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#2003 The Japan Institute of Metals
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.
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
1000 75
(a) (b)
800 Young's Modulus
50
600
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
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.
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)
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
(6) The current Mg base laminated composite possesses 9) H. A. Katzman: J. Mater. Sci. 22 (1987) 144–148.
10) F. Wu, J. Zhu, K. Ibe and T. Oikawa: Compos. Sci. Tech. 58 (1999) 77–
much higher longitudinal specific modulus and strength
82.
than metallic Mg, Al, Ti alloys and steel, as well as 11) L. B. Vogelesang and J. W. Gunnink: Mater. Design 7(6) (1986) 287–
other Al base laminated composites such as ARALL 300.
and CARALL. 12) C. T. Lin, P. W. Kao and F. S. Yang: Compos. 22 (1991) 135–141.
13) C. T. Lin and P. W. Kao: Mater. Sci. Engng. A190 (1995) 65–73.
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sponsorship from National Science Council under the project Krock, eds., Metal-Matrix Composites, (Academic Press, Inc., New
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