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Materials Science and Engineering A302 (2001) 258– 267

www.elsevier.com/locate/msea

EMI shielding effectiveness of metal-coated carbon fiber-reinforced


ABS composites
Shinn-Shyong Tzeng *, Fa-Yen Chang
Department of Materials Engineering, Tatung Uni6ersity, 7 -1 Teh-Hui Street, Taipei 104, Taiwan, ROC

Received 8 May 2000; received in revised form 24 September 2000

Abstract

EMI shielding effectiveness of copper- and nickel-coated carbon fiber-reinforced ABS composites was investigated. The coaxial
transmission line method was used to measure the EMI shielding effectiveness of the metal-coated carbon fibers/ABS composites.
The carbon fibers were coated with copper or nickel using the cementation and electroless deposition techniques. Measurements
of fiber length distribution in the composites indicated that the length of copper-coated carbon fibers was shorter than that of
nickel-coated carbon fibers after composite fabrication. As a result, their composites also showed poor EMI shielding
effectiveness. Among the metal-coated carbon fibers/ABS composites studied in this investigation, electroless nickel-coated carbon
fibers/ABS composites showed the best EMI shielding capability due to longer fiber length distribution and excellent bonding
between nickel coating and the fibers. The metal coatings, deposited using the cementation technique, tended to detach from the
fibers during the compounding process, and consequently, poor EMI shielding effectiveness was obtained for their composites.
© 2001 Elsevier Science B.V. All rights reserved.

Keywords: EMI shielding; Electroless deposition; Cementation

1. Introduction order to achieve the same shielding effect. Although


satisfactory shielding capability could be obtained by
Application of plastic materials on the housings of adding more carbon fibers, difficulty in producing com-
computer and other electronic devices has been growing posites with high fiber volume fraction arises when
in terms of their advantages over metals, such as light using extrusion or injection molding. The usage of more
weight, design flexibility, low costs, mass production carbon fibers also means a high production cost due to
capability, and etc. However, when using plastic hous- the high cost of carbon fibers. The above problems
ings, a serious problem with electromagnetic interfer- could be solved by applying a thin layer of metal on the
ence (EMI), which could cause noise signals and even surface of carbon fibers. In addition to the high electri-
malfunction of the electronic appliances, is encountered cal conductivity of metals, the use of metal-coated
due to their poor electrical conductivity. One of the carbon fibers also provides the polymer composites
effective techniques to improve the electrical conductiv- with high strength and modulus, low weight, and high
ity of plastics and to overcome the EMI problem is the aspect ratio of carbon fibers.
incorporation of conductive fillers in the polymer ma- Nickel and copper are the two main metals used as
trix [1–9]. Among the various conductive fillers, carbon coatings. Although the electrical resistivity of nickel is
fibers have been proved to be a good candidate for higher than that of copper, the latter is readily oxidized.
EMI shielding [5– 9]. However, since the electrical resis- Cementation and electroless deposition are two tech-
tivity of a carbon fiber is much higher than that of a niques frequently used in metal coating. The morphol-
metal, a greater amount of carbon fibers is needed in ogy, structure, and properties of nickel- and
copper-coated carbon fibers using cementation and
* Corresponding author. Tel.: +886-225-866484; fax: +886-225-
electroless techniques have been investigated by several
936897. researchers [7,8,10 –15]. However, few studies, to our
E-mail address: sstzeng@mse.ttit.edu.tw (S.-S. Tzeng). knowledge, have focused on the effects of different

0921-5093/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0921-5093(00)01824-4
S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267 259

metal coatings and different deposition techniques on tural parameters and electrical resistivity of these two
the EMI shielding effectiveness of metal-coated carbon types of fibers measured in our laboratory.
fiber-reinforced polymer matrix composites. In the
present investigation, two metal coatings, copper and 2.2. Metalization of carbon fibers
nickel, will be deposited on the carbon fibers respec-
tively using both cementation and electroless tech- Nickel and copper coated carbon fibers were used in
niques. The EMI shielding effectiveness of these this study in order to increase the conductivity of
metal-coated carbon fiber-reinforced polymer matrix carbon fibers, and consequently the EMI shielding ef-
composites will be measured and compared. fectiveness of their composites. Two deposition meth-
ods, electroless plating and cementation technique, were
adopted.
2. Experimental The electroless nickel coatings were deposited on
carbon fibers of 12 cm long using alkaline bath contain-
2.1. Materials ing nickel sulfate as the source of nickel and sodium
hypophosphite as the reducing agent. Table 2 lists the
Two types of PAN-based carbon fibers were used in bath composition and deposition conditions (tempera-
this study. They were TORAYCA T300C and T700SC, ture and pH value). Before deposition, the sizing of
manufactured by Toray Industries, Inc. in Japan. The carbon fibers was removed by immersing them into the
T300C fibers have a crosssection of kidney shape with acetone solution for 40 min, and they were then cata-
an average diameter of 7.2090.10 mm and the T700SC lyzed. A two-step pretreatment, sensitization and acti-
fibers have a circular cross-section with an average vation, was used for catalyzing the carbon fibers. The
diameter of 7.2490.42 mm. Table 1 shows the struc- sensitizer and activator were stannous chloride/hydro-
chloric acid (20 g l − 1 SnCl2·2H2O and 40 ml l − 1 HCl)
Table 1 and palladium chloride/hydrochloric acid (0.25 g l − 1
Structural parameters and electrical resistivity of carbon fibers PdCl2 and 2.5 ml l − 1 HCl) solutions, respectively.
Ultrasonic vibration was applied during the catalyza-
Fiber type d002 (A, ) Lc (A, )a Electrical resistivity (mVm)
tion treatment to facilitate uniform activation through-
T300C 3.53 17 16.01 9 0.85 out the entire surface of the carbon fibers. For the
T700C 3.52 17 15.73 9 0.81 electroless copper plating, the deposition bath contains
copper sulfate as the source of nickel, formaldehyde as
a
The stacking height Lc of the (002) layer planes was calculated
the reducing agent, sodium potassium tartrate as the
using Scherrer Formula and was calibrated for instrumental broaden-
ing using silicon as the standard. chelating agent, and sodium hydroxide as the buffering
agent. Table 3 lists the bath composition and deposi-
Table 2 tion conditions (temperature and pH value). Same fiber
Formulations and operation conditions of electroless nickel plating pre-treatments were used as that of electroless nickel
batha plating.
The cementation technique [14] is a simple method,
Chemical Formula Amount (g l−1)
which was borrowed from extractive metallurgy. The
Sodium hypophosphite NaH2PO2·H2O 20 principle of the cementation reaction is the displace-
Nickel sulfate NiSO4·6H2O 40 ment of a noble metal ion from a salt solution by a
Sodium citrate NaC6H5O7·2H2O 100 more reactive metal. Before deposition, the sizing of
Ammonium chloride NH4Cl 50 carbon fibers was removed by two different methods:
Ammonium hydroxide NH4OH pH adjustment
(1) immersing them into the acetone solution for 40
a
Bath temperature: 7090°C; pH value: 79; time: 110 min. min; or (2) heating under a nitrogen atmosphere to
700°C for 15 min. After removal of the sizing, they
Table 3 were then dipped in a known amount of glacial acetic
Formulations and operation conditions of electroless copper plating acid to activate the fiber surface for improving the
batha wettability of the carbon fiber surface with the metal to
Chemical Formula Amount
be coated. Nickel sulfate (NiSO4·6H2O, 70 g l − 1) and
copper sulfate (CuSO4·5H2O, 50 g l − 1) solutions were
Copper sulfate CuSO4·5H2O 20 g l−1 used, respectively in the deposition of nickel and cop-
Formaldehyde HCHO 5 ml l−1 per. Copper and nickel were deposited onto the carbon
Sodium potassium NaKC4H4O6·4H2O 25 g l−1
fiber from the corresponding salt solutions using two
tartrate
Sodium hydroxide NaOH pH adjustment
different displacing agents (Mg and Zn), which were in
the form of powders. All the depositions were carried
a
Bath temperature: 5070°C; pH value: 1113; time: 110 min. out at 90°C for 10 min.
260 S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267

coated carbon fibers were extracted from the ABS


composites using tetrahydrofuran (THF).
The electrical resistivity of nickel-coated carbon
fibers was measured at room temperature using four
point probe method on single fibers [16]. The electrical
contacts were made by using silver paint. A Keithley
model 580 micro-ohmmeter was used in the measure-
ments. After resistance measurement, the diameter of
the single fiber was measured using a laser diffraction
technique [17,18], and Fraunhofer diffraction approxi-
mation [19,20], according to the following expression
2uS
d= , (1)
l
was used to calculate the fiber diameter. In Eq. (1), u is
the wavelength of the He –Ne laser (= 0.6328 mm), S is
the distance between the fiber and the diffraction pat-
tern, and l is the distance between the first diffraction
nodes on both sides of the diffraction pattern. For the
fiber with an elliptical cross section (or close to that)
such as T300SC used in this study, five measurements
(measured every 36°) around the fibers were found to
minimize the measurement errors of fiber diameter
[18,20]. At least 20 single fiber samples were measured
for each type of sample, and the average and standard
deviation were calculated.
The coaxial transmission line method according to
ASTM ES-7-83 was used to measure the EMI shielding
Fig. 1. SEM micrographs of as-received carbon fibers: (a) T300C and effectiveness (SE) of the metal-coated carbon fibers/
(b) T700SC. ABS composites. The SE was evaluated by measuring
the attenuation or reduction of the electromagnetic
2.3. Fabrication of composites wave with the shield in the frequency range from 30 to
1000 MHz, and calculated and expressed in decibels
The metal-coated carbon fibers were chopped into 3 (dB) by using the following equation:
mm and then blended with ABS (Acrylonitrile-butadi-
ene-styrene) pellets in a Brabender Plasti-Corder SE(dB) = 10 log Pi /Pi = 20 log Ei /Ei = 20 log Hi /Et,
Torque Rheometer (PLE-330) at 220°C using a screw (2)
speed of 20 rpm. After being compounded, they were where Pt, Et, and Ht are power, electric field strength,
hot-compression molded into composite test sample for and magnetic field strength, respectively, of the trans-
measuring the EMI shielding effectiveness. mitted wave, and Pi, Ei and Hi are the same properties,
respectively, of the incident wave. The details of the
2.4. Characterization theory of EMI SE and the measurement methods could
be found in [21].
A Siemens D5000 X-ray diffractometer was used in
the X-ray analysis with CuKa radiation and a Ni filter
to analyze the structure of metal coatings. The operat- 3. Results and discussion
ing power was 40 KV and 15 mA. Step scanning was
used with an interval of 0.02° (2u) and a residence time 3.1. Morphology and structure of metal-coated carbon
of 1 s. fibers
The morphology of metal-coated carbon fibers and
their composites was observed using a JOEL JSM-6300 Fig. 1 (a) and (b) show the SEM micrographs of
scanning electron microscope with an accelerating po- as-received T300C and T700SC carbon fibers. As
tential of 20 KV. It has been shown that [7 – 9] the fiber shown in Fig. 1. T700SC carbon fibers have a smooth
length in the composites is an important parameter surface, whereas T300C fibers show surface striations
affecting the EMI SE value. For the measurement of along the fiber axis. In spite of the different surface
the fiber length distribution in the composite, the metal- conditions, these two fibers have similar structure
S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267 261

parameters (d002 and Lc) and electrical resistivity as 3 shows the SEM micrographs of electroless copper-
indicated in Table 1. However, the difference in surface coated T300C (Fig. 3a and b) and T700SC (Fig. 3(c)
condition will affect the adhesion between the fiber and and (d)) carbon fibers. Unlike the nickel, copper poorly
the metal coating as will be discussed later. Fig. 2 wets carbon [22]. Compared with the electroless nickel
shows the SEM micrographs of electroless nickel coated coating which shows good adhesion with carbon fiber
carbon fibers. The electroless nickel films could be surface, debonding was observed in electroless copper
deposited on the surface of both T300C and T700SC coating as indicated in Fig. 3. Also, the degree of
fibers with good adhesion as indicated in Fig. 2(a) and bonding is worse for T700SC carbon fibers with smooth
(c). It could be seen in Fig. 2(a) that the electroless surface and circular cross section when compared with
nickel layer was deposited following the contour of that for T300C carbon fibers, which show rough surface
non-circular cross section of T300C carbon fibers. It is and surface striation and have a non-circular cross-sec-
shown in Fig. 2(b) that reasonable uniformity of coat- tion. For T700SC fibers, the coating could be torn
ing thickness in the fiber bundle could be obtained. Fig. apart from the fiber easily as shown in Fig. 3(d),
whereas only debonding was observed for T300SC
fibers as shown in Fig. 3(b). Poor bonding was also
found for copper-coated carbon fibers using both elec-
troless plating and the cementation technique [13]. As
will be discussed later, the degree of bonding plays an
important role in the EMI shielding effectiveness of
metal-coated carbon fibers reinforced polymer matrix
composites.
Table 4 shows the result of deposition by the cemen-
tation technique for different types of carbon fibers and
different methods of removing sizing, and using differ-
ent displacing agents. It was found that deposition was
not successful when the sizing was removed by acetone.
However, metal coating could be formed when the
sizing was removed by heat treatment at 700°C under a
nitrogen atmosphere. It seems that heat treatment at
700°C not only removed the sizing, but also activated
the surface of carbon fibers. Table 4 also indicated a
strong influence of surface condition on the deposition.
Deposition on T700SC carbon fibers with a smooth
surface was not successful, whereas continuous coating
could be deposited on T300C carbon fibers, which show
surface striations as indicated in Fig. 1(a). For the
effect of reducing agent used in this study, Zn was
found to yield the better results. Non-continuous coat-
ing could be observed when using Mg as reducing agent
presumably due to the high reactivity of Mg. Fig. 4
shows the SEM micrographs of nickel-coated carbon
fibers by the cementation technique using Zn as the
reducing agent. As compared with electroless nickel
coating, which was deposited uniformly on the T300C
carbon fibers following the contour of the fiber surface
(Fig. 2a and b), poor bonding and non-uniform coating
were observed for cementation nickel on the same type
of fibers as shown in Fig. 4(a). Also, unlike the electro-
less nickel coating, which could be coated uniformly on
the individual fiber inside the fiber bundle, connection
of fibers by the coating was observed as shown in Fig.
4(b). Fig. 5(a) and (b) show the SEM micrographs of
copper-coated carbon fibers by the cementation tech-
nique using Zn and Mg as the reducing agent, respec-
Fig. 2. SEM micrographs of electroless nickel-coated carbon fibers: tively. As shown in Fig. 5(a), the morphology of
(a), (b) T300C and (c) T700SC. cementation copper coatings using Zn as the reducing
262 S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267

Fig. 3. SEM micrographs of electroless copper-coated carbon fibers: (a), (b) T300C and (c), (d) T700SC.

Table 4
Results of deposition using cementation techniquea

Displacing agent Cementation nickel Cementation copper

Fiber type Fiber type

T700C T300C T700SC T300C

Method of removing sizing Method of removing sizing

700°C Acetone 700°C Acetone 700°C Acetone 700°C Acetone

Mg × ×  × × ×  ×
Zn × ×  × × ×  ×

a
Note:  indicates continuous coating, × indicates not coated, and  indicates non-continuous coating.

agent is similar to that of cementation nickel. However, (111) peak was obtained in the pattern (a) of Fig. 6 for
a morphology of massive crystallites with facet was electroless nickel coating.
observed when using Mg as the reducing agent. A
massive crystallite structure without facet was observed 3.2. Conducti6ity of metal coating and EMI shielding
by Pai et al. [15] using Zn as the reducing agent. effecti6eness of composites
Fig. 6 shows the X-ray diffraction patterns of metal-
coated carbon fibers using the electroless and cementa- As discussed previously in the X-ray diffraction re-
tion deposition techniques. Besides the electroless nickel sults, crystalline nickel coatings were obtained using the
coating, crystalline metals were obtained by the cemen- cementation method, whereas amorphous or microcrys-
tation technique and electroless copper deposition. It is talline Ni –P alloy was deposited by the electroless
well established that the electroless nickel deposits using technique. Table 5 shows the measurement results of
sodium hypophosphite as a reducing agent are binary electrical resistivity of T700SC carbon fibers before and
alloys of nickel and phosphorus [23]. It was also re- after electroless nickel deposition. If we consider that
ported that the deposits plated from alkaline solution the fiber and Ni –P coating are two resistors in parallel,
had a lower phosphorus content and were crystalline, a resistivity of 1.4 mVm was calculated for the Ni –P
whereas the deposits from acid solution had a higher coating itself. This value is consistent with that (0.6 –1.4
phosphorus content and were known as amorphous or mVm) reported in the literature on Ni –P film with high
microcrystalline [24 – 26]. Therefore, a broad nickel phosphorus content [27]. It is obvious that the resistiv-
S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267 263

ity of electroless Ni – P coating is much higher than that


of pure nickel (0.073 mVm). However, it is much lower
than that of carbon fibers.
Fig. 7 shows the results of EMI shielding effective-
ness of various metal-coated carbon fiber reinforced
ABS composites. For comparison, measurements were
also made on pure ABS samples (curve a) and carbon
fiber (without metal coating)/ABS composites (curve e).
The amount of fiber addition was 30 phr for all the
composites. The relationship between electrical conduc-
tivity and fiber content had been measured in an earlier
study [28] for carbon fiber(CF)/ABS and nickel-coated
carbon fibers(NCF)/ABS composites which were fabri-
cated using the same processing procedures and equip-
ment as in this study. A percolation threshold below 20
phr was obtained for both CF/ABS and NCF/ABS
composites. It needs to be mentioned that a fiber con-
tent of 20 phr is equivalent to a fiber volume fraction of
 12% for CF/ABS composites or  7% for NCF/ABS
composites. Also, since the densities of copper and
nickel are very close (density of Cu= 8.96 g cm − 3,
density of Ni= 8.9 g cm − 3, and density of Ni –P (PB
10%)=8.0 –8.9 g cm − 3 [23]), the various metal-coated
carbon fiber/ABS composites have about the same vol-
ume fraction of fibers. Based on the average thickness

Fig. 5. SEM micrographs of cementation copper-coated carbon


fibers: (a) displacing agent: Zn and (b) displacing agent: Mg.

of 0.25 –0.4 mm, the volume fraction is about 12–14%.


Therefore, the fiber content of 30 phr used in this study
is well above the percolation threshold for composite
conductivity. Furthermore, a volume fraction of 12%
for CF/ABS composites is equal to a fiber content of 20
phr, which is above the percolation threshold. There-
fore, even that all the metal coatings were detached
during processing for a metal-coated CF/ABS com-
posite with a fiber content of 30 phr, the volume
fraction of uncoated fiber is still above the percolation
threshold for CF/ABS composites. Fig. 8 shows the
fiber length distributions of various metal-coated car-
bon fibers reinforced ABS composites. The fiber length
distribution was measured after extracting the fibers
from the composites using tetrahydrofuran (THF). As
indicated in Fig. 7, the nickel-coated carbon fibers
(curve d for cementation nickel (CN) and curve f for
electroless nickel (EN)) show better EMI shielding ef-
fectiveness than that of copper-coated carbon fibers
(curve b for cementation copper (CC) and curve c for
electroless copper (EC)) despite the fact that the resis-
tivity of copper (0.017 mVm) is much lower than that of
nickel (0.073 mVm). The main reason for this result is
Fig. 4. SEM micrographs of cementation nickel-coated carbon fibers attributed to the different fiber length distribution after
(displacing agent: Zn). processing. As shown in Fig. 8, the fiber length distri-
264 S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267

bution in CCCF/ABS (Fig. 8a) and ECCF/ABS (Fig.


8b) composites was obviously shorter than that in
CNCF/ABS (Fig. 8c) and ENCF/ABS (Fig. 8d) com-
posites. It has been reported [7 – 9,29] that the aspect
ratio of the fiber is the main factor to affect the
conductivity, and consequently the capability of EMI
shielding, of the fiber-filled composites. Longer fibers
have a higher aspect ratio and readily formed a conduc-
tive network. As shown in Fig. 8(a) and (b), the fiber
length, 3 mm long before composite fabrication, de-
creased to less than 0.5 mm after compounding and
hot-compression-molding for copper-coated CF/ABS
composites. It was also found that the fiber length
distribution for uncoated CF/ABS composites was
Fig. 7. EMI shielding effectiveness of various metal-coated carbon
fibers reinforced ABS composites: (a) pure ABS, (b) CCCF/ABS
composites, (c) ECCF/ABS composites, (d) CNCF/ABS composites,
(e) CF/ABS composites, (f) ENCF/ABS composites.

longer than that of copper-coated CF/ABS composites.


However, in contrast to copper coating, no matter
which technique was used, the effect of a nickel coating
on the fiber length distribution did not seem to be as
obvious as a copper coating did as indicated in Fig. 8.
In their study of the effect of reprocessing on the EMI
shielding effectiveness, Huang and Chiou [28,29] ob-
served a critical fiber length of 200 mm. When the
composites (both CF/ABS and NCF/ABS) were com-
pounded by the twin screw extruder, the fiber length
was below the critical length and the EMI SE value was
0 dB up to a fiber content of 30 phr. On the other hand,
if the Brabender Plasti-Corder was used for compound-
ing the composite, the fiber length was above the
critical length even after three processings, and the EMI
SE values were correlated well with the fiber length. In
other words, the EMI SE value decreased with increas-
ing number of processing cycles, which tended to de-
crease the fiber length. In our study, the composites
were compounded using the Brabender Plasti-Corder,
and the copper-coated carbon fiber/ABS composites
had the shortest fiber length. However, there were still
35% of the fibers for CCCF/ABS composites and 42%
Fig. 6. X-ray diffraction patterns of metal-coated carbon fibers: (a) of the fibers for ECCF/ABS composites with a fiber
electroless nickel deposits, (b) cementation nickel deposits, (c) electro- length above the critical length, whereas above 90% of
less copper deposits, and (d) cementation copper deposits. the fibers (except for composites with low fiber content
(i.e. 10 phr)) were below the critical length in reference
Table 5 [28,29] for composites with a EMI SE value of 0 dB.
Electrical resistivity of carbon fibers before and after electroless nickel
deposition
Another important parameter affecting the EMI
shielding effectiveness of metal-coated CF/ABS com-
Fiber Diameter (mm) Electrical posites is the adhesion between the metal coating and
resistivity (mVm) the fibers. A poor bonding of the coating will result in
the debonding or even peeling off of the coating during
T700SC 7.24 90.42 15.73 9 0.81
After electroless nickel 8.63 90.31 3.909 0.80
compounding process. As discussed previously, the ad-
deposition hesion with the fibers for electroless nickel coating was
much better than that for cementation nickel deposit.
S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267 265

Evidence of this could also be observed in the fracture posites as shown in the curve (d) and (f) of Fig. 7 in
surfaces of their composites as shown in Fig. 9. In Fig. spite of the lower electrical conductivity of electroless
9(a), the good bonding of the electroless nickel coating Ni –P coating as discussed previously. It was also noted
could be observed at the pull-out portion of the fibers. that although the ENCF/ABS composites has a lower
However, detachment of nickel coating from the fibers fiber volume fraction (12 –14%) compared with that
was found when using the cementation technique as (20%) of CF/ABS composites, a higher EMI SE value
shown in Fig. 9(c). The striations of the original fiber was obtained for ENCF/ABS composites due to the
surface could be seen clearly. As a result of good much higher electrical conductivity of electroless nickel-
bonding, the ENCF/ABS composites showed much bet- coated carbon fibers considering the relatively similar
fiber length distribution of both composites. On the
ter EMI shielding effectiveness than CNCF/ABS com-
other hand, the EMI shielding effectiveness of CNCF/
ABS composites was slightly lower than that of CF/
ABS composites. In addition to the higher fiber volume
fraction of CF/ABS composites and the detachment of
nickel coating from the fibers when using the cementa-
tion technique, that the number of longer fibers (400 –
700 mm) in CF/ABS composites (Fig. 8e) is more than
that in CNCF/ABS composites (Fig. 8c) may also
contribute to this result. Similar results were also ob-
tained for copper-coated CF/ABS composites. The
ECCF/ABS composites showed better EMI shielding
effectiveness than CCCF/ABS composites as shown in
curve (b) and (c) in Fig. 7 presumably due to the better
adhesion of copper coating by the electroless technique
as indicated in Fig. 9(b) and Fig. 9(d). Electroless
copper coatings on the pull-out fibers could be seen in
the fracture surface of ECCF/ABS composites as indi-
cated by the arrow sign in Fig. 9(b). On the other hand,
most of the cementation copper coatings were peeled
off and the striations of the original fiber surface were
revealed as indicated in Fig. 9(d). The fiber length
distribution of ECCF/ABS composites was also slightly
longer than that of CCCF/ABS composites as shown in
Fig. 8(a) and Fig. 8(b). It has been reported [13] that
the ultimate tensile strength of electroless copper-coated
carbon fibers is much higher than that of cementation
copper-coated carbon fibers. Also, the tensile fracture
of both electroless and cementation copper-coated car-
bon fibers showed delamination of the coating, which
suggested poor bonding between coating and the fiber.
As a result, the copper coating tended to be peeled off
during the compounding process, especially for cemen-
tation copper coatings as shown in Fig. 9(b) and Fig.
9(d).
Among the metal-coated CF/ABS composite samples
used in this study, ENCF/ABS composites performed
best in EMI shielding effectiveness. In fact, the EMI
shielding effectiveness of other samples was even worse
than that of CF/ABS composites without metal coat-
ings based on the same weight percentage of fibers. As
previously discussed, in addition to the good adhesion
between nickel coating and the fiber, the fiber length
distribution of ENCF/ABS composites, which was
Fig. 8. The fiber length distributions of various metal-coated carbon
fibers reinforced ABS composites: (a) CCCF/ABS composites, (b)
comparable to that of CF/ABS composite samples, is
ECCF/ABS composites, (c) CNCF/ABS composites, (d) ENCF/ABS also an important factor. On the other hand, it is
composites, and (e) CF/ABS composites. interesting to note that a copper coating, regardless of
266 S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267

Fig. 9. Fracture surfaces of various metal-coated carbon fibers reinforced ABS composites: (a) ENCF/ABS composites, (b) ECCF/ABS
composites, (c) CNCF/ABS composites, (d) CCCF/ABS composites, and (e) CF/ABS composites.

the deposition technique used, tended to decrease the 4. Conclusions


fiber length distribution in the composites. The reason
is probably because that copper is readily oxidized, and EMI shielding effectiveness of copper- and nickel-
the oxide layer makes the brittle carbon fibers to frac- coated carbon fiber-reinforced ABS composites was
ture more easily. It also needs to be mentioned that investigated. The coaxial transmission line method was
CCCF/ABS composites showed very low EMI SE value used to measure the EMI shielding effectiveness of the
in this study because of the worst adhesion between metal-coated carbon fibers/ABS composites. The car-
coating and the fiber and the shortest fiber length bon fibers were coated with copper or nickel using
among all the samples. cementation and electroless deposition techniques. Cop-
S.-S. Tzeng, F.-Y. Chang / Materials Science and Engineering A302 (2001) 258–267 267

per-coated carbon fibers/ABS composites showed poor [4] P.B. Jana, A.K. Mallick, J. Elastomers Plastics 26 (1994) 58.
EMI shielding effectiveness due to a shorter fiber length [5] W.-Y. Chian, Y.-S. Chiang, J. Appl. Polym. Sci. 46 (1992) 673.
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