemical Co Ltd.
KO, F.K. 1989. Preform Fiber Architecture for
Cerami-Matrix Composites. Ceramic Bulletin 68
(2): 401-14.
Koba, K., et al. 1989. Continuous Process for
Producing Long a-Alumina Fibers. US Patent

4 812 271. Mar. 14, 1989. Assigned to Mitsui
Mining Co Ltd.
LaBelie, Jr., H.E.1980. EFG, The Invention and
Application to Sapphire Growth. J . Crysf.
Growth 50 (1980): 8-1 7.
L,asday, S.B. 1993. Ceramic/Ceramic Composite
Components Advance Furnace Systems and
Processes. lndiistriai Heating LX (4): 26-9.
LeGrow, G.E., et al. 1987. Ceramics from
tlydridopolysilazane. A m Ceram. Soc. B d l . 66
(2): 363-67.
Milewski, J.V., et al. 1985. Growth of Beta-silicon
Whiskers by the VLS Process. 1. Mater. Sci. 20
(1985): 1160 66.
Milewski, J.V. 1991. Whiskers. In Concise
Encyciopediu oj Advanced Cmutric hlatwials, ed.
R.J. Brook, pp. 516-19. Oxford: Pergamon Press.
Mittnick, M A . 1990. Continuous S i c Fiber
Reinforced Metals. SME Metal Matrix Clinic,
13-14 R-ovember 1990, at Anaheim, Ca.
Mohn, W.R. and Vukobratovich, D. 1988. Engineered
Metal Matrix Composites for Precision Optical
Systems. SAMPE J . 24 (1):26--35.
Mortensen A. and Koczak, M.J. 1993. The Status of
Metal-Matrix Composite Research and
Development in Japan. ]OM 45 (3): 10-18.
Motojimi, S., et nl. 1989. Preparation of Whiskers
and Spring-like Fibres of Si,N, By Impurity-
Activated Chemical Vapor Deposition. J. Cryst.
Growth 96: 383-89.
hhik, S.K., et a / . 1991. Ceramic Matrix Composites
and its Application in Gas Turbine Engines.
Presented at the International Gas Turbine and
Aeroengine Congress and Exposition, 3-6 June
1991, in Orlando, F1.
Narasimhan, K. and Bhat, D.G. 1992. Process for
Producing Single Crystal Titanium Carbide
Whiskers. US Patent 5094711. Mar. 10, 1992.
Assigned to GTE Valenite Corporation.
Ngai, T. 1990. Carbon-Carbon Composites. In
lnternational Encyclopedia of Composites, ed.
Stuart M. Lee, pp. 158-87. New York: VCH
Ptiblishers.
Pearson, A. and Easley, M.A. 1992. Process For
Production of Small Diameter 'Titanium Carbide
Whiskers. US Patent 5 160 574. Nov. 3, 1992.
Assigned to Aluminum Company of America.
Petrovic, J.J. and Hurley, G.F. 1990.
Vapor-Liquid-Solid (VLS) S i c Whiskers:
Synthesis and Mechanical Properties. In Fiber
Reinforced Ceramic Conzposites, ed. K.S.
Mazdiyasni, pp. 93-121. New Jersey: Noyes
Publications.
Refcremes 167
Price, G.B. and Kielmeyer, W.H. 1980. Method for
Making I-ligh Purity, Devitrification Resistant,
Amorphous Silica Fibers. US Patent 4 200 485.
Apr. 29, 1980. Assigned to John-Manville Gorp.
Richerson, D.W. 1992. Modern Ceruniic Engineering,
2nd edn. New York: Marcel Dekker, Inc.
Schwartz, M.M. 1992. Composite Materials I$andbook,
2nd edn. ed. M.M. Schwartz. New York:
McGr a w-Hill , Inc .
Shalek, P.D. 1987. Process for Growing Silicon
Carbide Whiskers by Undercooling. US Patent
4 702 901. Oct. 27, 1987. Assigned to The United
States of America.
Shalek, P.D., Katz, J.D., Hurley, G.F. 1988.
Prealloyed Catalyst for Growing Silicon
Carbide Whiskers. US Patent 4 789 537. Dec. 6,
1988. Assigned to The United States of America.
Schramm, Dale E. 1988. Process for Producing
Silicon Carbide Whiskers. US Patent 4 789 536.
Dec. 6, 1988: Assigned to J.M. Huber Corp.
Sowman, H.G. 1988. Alumina-Boria-Silica Ceramic
Fibers from the Sol-Gel Process. In Soi-Cel
Technology for 7 h i n Films. Fibers. Prefornzs.
Electronics. und Specialty Shapes, ed. Lisa C .
Klein, pp. 162-83. New Jersey: Noyes
Publications.
'Takeda, M. rt al. 1992. Thermal Stability of the Low
Oxygen Silicon Carbide Fiber Derived From
Polycarbosilane. Ceram. Eng. Sci. Proc. 13 (7--8):
209-1 7.
Tanaka, M., Kawabe, T. and Kobune, M. 1986.
Method of Manufacturing Crystalline Silicon
Carbide Employing Acid Pretreated Rice
Husks. US Patent 4 591 492. May 27, 1986.
Assigned to Tateho Kagaku Kogyo Kabushiki.
Tech Trends 1990. Ceramic Matrix Composites:
Technology and fndustriul Applications. Paris:
lnnovation 128.
'Textron Specialty Materials 1993a. Boron
Aluminum Preform Sheets. Textron Specialty
Materials. Lowell, MA, USA.
Textron Specialty Materials 1993b. Continuous
Silicon Carbide Metal Matrix Composites.
Textron Specialty Materials. Lowell, MA, USA.
Tricoles, G.P. 1988. Radome Electromagnetic
Design. In Antenna Handbook, ed. Y.T. Lo and
S.W. Lee, pp. 31-1 to 31-31. New York: Van
Nostrand Reinhold.
Tsirlin, A.M. 1985. Boron Filaments. In Strong Fibres,
ed. W. Watt and B.V. Perov, pp.155-99. Vol.1 of
Handbook of Composites, Series ed. A. Kelly and
Yu. N. Rabotnov. Amsterdam: Elsevier Science
Publishers R.V.
168 Boron, high silica, quartz and ceramicfibers
Wagner, R.S. 1970. VLS Mechanism of Crystal
Growth. In Whisker Technology. ed. Albert P.
Levitt, pp. 47-119. New York John Wiley &
Sons.
Wawner, F.E. 1988. Boron and Silicon
Carbide/Carbon Fibers. In Fibre Reinforcements
for Composite Materials, ed. A.R. Bunsell, pp.
371425. Vol. 2 of Composite Materials Series,
Series ed. R.B. Pipes. Amsterdam: Elsevier
Science Publishers B.V.
Weddell, J.K. 1990. Continuous Ceramic Fibers. 1.
Text. Inst. 81 (4): 333-59.
Withers, J.C., Loutfy R.O. and Lee, C.T. 1988.
Process to Produce Titanium Diboride Whiskers
as Reinforcement for Metal and Ceramic
Composites. NSF Grant ISI-8760300. National
Science Foundation, Washington D.C. October
1988.
Xiao, H., Ai, X and Yang, H.S. 1993. Effect of
whisker orientation on toughening behavior
and cutting performance of SiCW-A1203 com-
posite. Mat. Sci. Technol. Vol. 9:21-25.
Yajima, S. 1985. Silicon Carbide Fibers. In Strong
Fibres, ed. W. Watt and B.V. Perov, pp. 201-37.
Vol.1 of Handbook of Composites, Series ed. A.
Kelly and Yu. N. Rabotnov. Amsterdam:
Elsevier Science Publishers B.V.
Yamamoto, A. 1985. Process for Preparing Silicon
Carbide Whiskers. US Patent 4 500 504. Feb. 19,
1985. Assigned to Tokai Carbon Co Ltd.
Yamamura,T., et al. 1988. Development of a New
Continuous Si-Ti-C-0 Fibre Using an
Organometallic Polymer Precursor. 1.Mater. Sci.
23: 2589-94.