Formation

of Ceramic Matrix
Composites Using Polymer
Precursors
A LICIA D IA S
Introduction: Ceramic Matrix Composites
Ceramic materials have attractive properties for
high performance applications
Many drawbacks/limitations
Brittle
Extremely high melting temps

Ceramic matrix composites (CMCs) can make

ceramic parts practical for more applications
CMCs can still be difficult to process
One method being developed: Polymer
Infiltration and Pyrolysis (PIP)

Turbine blades made from CMCs

Introduction: Polymer Derived Ceramics
PDCs have been used for ~40 years
Involve curing & pyrolysis of preceramic
polymer
Preceramic composed of organo-silicon
monomers

Cracking & porosity are major issues

Shrinkage occurs in transition to ceramic
Gases escape during pyrolysis
Difficult to get fully dense part
Issues carry over into PIP
Introduction: PIP
General process:
Infiltrate reinforcement with polymer
precursor
Shape/Mold
Cure at low temperature
Pyrolysis at high temperature (1000-
1400C)
Reinfiltration/Pyrolysis
Introduction: PIP
Polymer Infiltration and Pyrolysis (PIP) Process
Standard PMC Processing Steps

Lay-Up Autoclave
Resin Fabric Cure
Prepreg

Filler
Filament
Winding
Tow Vacuum Bag De-Tool

Ceramic Processing Steps

Seal Final
Coat & Machine Reinfiltration Green
NDE/QA Pyrolyze Pyrolysis Machine
if reqd
Nicalon Reinforced Polysilazane
Early development by Dow Corning in 1999
Reinforcing preceramic polymer matrix with
SiC (Nicalon) fibers
Hand layup & autoclave molding produced
best results
Reinfiltration & pyrolysis repeated 12-16 times
Resulting porosity of <5%
 continuous and shows very little bridging between fibers.
Coating thickness ranges from 0.3 to 0.7 #m. A typical as-
made microstructure for the composite is shown in Fig. 3.
The optical micrograph shows warp and fill fibers from the

Nicalon Reinforced Polysilazane

0!/90! ply lay-up used to fabricate these two dimensionally

Table 1
2 types of reinforcing fibers used: Ceramic Grade (CG) and HI Nicalon:
Comparision of CG Nicalon and HI-Nicalon fiber properties

CG Nicalon HI-Nicalon

Tensile strengh (GPa) 2.97 2.76

Elastic modulus (GPa) 193 269
Filaments diameter (#m) 15 14
Bulk density, (g cm "3) 2.55 2.74
Filament/tow 500 500
Denier (g 9000 m "1) 1800 1800

Composition (wt%)
Silcon 58 63.7
Carbon 31 35.8
Oxygen 11 0.5
Fig. 2. SEM o
Comparison of Fiber Properties
Nicalon Reinforced Polysilazane
R. Jones et al. / Composites: Part A 30 (1999) 569575 571

Table 2
CMC properties

Results of Temperature (!C) CG Nicalon CMC HI-Nicalon CMC

composite Tensile strengh (MPa)

testing: 20
1000
250
265
360
360
1200 290 347

Tensile modulus (GPa)

20 95.2 120
1000 88.4 115
1200 85.0 100

Double notch shear strengh (MPa)

20 35 37
1000 26 37
1200

Compression strengh (MPa)

20 431

Density (g cm "3)
20 2.12.2 2.22.3

those reinforced with HI-Nicalon. Table 2 summarizes the

Carbon Nanotube Reinforced
Composites
Carbon fiber common reinforcement for high performance composites
2011 study by National University of Defense Technology
Create composites reinforced by carbon fiber AND multi-walled carbon
nanotubes (MWNTs)

4-Step process
Nanotubes added to A-PMS precursor
Carbon-Fiber preforms infiltrated with precursor
Parts cured for 1 hr @ 470C
Reinfiltrated/re-cured 10x

Multi-Walled Carbon Nanotube

for 1 h, under N2. This process was then repeated. Finally, the sam- the mechanical properties tests were performed, scanning electron 3. Results and discussion
the pyrolyzed products was studied using X-ray diffraction (XRD, tion of PMS wi
ples were pyrolyzed at 1300 !C for 1 h; this process was carried out microscopy (SEM, JSM-5600LV) was employed to observe the frac-
Siemens D500, Cu Ka). The Archimedes principle was employed to ultrasonic condi
in N2 ambience. All of the above procedures make up one cycle of ture surfaces of the composites. Detailed information on the mor- After 350 ultrasonic treatment, the dispersion state of the MWNTs
measure the bulk densities of the resulting composites. The flexural in the (a) was investigated using SEM. Fig. 1a shows the A-
A-PMS ing the ultrason

Carbon Nanotube Reinforced

this process. In this study, 10 cycles were performed. phologies
strength wasof the composites
measured was obtained using
using a three-point-bending transmission
test on speci-
300
spectra for A-PM
PMS containing the homogeneously dispersed MWNTs with no
Fourier transform infrared (FT-IR) spectra were obtained in the electron
mens microscopy4.0(TEM,
of dimensions mm "HF-2000
4.5 mm "Hitachi,
60 mm, Japan). Before
with a 50 mm TEM 250 SiH absorption
entanglement and agglomeration. The higher magnification

Load (N)
range of 4000400 cm!1, using a Nexus 670 Fourier transform infra- observation,
span and a 0.5 the samples
mm/min were milled
crosshead in an agate mortar
speed (Instron-1342). and ultra-
To deter- 200 image shows that some individual MWNTs partly pro- tude after the u
(Fig. 1b)
red spectrophotometer. KBr discs were used, which were prepared sonically
mine dispersed
the fracture in ethanol,
toughness andedge
(KIC), single thennotched
transferred on carbon-
beam (SENB) Cf/SiC/1.5wt.%
150out of the surface of the precursor, MWNTs unchanged; this
truded and that some pores
by compressing a finely ground mixture of about 5 mg of the sample coated copper grid. on notched specimens of dimensions acted with the r

Composites
tests were applied in the100
surface resulted from the removal of MWNTs;MWNTs
Cf/SiC/0.5wt.% these findings
and 300 mg of KBr powder. Thermal analysis (TG, Netzsch STA 449C) 4.0 mm " 8.0 mm " 60 mm (with a notch 0.3 mm in width and To improve th
indicated
50
that the MWNTs were well-dispersed
Cf/SiC in the A-PMS, and
4.0 mm in depth), with a 0.05 mm/min crosshead speed and a the samples we
was performed by raising the temperature at the rate of 25 !C/min, that the MWNTs were well wetted by the precursor. shows FT-IR spe
up to a temperature of 1300 !C, in flowing Ar gas. The structure of 3. Results and discussion In view of the0.2fact that
0.4the A-PMS
0.6 was0.8synthesized
1.0 via1.2the reac- PMS/MWNT co
the pyrolyzed products was studied using X-ray diffraction (XRD, tion of PMS with excess Displacement
SbCl3 at room (mm) temperature and under 2106 cm!1whi
Siemens D500, Cu Ka). The Archimedes principle was employed to After
350 ultrasonic treatment, the dispersion state of the MWNTs ultrasonic conditions, the A-PMS structure may have changed dur- tionsignificant
measure the bulk densities of the resulting composites. The flexural (a) ing the460
ultrasonic dispersion of the MWNTs. Fig. 2 shows the FT-IR
Results: in the
300A-PMS was investigated using SEM. Fig. 1a shows the A-
spectra for(b)
that some SiH

Flexural strength (GPa)

strength was measured using a three-point-bending test on speci- A-PMS, and for A-PMS after ultrasonic treatment. The could be describ
PMS250 containing the homogeneously dispersed MWNTs with no
mens of dimensions 4.0 mm " 4.5 mm " 60 mm, with a 50 mm SiH absorption
420 peak at 2106 cm!1 decreased slightly in magni-
Flexural strength and fracture toughness increased w/ MWNT content entanglement and agglomeration. The higher magnification

Load (N)
span and a 0.5 mm/min crosshead speed (Instron-1342). To deter- 200 tude after the ultrasonic treatment, while the other peaks remain # SiAH HASi
(Fig. 1b) image shows that some individual MWNTs partly pro- unchanged; this indicated that the SiH groups in the A-PMS re-
mine the fracture toughness (KIC), single edge notched beam (SENB) C
150 out of the surface of the precursor,
f /SiC/1.5wt.% MWNTs 380
truded and that some pores
For 1.5 wt% MWNT: 30% increase in both areas over CF reinforced CMC
tests were applied on notched specimens of dimensions in the
100surface resulted from the removal Cf/SiC/0.5wt.%
of MWNTs; MWNTs
acted with the residual SbCl3 under the ultrasonic treatment.
these findings To improve the ceramic yields of the A-PMS/MWNT composites,
340
Moreover, th
4.0 mm " 8.0 mm " 60 mm (with a notch 0.3 mm in width and indicated
50 that the MWNTs were C /SiC
well-dispersed
f in the A-PMS, and cured A-PMS/M
the samples were cured after each infiltration procedure. Fig. 3
4.0 mm in depth), with a 0.05 mm/min crosshead speed and a that the MWNTs were well wetted by the precursor. 2158 cm!1), cor
shows FT-IR spectra for the A-PMS, cured A-PMS, and cured A-
0.2 fact that
0.4 the 0.6 0.8 synthesized
1.0 1.2 300 and the change
In view of the A-PMS was via the reac- 0
PMS/MWNT composite. 0.2 0.4 Fig.0.6 3 0.8
shows 1.0 that
1.2 the
1.4 peak1.6 at
The pyrolysis
tion of PMS with excess Displacement (mm) temperature and under
SbCl3 at room 2106 cm!1which was MWNTs attributedcontents (wt.%)
to the Si-H stretching vibra-
MWNTs was inv
ultrasonic conditions, the A-PMS structure may have changed dur- tionsignificantly decreased in magnitude after curing, indicating
350 460 that both the cu
(a)

Fracture toughness (MPam1/2)

ing the ultrasonic dispersion of the MWNTs. Fig. 2 shows the FT-IR that some SiH was consumed in the curing process. The reaction
(b) (c) posite exhibited

Flexural strength (GPa)

300 could 22
be described by the following scheme:
spectra for A-PMS, and for A-PMS after ultrasonic treatment. The approximately 4
250 420
SiH absorption peak at 2106 cm!1 decreased slightly in magni- almost no weigh
21
Load (N)

200 tude after the ultrasonic treatment, while the other peaks remain # SiAH HASi #!# SiASi # H2 samples were c
380
unchanged; this indicated that the SiH groups in the A-PMS re- 20 works and 3-dim
150 Cf/SiC/1.5wt.% MWNTs
the temperature
acted with the residual SbCl3 under the ultrasonic treatment. Moreover,
19 the SiH peak for both the cured A-PMS and the
100 Cf/SiC/0.5wt.% MWNTs downwards. The
To340
improve the ceramic yields of the A-PMS/MWNT composites, cured A-PMS/MWNT composite split into two peaks (2104 and
Cf/SiC the samples un
50 the samples were cured after each infiltration procedure. Fig. 3 2158 cm 18 !1), corresponding to the formation of SiC units [25]
tures. The weigh
300 and the
shows FT-IR 0spectra
0.2
for
0.4
the0.6
A-PMS,
0.8
cured
1.0
A-PMS,
1.2 1.4
and1.6cured A- 17change of the chemical environment. A-PMS/1.5 wt.%
0.2 0.4 0.6 0.8 1.0 1.2 PMS/MWNT composite. Fig. 3 shows The pyrolysis 0 behavior
0.2 0.4
of the0.6cured0.8 A-PMS
1.0 and1.2 A-PMS/1.5
1.4 1.6 wt.%
MWNTs contents (wt.%) that the peak at MWNTs contents (wt.%)
the introduction
Displacement (mm) 2106 cm!1which was attributed to the Si-H stretching vibra- MWNTs was investigated using TG (see Fig. 4). In Fig. 4, we can see loss was observ
tionsignificantly decreased in magnitude after curing, indicating that both the cured A-PMS and the A-PMS/1.5 wt.% MWNT com- entirely converte
Fracture toughness (MPam1/2)

Fig. 7. (a) Load-displacement curves for the obtained composites, (b) flexural
460
that some(c)
SiH was consumed in the curing process. The reaction posite exhibited
strength, three-stage
and (c) fracture weight
toughness of loss, composites
the obtained with lossesas aoccurring
function of at yield of the cur
(b)
Flexural strength (GPa)

22 approximately
MWNT content. 400 !C, 800 !C and above 800 !C. In the first stage, composite excee
could be described by the following scheme:
420
almost no weight loss could be observed. That indicated that the
21
samples were converted into semi-organic structures with net-
# SiAH
20
HASi #!# SiASi # H2 works and 3-dimensional structure. During the second stage, when
380 the temperature was above 400 !C, the TG curves slope rapidly
19 downwards. The weight loss was approximately 18%, meaning that
Moreover, the SiH peak for both the cured A-PMS and the
340 the samples underwent a rapid conversion into inorganic struc-
cured18A-PMS/MWNT composite split into two peaks (2104 and
tures. The weight loss in the cured A-PMS was higher than in the
2158 cm ), corresponding to the formation of SiC units [25]
!1
A-PMS/1.5 wt.% MWNT composite, which could be attributed to
17
300 0 of0.2
and the change 0.4 0.6 environment.
the chemical 0.8 1.0 1.2 1.4 1.6
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 the introduction of the MWNTs. In the last stage, almost no weight
Additive Manufacture of SiCN Matrix
Most recent development (2016)
Polysilazane matrix reinforced by SiC fiber
AM of preceramic used to form defect-free matrix
10-100 nm thick layer deposition
Thin layers rapid pyrolysis

Process (repeated 8-80 times)

SiCN deposited on end of fiber tow
Cross linked at 300-350C
Pyrolysis in infrared radiation furnace
Cooled in heat sink

Done manually in glove box (potential for automation)

Additive Manufacture of SiCN Matrix
Results:
Defect free matrix achieved
# cycles porosity
Higher UTS than uncoated fibers
Slightly higher ductility than
uncoated fibers
Research still preliminary/small
scale
Additive Manufacture of SiCN Matrix
Results:
Defect free matrix achieved
# cycles porosity
Higher UTS than uncoated fibers
Slightly higher ductility than
uncoated fibers
Research still preliminary/small
scale
Conclusions
CMCs are the future of high performance
materials
Can PIP be improved to the point that its practical
for widespread use?
2 necessary improvements
Improved density
Industrialized process

Will always be specialized process