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Materials Transactions, Vol. 44, No. 8 (2003) pp.

1613 to 1619
#2003 The Japan Institute of Metals

Fabrication of High Performance Magnesium/Carbon-Fiber/PEEK


Laminated Composites
M. C. Kuo1;2 , J. C. Huang1; * , M. Chen1 and M. H. Jen3
1
Institute of Materials Science and Engineering; Center for Nanoscience and Nanotechnology, National Sun Yat-Sen University,
Kaohsiung, Taiwan 804, R. O. China
2
Department of Applied Fiber Style, Kun Shan University of Technology, Tainan, Taiwan 700, R. O. China
3
Department of Mechanical and Electro-Mechanical Engineering, National Sun Yat-Sen University,
Kaohsiung, Taiwan 804, R. O. China

Low density and high performance Mg-based laminated composites were fabricated by means of sandwiching the AZ31 Mg foils with the
carbon-fiber/polyether ether ketone (PEEK) prepreg through hot pressing. Proper surface treatments of AZ31 sheet using CrO3 base etchants are
necessary in order to achieve good interface bonding characteristics. The resulting Mg base laminated composite, with a low density of 1.7 Mg/
m3 , exhibits high modulus of 75 GPa and tensile strength of 932 MPa along the longitudinal direction. The experimentally measured tensile
modulus and strength data along both the longitudinal and transverse directions are within 90–100% of the theoretical predictions by rule of
mixtures, suggesting that the bonding between layers and the load transfer efficiency are satisfactory.

(Received January 23, 2003; Accepted June 2, 2003)


Keywords: magnesium alloy, fiber reinforced composite, polyether ether ketone polymer, hot pressing, tensile test

1. Introduction cated graphite magnesium composites. In addition, SiC


coating on graphite fibers to improve the wetting behavior
Magnesium alloys have attracted considerable attention between graphite fibers and molten magnesium has been
and interest worldwide during the past few years. Because of conducted.10)
its low density of 1.7–1.8 Mg/m3 (similar to or only slightly So far, CF/Mg composites were mainly fabricated by
higher than the densities of most polymers and polymer means of liquid metal infiltration, CVD, powder infiltration
composites), this metal provides the possibility of weight and hot-forming, but none of the resulting composites could
saving in various metallic structures in aircraft, vehicles and fully utilize the fiber properties. It would be interesting to
other transportation equipment.1–3) Moreover, magnesium explore the feasibility to laminate the Mg sheet directly with
alloys have been, or have potential to be, applied in other the well established CF/PEEK prepreg, similar to the
areas due to their characteristic natures of high specific previous cases developed for the Al base laminated compo-
strength and stiffness, superior damping capacity, high sites.11–13)
thermal conductivity, high dimensional stability, and good It is well-known that fiber-reinforced aluminum laminates
machinability.4) (FRALL) have been successfully fabricated and commer-
On the other hand, it is well known that the carbon fiber cialized.11) The aramid fiber-reinforced aluminum laminates
(CF) reinforced polyether ether ketone (PEEK) polymer (ARALL) were marketed by the Aluminum Company of
composites (CF/PEEK) possess extraordinary specific America for the applications such as aircraft lower wing skin,
strength and stiffness along the longitudinal (or fiber) fuselage and tail skins.12) Moreover, carbon fiber-reinforced
direction, as compared with steel, Al or Ti alloys.5,6) The aluminum laminates (CARALL) show a superior crack
CF/PEEK composite appears to be a shining star among all propagation resistance under tension-tension fatigue.13) All
PEEK composites, and is being considered as the candidates the above developed FRALLs contain epoxy-resin polymer,
to replace the conventional epoxy based composites for consisting of alternating layers of thin aluminum sheets
aerospace applications. bonded by layers of high-strength fiber/epoxy prepreg. The
Meanwhile, carbon fibers reinforced magnesium compo- service temperature is not expected to exceed 373 K.
sites have been recognized as new promising structural In this study, the laminated composites are developed for
materials, due to their high specific strength and stiffness, the Mg base alloys, using the widely applied AZ31 sheets,
high electrical and thermal conductivities. The main problem reinforced with the high strength unidirectional CF/PEEK
of fabricating these materials is that the molten magnesium prepreg. The PEEK polymer can sustain its mechanical
does not wet or bond to carbon fibers. As a result, it is difficult properties up to 423 K or even 473 K,14,15) thus it is postulated
to achieve efficient load transfer from the matrix to the fibers that the current Mg base Mg/CF/PEEK laminated compo-
in accordance with the rule of mixture (ROM). There have sites might be utilized at higher temperatures. Commercial
been many developments proposed to solve this problem, Mg materials usually exhibit tensile strength around 200–
including coating of titanium-boron by chemical vapor 300 MPa at room temperature. It is aimed also to further
deposition (CVD) on carbon fibers7) or coating of silicon strengthen the Mg alloys. Since the Mg volume fraction for
dioxide on carbon fibers.8,9) Katzman9) successfully fabri- the current developed composites is always above 60%, the
composite is regarded as an Mg base laminated composite.
*Corresponding author, E-mail: jacobc@mail.nsysu.edu.tw
1614 M. C. Kuo, J. C. Huang, M. Chen and M. H. Jen

2. Experimental the surface roughness of the Mg sheet, the removal of Mg


oxide by proper etchants, the packing sequence, the hot press
The AZ31 (Mg–3 mass%Al–1 mass%Zn–0.2 mass%Mn) temperature, pressure, duration, and the cooling rate. It was
Mg ingot was supplied by CDN Genova Ventures LTD., found that the surface-etching step appeared to be most
Canada. The alloy was hot rolled into thin sheet measuring critical. Initially, the AZ31 sheets were hot bonded with the
2 mm in thickness, with an average grain size of 34 mm and a APC-2 prepreg without any etching process, but only
density of 1.77 Mg/m3 . Then the 2 mm AZ31 Mg sheets were roughened by sandpaper grounding. Upon cooling, the
further warm rolled at 573 K to a final thickness of 0.5– resulting laminate always showed severe delamination along
0.6 mm. The grain size became around 10 mm. the interface between the AZ31 and APC-2 layers, apparently
The polymer material used is the AS-4 continuous carbon due to the poor bonding and the large difference of CTE
fiber reinforced PEEK prepreg, designated as APC-2 and between the carbon fiber and Mg alloy.
fabricated by the ICI/Fiberite Company, USA. The matrix of In order to overcome the delamination problem, a poly-
APC-2 is a tough, ductile, and semicrystalline thermoplastic olefin-based adhesive was firstly tried. Three layers of
PEEK polymer with a glass transition temperature Tg of polyolefin adhesive films with a layer thickness of
416 K and melting temperature Tm of 616 K. The density of 0:1 mm was placed between the AZ31 sheet and APC-2
the PEEK polymer is 1:3 Mg/m3 . The APC-2 prepreg prepreg to act as a binder. The AZ31 sheets were also
contains 61 vol% or 68 mass% continuous AS-4 carbon roughened with sandpapers prior to lamination. The forming
fiber (with a diameter of 7 mm and density of 1:77 Mg/ temperatures were kept low at 473 K in preventing from
m3 ) in the PEEK polymer matrix. The resulting density and adhesive decomposition, with the same forming pressure of
the thickness of one single prepreg layer are about 1.6 Mg/m3 1.4 MPa and time duration of 15 min. It was shown that the
and 120–150 mm, respectively. Mg/APC-2 laminate bonded with the 3-layer polyolefin
Prior to lamination with the APC-2 prepreg, the slimmed adhesive at 473 K showed no delamination at the interface,
AZ31 sheets were subjected to pretreatment by special but the adhesive would be squeezed by the forming pressure
chemicals in order to create the rough surfaces for better and flow out of the sheets. The viscous flow of the adhesive
bonding with the APC-2 prepreg. The first try was to could result in sliding of the AZ31 sheet and the APC-2
mechanically polish the sheet surface using #100 SiC prepreg with each other under a pressure of 1.4 MPa at 473 K.
abrasive papers without chemical etching. The following A lower holding temperature coupled with a lower forming
groups were etched by various chemical combinations pressure would reduce the sliding problem, but the bonding
including HCl, HNO3 , H2 SO4 , (NO2 )3 C6 H2 OH, and CrO3 - quality became degraded. The adhesive seemed to offer a
base etchants, etc. bonding with minimum delamination; however, the bonding
Various layers of the APC-2 prepreg were sandwiched strength was found to be low. It appears easy to tear off the
with the AZ31 sheets to produce Mg/CF/PEEK laminated lamina from the interface. Meanwhile, the service temper-
composites. The stacking sequence was AZ31/APC-2/ ature of the bonded laminated composite with adhesive
AZ31/APC-2/AZ31 in unidirectional array (with the rolling would be again lower than 373 K.
direction parallel to the continuous fiber direction). Forming In order to bond the laminate without using the adhesive,
of the Mg/APC-2 composite was conducted by means of hot numerous combinations of HNO3 , H2 SO4 , and other base
pressing at 623–703 K under a pressure of 1–10 MPa for a chemical etchants were tried, and the etchant combinations
time duration of 10 min to 1 h. The hot pressing was with transition-metal ions appeared to be most effective. The
conducted under vacuum at 7  103 Pa. picric acid ((NO2 )3 C6 H2 OH) based etchant would result in
Tensile tests were conducted in accordance with the better bonding, but partial delamination still occur from the
ASTM standard E8M-89. The gauge length is set to be composite edge. It was later found that the CrO3 based
40 mm. The loading direction is parallel to the longitudinal coupling agent resulted in satisfactory bonding. The laminate
fiber direction, and the loading strain rate is 4  104 s1 . pretreated by this promising coupling agent revealed no
A strain gage was attached on the gauge for the measurement delamination throughout the processing and subsequent
of elastic modulus and failure elongation. The fractured machining and tensile loading. The detailed bonding mech-
specimens are observed by a JEOL JEM-6400 scanning anisms are still under investigation and will be presented
electron microscope (SEM), operating at 20 kV. elsewhere. It is postulated, as shown in Fig. 1, that the
electron configuration of chromium might account for the
3. Results unique characteristics of CrO3 base coupling agent; the

3.1 Fabrication
The delamination between the Mg and APC-2 pregreg has CrO3
H2O H2CrO4
been the major issue during fabrication. It was expected that
the poor bonding between the prepreg and Mg alloy might be H2CrO4 + Mg
2 + MgCrO4 +
+
2H
due to the difference of surface energies between Mg and 0 Mg O
MgCrO4 + 400 C
carbon fiber and also to the large difference of coefficient of C O Cr
O
thermal expansion (CTE).16) Without proper treatments, the O C + H2O
PEEK Coordination
laminated composite was found to split severely upon
cooling. Fig. 1 The proposed coordination mechanism for the PEEK and
The processing variables examined in this study include chromium ion.
Fabrication of High Performance Magnesium/Carbon-Fiber/PEEK Laminated Composites 1615

unoccupied d orbital in the electron configuration of the layers. The thickness of the resulting laminated composites
chromium atom could make its ion characteristically forming depends on the layer number. For example, a five layer
coordination compounds.17) In this case, the oxygen atom in composite containing three Mg foils (each 0:55 mm thick)
the backbone of PEEK has lone-paired electrons and, and two APC-2 plies (each 0:55 mm thick with 4 APC-2
consequently, this oxygen atom may be able to form a ligand layers) will measure 2:7{2:8 mm in thickness. In that case,
bonding to the chromium ion, resulting in coordinate the resulting Mg base composite after hot pressing would
covalent bond. Instead of the week van der Waals bonding contain 61 vol% AZ31 Mg and 39 vol% APC-2 prepreg (i.e.,
formed between Mg and PEEK when using other surface 24 vol% carbon fibers and 15 vol% PEEK polymer).
etchants, the laminate pretreated with chromium oxide base
coupling agent could impart a characteristic coordinate 3.2 Room temperature tensile properties
covalent bond at the interface between the APC-2 prepreg The room temperature ultimate tensile stress-strain curves
and Mg phase. As a consequence, this laminate exhibited a at 4  104 s1 for the longitudinal and transverse specimens
good bonding and no delamination along the interface during are shown in Figs. 3(a) and 4(a), respectively. The enlarged
slow or rapid cooling, as well as following aging and view of the elastic portion is shown in Figs. 3(b) and 4(b), in
machining. which the Young’s modulus for the Mg/CF/PEEK laminated
For forming of the composites without adhesive, the composite was calculated. Table 1 lists the data on the
pressing temperature needs to be above the Tm of the PEEK experimentally measured mechanical properties of the AZ31
polymer (638 K); and 673 K was found to be optimum, Mg matrix, the reinforcement layer (CF/PEEK) and the Mg/
similar to the finding in previous literature.18) At even higher CF/PEEK composite, as well as the theoretically predicted
temperatures, the out-flow of the melted polymer became values in accordance with the rule of mixture (ROM).
serious and difficult to control. With a high pressing load As shown in Table 1, the laminated Mg composite exhibits
greater than 2 MPa, the molten polymer would be squeezed anisotropic behavior. The ratios of the stiffness and tensile
out from the laminate. The loading pressure can be varied in strength along the longitudinal and transverse directions are
accordance with the pressing temperature. A lower temper- 2.4 and 4.9, respectively. Along the longitudinal direction,
ature can be coupled with a higher loading pressure. the stiffness increases from 45 GPa of the AZ31 Mg base
Figure 2 shows the enlarged schematic drawing of the alloy to 75 GPa of the composite; and the strength increases
resulting Mg based laminated composite, containing five from 290 MPa of AZ31 to 932 MPa of the composite, both a
significant increment. The high tensile strength of 932 MPa
for the Mg base composite is also much higher than the
‘ultrahigh strength’ of 610 MPa for the newly developed Mg–
AZ31 Sheet
thickness 0.5-0.6 mm Zn–Y alloys.19) It appears that the current fabrication method
1
2
for the Mg/CF/PEEK laminated composite is feasible,
3
4
effective, and easy-to-process, as compared with the liquid
5 metal infiltration method mentioned above.
The longitudinal specific stiffness and specific strength,
with the consideration of density, of the Mg/CF/PEEK
2.7-2.8 mm laminated composite are about 2–3 times of those of AZ31.
In other word, when applied as a long beam or long plate, the
CF/PEEK prepreg Mg/CF/PEEK laminated composite provides a much more
thickness 0.5-0.6mm
promising material than Mg alloys for the purpose of weight-
Fig. 2 Schematic drawing of the Mg based laminated composite, layers 1, saving structural characteristics.
3 and 5 are Mg and layers 2 and 4 are APC-2 (with 4 foils). The In comparison with other metallic alloys, the current Mg
longitudinal direction is indicated. based laminated composite also exhibited much higher
Engineering Stress, S/MPa

Engineering Stress, S/MPa

1000 75
(a) (b)
800 Young's Modulus
50
600

400 74.6 GPa


25
200

0 0
0.00 0.02 0.04 0.06 0.08 0.0000 0.0002 0.0004 0.0006 0.0008 0.0010
Engineering Strain, e Engineering Strain, e
Fig. 3 (a) Room temperature tensile stress strain curve of the Mg/CF/PEEK Mg based laminated composite along the longitudinal
direction, and (b) extraction of the Young’s modulus of the Mg/CF/PEEK Mg based laminated composite.
1616 M. C. Kuo, J. C. Huang, M. Chen and M. H. Jen

Engineering Stress, S/MPa

Engineering Stress, S/MPa


250 35
(a) 30
(b)
200 Young's Modulus
25
150 20
100 15 30.8 GPa
10
50
5
0 0
0.00 0.01 0.02 0.03 0.04 0.0000 0.0002 0.0004 0.0006 0.0008 0.0010
Engineering Strain, e Engineering Strain, e
Fig. 4 (a) Room temperature tensile stress strain curve of the Mg/CF/PEEK Mg based laminated composite along the transverse
direction, and (b) extraction of the Young’s modulus of the Mg/CF/PEEK Mg based laminated composite.

Table 1 Summary of the mechanical properties along the longitudinal (L) and transverse (T) directions. The volume fractions of AZ31,
carbon fiber, and PEEK in the resulting Mg/CF/PEEK composite are 61%, 24%, and 15% in volume, respectively.

Property AZ31 CF PEEK CF/PEEK CF/PEEK Mg/CF/PEEK Mg/CF/PEEK


Mg (L) (L) (T) (L) (T)
Exp Exp Exp Theo Exp Theo Exp Theo Exp Theo Exp
3
Density d (Mg/m ) 1.77 1.77 1.30 1.60 1.60 1.70 1.70
Stiffness E (GPa) 45 230 3.6 142 134 9 8.9 82.8 74.6 31.0 30.8
YS (MPa) 220 — 91 — — — 225 — 125
UTS (MPa) 290 3400 170 2127 2130 20 80 975 932 185 188
Specific stiffness
E=d
(GPa/Mg/m3 ) 25.4 129.9 2.8 83.8 5.6 43.9 18.1
Specific strength
UTS/d
(MPa/Mg/m3 ) 164 1921 131 1331 50 548 111
Elongation 15 1.1 50 1.5 1.3 6 3
(%)
Exp: Experimental data, Theo: Theoretical data.

specific modulus and tensile strength in the longitudinal 3.3 SEM observations
direction, as compiled in Table 2. In general, the specific As shown in Fig. 5(a), there are fiber pull-out and carbon
properties of the current Mg based composite along its fiber broken phenomena in the APC-2 layer under the
longitudinal direction are around double or triple of those for longitudinal tensile loading, accounting for the load transfer
the metallic alloys. of tensile stress from matrix to carbon by means of interfacial
shear stress. In Fig. 5(b), it is apparent that the failure
positions of Mg and fibers are closely related. Good bonding
between APC-2 and Mg is evident. Occasional debonding of
PEEK resin and carbon fibers within APC-2 can also be seen
Table 2 Comparison of the current Mg laminated composites with other
commercial structural metallic alloys, such as AZ91 Mg, 6061 Al, Ti– in Figs. 5(b) and (c). The ductile behavior of the AZ31 Mg
6Al–4V and 1040 steel. matrix can be realized by the abundant dimples in Fig. 5(d). It
seems that the overall failure of the laminated composite,
Property Mg/CF/PEEK Mg alloy Al alloy Ti alloy Steel
under longitudinal loading, starting from Mg failure, and
(AZ91) (6061) (Ti–6Al–4V) (1040)
ending with carbon fiber broken and pull out. Multiple failure
d (Mg/m3 ) 1.70 1.77 2.70 4.20 7.80
modes were observed, also evident from the multiple jerky
E (GPa) 75 45 72 135 210
steps in Fig. 3(a). The load transfer from the Mg matrix to
UTS (MPa) 932 290 350 1000 600
continuous fiber seemed to be highly efficient.
E=d 44 25 27 32 27
On the other hand, much simpler failure was observed
(GPa/Mg/m3 )
when loaded along the transverse direction. The fracture
UTS/d 548 163 130 238 77
surfaces of both Mg and APC-2 are flat, as shown in Fig. 6(a)
(MPa/Mg/m3 )
and the flow stress curve in Fig. 4(a) is also smooth until near
Fabrication of High Performance Magnesium/Carbon-Fiber/PEEK Laminated Composites 1617

(a) (b)

(c) (d)

__
10 µm
Fig. 5 SEM micrographs of the fractured specimens of Mg/CF/PEEK laminated composite, taken from the longitudinal specimens.

(a) (b)
Mg

____ __
100 µm 10 µm

(c) (d)

__ __
2 µm 10 µm

Fig. 6 SEM micrographs of the fractured specimens of Mg/CF/PEEK laminated composite, taken from the transverse specimens.

overall fracture. Occasional delamination between Mg and mode in Mg in Fig. 6(d) appears the similar for both the
APC-2 can be seen in Fig. 6(b), and this delamination transverse and longitudinal specimens. The final failure at
behavior seems to be responsible for the sudden drop of flow 188 MPa seems to correspond to the fracture of Mg matrix,
stress at e  0:02{0:026 in Fig. 4(a). As tilted to near edge-on since it partitions the same ratio of load (188 MPa over
for the fibers, debonding between carbon fiber and PEEK has 290 MPa for the UTS of the Mg matrix, i.e. 188/290 or
been found, as indicated by arrows in Fig. 6(c). The fiber 65%) as its volume fraction (61%).
itself would carry no load under transverse tests. The fracture
1618 M. C. Kuo, J. C. Huang, M. Chen and M. H. Jen

Table 3 Comparison of the current Mg laminated composites along the longitudinal (L) and transverse (T) directions with previously reported data on the
ARALL (2024Al/AF/epoxy)22) and CARALL (2024Al/CF/epoxy).12,13)

Property Mg/CF/PEEK Al/AF/epoxy Al/CF/epoxy Mg/CF/PEEK Al/AF/epoxy Al/CF/epoxy


ARALL CARALL ARALL CARALL
(L) (L) (L) (T) (T) (T)
d (Mg/m3 ) 1.70 2.29 2.35 1.70 2.29 2.35
E (GPa) 75 64 84 31 49 56
YS (MPa) 225 395 485 125 228 255
UTS (MPa) 932 717 750 188 317 285
Elongation 6 2.5 1.4 2.5 12.7 9.4
(%)
E=d 44 28 36 18 21 24
(GPa/Mg/m3 )
UTS/d 548 313 319 111 138 121
(MPa/Kg/m3 )

Present work.

4. Discussion matrix used was typically the high strength aircraft-used


2024-T3 Al, with a density of 2.77 Mg/m3 and tensile
4.1 Theoretical predictions modulus, YS, UTS and elongation of 71 GPa, 355 MPa,
Theoretical predictions for the elastic modulus were done 445 MPa, and 12%, respectively,21) and the polymer matrix
according to the well-known ROM.20) of the prepreg is epoxy. Table 3 compares the current results
EL ¼ Vf Ef þ ð1  Vf ÞEm ð1Þ on AZ31Mg/CF/PEEK with previously reported data on
2024Al/AF(CF)/epoxy,12,13,22) with similar fiber volume
and fractions.
Ef E m It can be seen that the current Mg base laminate composite
ET ¼ ð2Þ
Ef ð1  Vf Þ þ Em Vf possesses the lowest density, but the highest longitudinal
tensile strength. The longitudinal specific modulus and
where EL and ET are the modulus for the longitudinal and specific strength of Mg/CF/PEEK are both much higher
transverse directions, Vf the fiber volume fraction, Ef and Em than those of the aluminum counterparts. Nevertheless, due
the fiber and matrix modulus. These equations were first
to the Mg matrix alloy used in this study is the relatively
applied to calculate the theoretical modulus and strength for
lower strength AZ31 Mg alloy, with a lower tensile modulus,
the APC-2 pregreg. The values for the Mg/APC-2 can be
YS, and UTS of 45 GPa, 220 MPa, and 290 MPa (much lower
simply evaluated by eq. (1) using their corresponding data.
than those of 2024 Al), the transverse properties of Mg/CF/
As for the tensile strength, another set of equations were PEEK are slightly inferior to those of ARALL and CARALL.
used20) for the strength of the APC-2 prepreg. Since the transverse properties are basically determined by
L ¼ Vf f þ ð1  Vf Þm ð3Þ the matrix material, it is postulated that improvement can be
made with the replacement of AZ31 by other higher strength
and
rffiffiffiffiffiffi! Mg base alloys.
Vf
T ¼ m 12 ð4Þ
 5. Conclusion

The final strength for combining the Mg and APC-2 was (1) For better bonding between Mg and APC-2 prepreg,
simply calculated by eq. (3). proper surface treatments, including roughening and
From Table 1, it can be seen that both the measured special etching, of the AZ31 Mg alloy are necessary.
stiffness and strength of the laminated composite are very (2) The resulting Mg/CF/PEEK laminated composite can
close to the calculated value. Basically, the agreement effectively enhance the tensile stiffness and strength of
between the experimentally obtained and theoretically AZ31 Mg alloy to nearly 100% ROM values.
predicted values is above 90%. It indirectly suggests that (3) With the addition of 39 vol% APC-2 prepreg, the Mg/
there exists a perfect interface bonding between Mg and CF/PEEK laminated composite can triple the UTS of
APC-2 prepreg. The load transfer was efficient across the AZ31 Mg alloy to as high as 932 MPa.
interface. (4) Based on SEM examinations, the interfacial bonding
between APC-2 and Mg alloy is satisfactory. As a
4.2 Comparison with previous results on ARALL and result, the tensile load transfer can be prevailed by
CARALL means of shear stress occurring on the interface.
Previous efforts have resulted in promising aluminum base (5) The final failure of the composite under longitudinal
laminated composites,11–13) such as the aramid fiber-rein- loading is due to the failure of carbon fibers; while that
forced aluminum laminates (ARALL) and carbon fiber- under transverse loading is due to the Mg fracture.
reinforced aluminum laminates (CARALL). The aluminum
Fabrication of High Performance Magnesium/Carbon-Fiber/PEEK Laminated Composites 1619

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