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Effects of Sizing Materials on the Properties of Carbon

Fiber-Reinforced Polyamide 6,6 Composites

N. Gamze Karsli,1 Cem Ozkan,2 Ayse Aytac,1 Veli Deniz1

Department of Chemical Engineering, Engineering Faculty, Kocaeli University, 41380 Izmit, Kocaeli, Turkey

Department of Polymer Science and Technology, Kocaeli University, 41380 Izmit, Kocaeli, Turkey

This article aims to study the effect of the sizing mate- [1,2]. In addition, the polyamides (PAs) have been studied
rials type on the mechanical, thermal, and morphologi- as matrix material in thermoplastic composite due to their
cal properties of carbon fiber (CF)-reinforced
polyamide 6,6 (PA 6,6) composites. For this purpose,
low cost, ease of handling, and good mechanical proper-
unsized CF and sized CFs were used. Thermogravimet- ties when processed with CF reinforcement [2–7].
ric analysis was performed, and it has been found that Properties of CF-reinforced composites are determined
certain amounts of polyurethane (PU) and PA sizing not only by the properties of the CF and the matrix, but
agents decompose during processing. The effects of also are influenced by the mutual interphase interactions
sizing agent type on the mechanical and thermome-
chanical properties of all the composites were investi- among these constituents [1]. A better interaction between
gated using tensile, Izod impact strength test, and the matrix and fibers help to transfer the load efficiently
dynamic mechanical analysis. Tensile strength values from fibers through the matrix, resulting in structural
of sized CF-reinforced composites were higher than coherence and stronger composites [8]. Because of the
that of unsized CF-reinforced composites. PA and poly-
urethane sized CF-reinforced composites exhibited the unreactive nature of thermoplastic polymers and the sur-
highest impact strength values among the other sized face of CF, the interaction of the CFs and thermoplastic
CF-reinforced composites. PU and PA sized CF- matrices is usually weak [3]. Due to these reasons, the
reinforced composites denoted higher storage modulus majority of efforts have been focused on increasing fiber-
and better interfacial adhesion values among the other
matrix adhesion using various modification methods [9].
sizing materials. Scanning electron microscope studies
indicated that CFs which were sized with PU and PA Some of these methods have been developed to change
have better interfacial bonding with PA 6,6 matrix the fibers surface wettability for the improvement the
among the sized CFs. All the results confirmed that PA adhesion between CF and polymer matrix [8]. Sizing or
and PU were suitable for CF’s sizing materials to be coating is a kind of simple and efficient method used for
used for PA 6,6 matrix. POLYM. COMPOS., 34:1583–
1590, 2013. VC 2013 Society of Plastics Engineers these purposes [10]. In this method, CF surfaces are
coated by a sizing material, which is usually in the form
of solution or emulsion composed of polymeric compo-
INTRODUCTION nents [1]. It was reported in literature that use of sized
CF in the composites plays a crucial role for the control-
Thermoplastic polymer based composite materials ling of mechanical properties [10].
have received more interest for structural applications In literature there are some studies which were investi-
over the last 40 years. Particularly, carbon fiber (CF)- gated the influence of sizing agent type on the properties
reinforced thermoplastic composites are widely used in of CF-reinforced polymer composites. Dilsiz and Wight-
aerospace, enginery, marine, and automobile industries man [11] investigated the influences of polyurethane (PU)
due to their superior properties such as high-specific and poly(ether imide) sizing on the surface energy of CFs.
strength and stiffness, lower density, and flexible designs The surfaces of unsized and sized fibers were also ana-
lyzed by X-ray photoelectron spectroscopy. They found
Correspondence to: Ayse Aytac; e-mail: aaytac@kocaeli.edu.tr that the sizing materials on the CF surface reduced the sur-
Ayse Aytac is currently at Chemical Engineering Department, Engineer- face energy and decreased the number of hydroxyl groups
ing Faculty, Kocaeli University, 41380 Izmit, Kocaeli, Turkey. on the fiber surface. Dai et al. [1] studied the effect of siz-
Contract grant sponsor: Ministry of Science Industry and Technology of ing on surface properties of CF and the fiber=epoxy (EPO)
Turkey; contract grant number: SANTEZ 01020.STZ.21011-2.
DOI 10.1002/pc.22556
interfacial adhesion by comparing with unsized CF. They
Published online in Wiley Online Library (wileyonlinelibrary.com). found that there was a low amount of activated carbon
C 2013 Society of Plastics Engineers
V which was able to bond potentially with the hydroxyl and

EPO groups, on the surfaces of unsized CF. Zhang et al. Turkey (Aksaca). CFs, unsized and sized with five differ-
[8] analyzed the effect of the molecular weight of sizing ent kinds of sizing agents were used as reinforcement
agents on the properties of CF-reinforced composites using materials. These sizing agents were PU, PA, PI, phenoxy
different characterization techniques. Their study showed (PHE), and epoxy=phenoxy (EPO_PHE). PA 6,6 was
that the moderate molecular weight of sizing agent dried in a vacuum oven at 80 C for 24 h before the com-
enhanced the adhesion between the fiber and matrix. In pounding process. CF loading level in the composites was
another study, Zhang et al. [12] aimed to study the influ- fixed at 30% by weight and fiber length was 0.6 cm. The
ence of the concentration of the sizing agent on the proper- composites were processed in a DSM Xplore micro-
ties of CF and CF’s composites. They showed that compounder at 285 C, 100 rpm and 3 min. All the com-
concentrations of the sizing agent have different effect on pounds were subsequently injection molded using a
the wetting performance of CFs. They used sizing agent in laboratory scale injection molding machine (DSM Xplore
three different concentrations and they found that the opti- 12 ml Micro-Injection Molder) with barrel temperature
mum sizing concentration was 1.5% (by wt). Luo et al. 285 C, mold temperature 80 C; and injection pressure
[13] investigated the role of sizing on CF and the mecha- was 10 bars.
nism of adhesion in CF=polymer matrix composites. They Thermal degradation of sizing agents on the CF sur-
used two types of sizing materials on CFs for this purpose. face was measured using Perkin Elmer TGA Instrument.
The results of atomic force microscopy image analysis Measurements were performed between the temperatures
showed that surface of carbon became smoother after siz- from 25 to 900 C, with a heating rate of 10 C=min under
ing. Besides, the total and the polar component surface nitrogen atmosphere.
energies of the sized CF have found to be decreased Tensile tests were applied according to ASTM D 638-
slightly when compared with unsized CF. Xu et al. [14] 10 [16] using a computer controlled Lloyd Instrument-
modified the polyacrylonitrile-based CFs with nitric acid LRX Plus model universal testing machine. Tensile
and maleic anhydride (MA) to improve the interaction strength and strain at break values of composites were
between CF surface and polyimide (PI) matrix. They determined at 5 mm=min crosshead speed. The Izod
investigated the characteristic changes on the surface after impact strength tests were performed according to ISO
modification and surface reactions taken place using vari- 180 by a Ceast machine model 9050 with a 5.5-J hammer
ous characterization techniques. They suggested that the and impact velocity 3.46 m=s. Five specimens of each
chemical modification of CF surface with MA might fol- sample were tested and the average value of each set of
low the Diels Alder reaction mechanism. Clark and Secrist tests were reported with standard deviations in both ten-
[15] characterized the mechanical properties of nylon 6,6 sile and impact characterizations.
composites reinforced with the four different CFs which DMA was carried out in the tension mode using
were treated with different sizing agents and methods. Metravib DMA50 analyzer. Storage modulus (E0 ) and tan
These treatments were air oxidation, anodic oxidations and delta (tan d) values of composites were measured. Com-
two different nylon compatible sizing agents. They per- posites were tested under the condition of 1.5 3 1025 m
formed fiber length distribution analysis and they found dynamic displacement and 1 Hz frequency. The scanning
similar fiber length distributions for all the samples stud- was carried out from 25 to 200 C at 1 C=min heating
ied. Their results showed that tensile, impact strengths and rate.
electrical conductivity could be affected by modification of Morphologies of tensile fractured surfaces of compo-
the surface treatment of CF. sites were examined using SEM (JEOL JSM-6510).
The aim of this study is to examine the influence of Before the examinations, surfaces of composites were
sizing agent type on the performance of CF-reinforced sputter coated with gold and palladium.
polyamide 6,6 (PA 6,6) composites. Unsized CF and CFs
which were sized with five different kinds of sizing
agents were used in this study. Thermogravimetric analy- RESULTS AND DISCUSSIONS
sis (TGA) was performed for investigation of thermal
TGA of Sized CFs
degradation of sizing agents on the CF surface. The
effects of sizing agent type on the mechanical and ther- The thermal stability of sized CF, i.e., thermal resist-
momechanical properties of prepared composites were ance of sizing materials has been analyzed using TGA
investigated using tensile, Izod impact test and dynamic under nitrogen atmosphere. Initial decomposition temper-
mechanical analysis (DMA). Scanning electron micro- ature (Td) and the decomposition temperature at maxi-
scope (SEM) is also used for analyzing the fracture surfa- mum rate (maxTd) of the sizing material were determined.
ces of the composite materials. TGA curves of CFs which sized with five different agents
were given in Fig. 1a–e and the thermal decomposition
data were listed in Table 1 as the Td and maxTd. It can be
seen from the TGA curves that the lowest decomposition
PA 6,6 (Eplamid 66) was used as matrix material and temperature is about 270 C and the highest temperature
supplied from Epsan (Turkey). CF was supplied from at which weight loose was ended is approximately 500 C

1584 POLYMER COMPOSITES—2013 DOI 10.1002/pc

FIG. 1. TGA curves of carbon fibers coated with different sizing materials, (a) PU, (b) PA, (c) EPO_PHE,
(d) PHE, and (e) PI.

for all the sizing agents studied. This is very critical, Table 1 that, PU and PA sizing materials start to decom-
because all the composites were compounded at 285 C pose at 270 and 280 C, respectively. It can be inferred
in microcompounder. As seen from these figures and from this results that some amounts of PU and PA sizing
agents decompose during processing. The other sizing
TABLE 1. Initial decomposition temperature Td ( C) and the decompo- materials, on the other hands, are thermally stable at the
sition temperature at maximum rate maxTd ( C) values of sizing processing temperatures.

Sizing material Td ( C) Td ( C) Tensile Test of Composites

PU 270 386 Tensile properties of composites as a function of fiber

EPO_PHE 305 425 sizing agent type were given in Figs. 2–4. Stress–strain
PI 310 387 curves of neat PA 6,6 and composites can be shown in
PHE 345 433 Fig. 2 and tensile strength and strain at break values were
PA 280 448
obtained from these curves. It can be seen from Fig. 2

DOI 10.1002/pc POLYMER COMPOSITES—2013 1585

FIG. 2. Stress–strain curves of neat PA 6,6 and PA 6,6=CF FIG. 4. Effect of sizing agent type on the strain at break values of PA
composites. 6,6=CF composites.

that a ductile type of curve was obtained for neat PA 6,6 sized CF can be explained by the enhanced adhesion
and the behavior of PA 6,6 matrix became brittle with the between fiber and PA 6,6 matrix.
addition of short CF. Young’s modulus of the composites Strain at break values of composites with respect to
increased with addition of fiber, while the toughness of different sizing materials were given in Fig. 4. As it is
composites decreased. known, the strain at break value of neat PA 6,6 decreases
Tensile strength values of composites with respect to with the addition of the fiber. This is due to the decreas-
sizing agent type were given in Fig. 3. It is shown in the ing of the chain mobility of the polymeric matrix [17]. In
figure that tensile strength of composites increased with this study, the highest strain at break value was obtained
the addition of CF. In addition to this, tensile strength of for the PA sized CF-reinforced composite. Besides, it was
sized CF-reinforced composites was higher than that of observed that strain at break values of sized CF-
unsized CF-reinforced composites. According to this reinforced composites were higher than unsized CF-
result, surface sizing enhances the interfacial bonding by reinforced composite. It can be concluded that surface
modifying chemical structure of the CF surface, hence treatment using sizing materials enhanced the tensile
promoting more fiber–matrix interaction at the interface strain at break values of the composites by improving the
and provides better adhesion between fiber and matrix. It interfacial adhesion. Moreover, sizing treatment methods
is known that better adhesion between fiber and matrix hindered the debonding and pull out of the fibers as dem-
facilitates stress transfer from matrix to fiber [17,18]. In onstrated in Fig. 5a and b [19].
this study, the maximum tensile strength value was
observed with PA sized CF-reinforced composites. Izod Impact Strength Test of Composites
Increase in tensile strength values with the addition of PA
The unnotched impact energy is the sum of the energy
absorbed in fracture initiation and crack propagation [20].
The PA 6,6 matrix is a relatively high strength and duc-
tile thermoplastic polymer. Generally it can be said that
the addition of fiber into polymer matrix makes the poly-
mer more ductile and brittle by means of reducing impact
strength of fiber-reinforced composites [20,21]. As a
result, the fracture behavior of the matrix is very different
before and after the addition of fibers [22]. Moreover, the
addition of fiber to the matrix makes the initiation of
cracks easier because of the high stress concentration at
fiber ends [20].
The unnotched Izod impact energy values of composites
with respect to sizing agent type were given at Fig. 6.
Although the impact strength value of neat PA 6,6 was
measured as 80 kJ=m2, the impact strength values of CF-
reinforced composites were between 50 and 60 kJ=m2 [21].
FIG. 3. Effect of sizing agent type on the tensile strength values of PA PA and PU sized CF-reinforced composites gave the high-
6,6=CF composites. est impact energy values among the other sized CF-

1586 POLYMER COMPOSITES—2013 DOI 10.1002/pc

FIG. 5. Scanning electron micrographs of tensile fracture surfaces of PA 6,6=CF composites, (a) unsized
(31000) and (b) PA (31000).

reinforced composites. Besides, the lowest impact strength agents reinforced PA 6,6 composites were investigated to
values were obtained for the samples of unsized CF- elucidate interface interactions under dynamic conditions.
reinforced composites. In other words, sizing process The effect of sizing agent type on the storage modulus
increased the impact strength independently from the sizing (E0 ) and damping factor values (tan d) at 30% fiber load-
materials types studied. This increase can be explained by ing level were given in Figs. 7 and 8, respectively as a
the increase of interaction between fiber surface and matrix. function of temperature. It can be seen from Fig. 7 that
A ductile polymer which has high impact strength absorbs there has been a remarkable increase in the storage modu-
most of the impact energy and an initiated crack expands lus values of PA 6,6 matrix with the addition of the CFs.
slowly. But in the fiber-reinforced systems, if the adhesion This increment is due to the increasing of composites’
between the fiber and matrix is weak, the crack does not stiffness with the reinforcing effect of the CFs. Besides,
pass through the fiber and prefers to propagate along the there is an effect of the sizing materials’ type on the stor-
weak fiber=matrix interfaces, and the poor adhesion age modulus of the composites, because of the more effi-
between the fiber and matrix increases the stress concentra- cient stress transfer from fiber to matrix [23,24]. The
tion sites in the matrix [22]. Therefore, impact strength of effect of sizing agent type on the storage modulus of
the fiber-reinforced composites decreased due to the poor composites can be seen by comparing storage modulus
adhesion between fiber and interface. Because of this it can values of unsized CF reinforced and different sized CF-
be said that, PU and PA sizing materials adhered to the PA reinforced composites. It is seen from Fig. 7 that the stor-
6,6 matrix better than the other sizing materials. age modulus of sized CF-reinforced composites exhibited
higher values than the unsized CF-reinforced composites.
Although PU sized CF-reinforced composites had the
DMA of Composites highest storage modulus among all samples, PA sized
CF-reinforced composites gave slightly lower values than
The dynamic mechanical properties of CF which
these values.
unsized and sized with five different kinds of sizing

FIG. 6. Effect of sizing agent type on the impact strength values of PA FIG. 7. Effect of sizing agent type on the storage modulus values of
6,6=CF composites. PA 6,6=CF composites.

DOI 10.1002/pc POLYMER COMPOSITES—2013 1587

The ratio of loss modulus to storage modulus is calcu-
lated as the damping factor (tan d). The area under the
damping factor curve gives an indication of the total
amount of energy that can be absorbed by the material
during an experiment [25,26]. In literature, it was
reported that fibers take over the most part of the stress
and allow only a small part of it to strain the interface
and energy dissipation occurs at the interface. Therefore,
a composite material with stronger interfacial bonding
between the fibers and matrix will be in tendency to dis-
sipate less energy and showing low intensity of damping
peak with compare to a material with poorly bonded
interface [23,27–29]. The effects of surface sizing of
fibers on the damping factor values of the composites
were evaluated and damping factor of composites were
FIG. 8. Effect of sizing agent type on the tan delta values of PA
6,6=CF composites.
given in Fig. 8. Unsized CF-reinforced composites

FIG. 9. Scanning electron micrographs of tensile fracture surfaces of PA 6,6=CF composites, (a) unsized
(3500), (b) PU (3500), (c) PA (3500), (d) EPO_PHE (3500), (e) PHE (3500), and (f) PI (3500).

1588 POLYMER COMPOSITES—2013 DOI 10.1002/pc

exhibited higher tan d peak value as compared to sized adhesion, lower tan d peak intensity of PU sized CF-
CF-reinforced composites. This result may be attributed reinforced composite corresponds to better adhesion
to more energy dissipation due to the internal friction at between PU sized CFs and PA 6,6 matrix. It was seen in
the poorly bonded interface [30]. The PU sized CF- the scanning electron micrographs that PU and PA sized
reinforced composites showed lower tan d peak intensity CFs have better interfacial bonding with PA 6,6 matrix
than the other sized CF-reinforced composites. Because among the other sized CFs. The results obtained in this
there is a relation between the tan d peak intensity and study confirmed that the selection of sizing materials had
fiber–matrix adhesion, lower tan d peak intensity obtained a critical effect on the properties of CF-reinforced poly-
for PU sized CF-reinforced composite could be thought meric composites. As a result, PA and PU are suitable
as an evidence of better adhesion between PU sized CF CF’s sizing materials to be used for PA 6,6 matrix.
and PA 6,6 matrix.

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1590 POLYMER COMPOSITES—2013 DOI 10.1002/pc