Materials Science and Engineering A 492 (2008) 383–391

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Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

Mechanical behaviors of Al2 O3 nanoparticles

reinforced polyetheretherketone
Pan Guoliang, Guo Qiang ∗ , Tian Aiguo, He Zhiqiang
School of Materials Science and Engineering, Shanghai University, Shanghai 201800, PR China

a r t i c l e i n f o a b s t r a c t

Article history: In order to improve the mechanical properties of Polyetheretherketone (PEEK), nanometer Al2 O3 parti-
Received 23 November 2007 cles were used as fillers. The effect of size and content of Al2 O3 particles, various coupling agents and
Received in revised form 25 March 2008 dispersing methods on the mechanical properties were all studied. The reinforced PEEK filled with 15 nm
Accepted 7 May 2008
and 5 wt.% Al2 O3 particles possessed higher tensile, flexural and impact performance than that filled
with 90 nm and 10 wt.% Al2 O3 particles possessed. Especially, the impact strength of the PEEK filled with
Keywords:
titanate treated nanometer Al2 O3 particles was about eight times that of neat PEEK. Furthermore, the
PEEK
higher tensile, flexural, compression and impact strength of PEEK filled with nanometer Al2 O3 particles
Alumina
Mechanical behavior
than that of PEEK filled with nanometer SiO2 particles were presented. In addition, through the analy-
Fracture sis of fractographs for tensile specimens by scanning electrical microscope (SEM), the relativity between
Composite mechanical characteristics and fracture mechanism were discussed.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction dispersing methods on mechanical behaviors are all investigated in

PEEK is a kind of high performance engineering plastic with
outstanding performance: high mechanical properties, high tem-
perature resistance and self-lubrication etc. However, higher
mechanical properties are required under some special severe
conditions such as used as gears, piston rings and slide bearings
[1]. Inorganic nanometer particles of which diameter is less than
100 nm possess the properties of great specific surface area, high
surface energy and large number of atom surface defects in com-
parison with normal size inorganic particles. The filling of inorganic
nanometer particles into PEEK matrix has been done in many liter-
atures to improve the strength, rigidity and tenacity of PEEK [2–6].
However it is difficult to keep the scale and dispersion homoge-
nization of inorganic nanometer particles in PEEK due to the easy
reunion of nanometer particle, the insolubility of PEEK and its high
melting process temperature of above 400 ◦ C [7]. It has appeared in
the literatures that PEEK matrix was filled with nanometer parti-
cles: Al2 O3 , SiO2 , SiC, Si3 N4 , AlN and ZrO2 etc. those all emphasized
on the improvement in friction and wear properties [8–17], but
less report emphasized on the effect of the diameter and mass frac-
tion of filled nanometer Al2 O3 particles on mechanical properties of
PEEK. In addition, the effect of different coupling agents and various
∗ Correspondence author. Tel.: +86 21 69982791; fax: +86 21 69982840.
E-mail addresses: guoq@shu.edu.cn, pangl 419@yahoo.com.cn (G. Qiang).
this paper.
2. Experimental
2.1. Preparation of polymer specimens
PEEK powder of 250 ␮m in diameter is supplied by Jilin Univ. and
that of 50 ␮m in diameter is from Victrex Co. Ltd. The Al2 O3 particles
of 15 nm in diameter are prepared by Jiangsu Univ. and that of 90 nm
in diameter are purchased from Bona Technology Co. Ltd. The SiO2
particles of 12 nm in diameter are supplied by Degussa-huls Pacific
Co. Ltd. Titanate, Stearic acid, Sodium stearate and Silane which
selected as coupling agents are all purchased from SINOPHARM
Group Corp.
Inorganic nanometer fillers were firstly mixed with coupling
agents in absolute ethanol, and then blended with PEEK powder,
finally prepared by heat compression moulding. Four kinds of dis-
persing methods were used to blend the mixture with PEEK powder.
The first one is dry powder direct mechanical mixing method
(DMM), which is to dry the mixed solution of fillers by heating
at 110 ◦ C for 3 h, and mixed it with dry PEEK powder by mechan-
ical method. The second one is liquid-solid mechanical dispersing
method (LSMD), which is to blend the mixed solution with PEEK
powder by mechanical dispersion directly, then to filtrate and dry
it at 110 ◦ C for 8 h. The third one is ultrasonic dispersing method
(UD), which is to disperse PEEK powder in mixed solution with

0921-5093/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2008.05.026
384 P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391

Titanate
BMD
B141

95
5
–
–

Titanate
U141

UD
95
5
–
–

Titanate
LSMD
L141

95
5
–
–

Silane
LSMD
L434

90

10
–
–
–

Silane
LSMD
L424

95
–
–
–
5

Fig. 1. DSC curves of specimens D000, L120 and L121.

Titanate
LSMD

ultrasound for 1.5 h. Absolute ethanol was selected as liquid

L131

90

10

medium, and the mixture was stirred by a glass stick continuously

–

–
–

during the ultrasonic dispersion. The last one is ball milling dis-
persing method (BMD), which is to blend the mixed solution with
Sodium stearate

PEEK powder in a ball mill for 1.5 h. Some Si3 N4 balls of 2–6 mm in
diameter was set in the machine to milling the mixture and abso-
lute ethanol was also used as liquid medium. During the molding
LSMD
L123

process, the material was heated to 340 ◦ C under the pressure of

95

20 MPa and kept for 30 min, then heated to 365 ◦ C, followed by cool-
–
5
–
–

ing to 100 ◦ C in the mould while kept the pressure, finally opened
the mould and cooled to room temperature. The diameter and con-
Stearic acid

tent of inorganic nanometer particles, coupling agents and various

LSMD

dispersing methods are all listed in Table 1.

L122

95
–
5
–
–

2.2. Differential scanning calorimeter analysis

Titanate
LSMD
L121

A PerkinElmer differential scanning calorimeter (DSC) was used

95
Composition of inorganic nanometer particles/PEEK composites and dispersing methods

–
5
–
–

to obtain the thermograms of neat PEEK and inorganic nanome-

ter particles reinforced PEEK. The temperature used was 50–450 ◦ C
with a helium atmosphere and the samples were heated at
LSMD
L120

10 ◦ C min−1 . The glass transition temperature (Tg ), melting tem-

95
–
5
–
–

perature (Tm ) and enthalpy of melting (Hm ) of samples were all

calculated. Crystallinity () is an important factor which would be
positive with mechanical properties of PEEK and could be calcu-
Titanate
DMM
D221

lated as Eq. (1).

95

 
–
–
5
–

Hf
= × 100% (1)
Hf∗
Titanate
DMM
D121

where the melting enthalpy (Hf ) can be obtained from the area
95
–
5
–
–

that is enclosed by the peak of DSC melting curves and the baseline.
And Hf∗ is the melting enthalpy while the crystallinity is 100%.
D000

100
–
–
–
–
–
–

2.3. Atomic force microscope analysis

PEEK (˚ 250 ␮m, wt.%)

Dispersion of nanometer particles in PEEK matrix was examined

Surface treating agent
PEEK (˚ 50 ␮m, wt.%)

by atomic force microscopy (AFM) using a Nanoscope E atomic force

Dispersing method
Prescription code

microscope (Digital instrument, USA) at room temperature. Spec-

˚ 90 nm Al2 O3
˚ 15 nm Al2 O3

˚ 12 nm SiO2

imens of D121, L121 and L131 were chosen to be inspected, which

was about 10 mm × 10 mm × 3 mm in size. Transect of specimen
Table 1

was wheted by metallographic abrasive paper and polished by pure

water before examination.
 P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391 385

Fig. 2. AFM micrograph of dispersion of nanometer Al2 O3 particles in the PEEK composites. (a) D121; (b) L121; (c) L131.
386 P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391
Fig. 3. Effect of diameter of nanometer Al2 O3 particles on the mechanical prop-
erties. (a) tensile, compressive and flexural strength; (b) impact strength and ball
indentation hardness.
2.4. Mechanical properties examination
Tensile and compressive tests were carried out on a universal
testing machine (CSS-441000) under ambient condition at a nom-
inal strain rate of 1.5 mm min−1 and 1 mm min−1 , respectively. The
dimension of tensile specimens meets the requirement of National
Standard Testing Methods GB/T1041-92. Impact strength of the
samples was measured with XCJ-4 Impact Tester at room temper-
ature according to GB/T16420-1996. Ball indentation hardness of
the samples was measured with PHBI-625 Plastic Ball Indentation
Hardness Tester according to GB2298-82. Flexural tests were car-
ried out on a universal material testing machine (INSTRON 1195,
INSTRON Corporation, U.K.) according to GB/T 16419-1996, and the
specimens were tested with a crosshead speed of 1.0 mm/min. The
flexural strength was calculated as Eq. (2).
−1
f = 1.5L0 · P · (B · H 2 )
where  f is flexural strength, L0 is the span between two acting
points on specimen, P is the force loaded on specimen according to
a given flexibility, B is the width of specimen and H is the thickness
of specimen.
2.5. Fractograph analysis
A JXA-840A scanning electron microscope (SEM) was used to
evaluate the fractograph of tensile testing specimens. The fractured
surfaces were cleaned with pure alcohol to eliminate impurities and
coated with a thin evaporated layer of gold to improve conductivity
before examination.
3. Results and discussion
3.1. Thermal behaviors of PEEK filled with Al2 O3 nanoparticles
Thermal and crystallization behaviors of composites were
studied by DSC experiments. The results showed that the glass
transition temperature (Tg ) of neat PEEK is 118 ◦ C however that of
L120 and L121 both filled with 5 wt.% and 15 nm Al2 O3 particles
are all about 138 ◦ C. The melting temperature (Tm ) of neat PEEK
is 343 ◦ C, however that of L120 and L121 are 340 ◦ C and 341 ◦ C,
respectively. As is shown in Fig. 1, the Hf of specimens D000, L120
and L121 are 42.42, 24.37 and 28.18 J/g, respectively, which demon-
strates that the crystallinity has decreased for the filling of inorganic
nanometer particles. It is possible that the filling of nanometer par-
ticles would result in the improvement of rigidity of PEEK chain
segment, and obstruct the ordered arrangement of PEEK chain
segment.
3.2. Dispersion of nanometer Al2 O3 particles in PEEK
As is shown in Fig. 2(a), which is the AFM micrograph of PEEK
filled with 5 wt.% and 15 nm Al2 O3 particles and dispersed by dry
powder direct mechanical mixing method. The white spots in figure
are nanometer Al2 O3 particles which almost keep uniform disper-
sion without any visible aggregating, and the maximal scale of it is
about 90 nm.
Fig. 2(b) shows the micrograph of specimen L121 which is of the
same components with D121 but dispersed by LSMD. The maximal
scale of Al2 O3 particles is about 40 nm which is smaller than that
of D121. Composition and dispersing method of specimen L131 is
the same as L121 except that the content of Al2 O3 particles is 10%.
As is shown in Fig. 1(c), the maximal scale of Al2 O3 particles in
it approaches 100 nm, which indicates that the nanometer struc-
ture composites could be achieved by these preparation methods.
According to Fig. 2(b) and (c), as the dispersing homogenization of
specimen is concerned, it can be found that filling of 5 wt.% Al2 O3
is superior to that of 10 wt.% Al2 O3 and liquid-solid mechanical dis-
persing method is better than dry powder direct mechanical mixing
method.
(2)
Fig. 4. Effect of diameter and mass fraction of Al2 O3 particles on tensile and flexural
modulus.
 P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391 387

Fig. 5. SEM micrographs with different magnification of tensile fracture surface for neat PEEK and composites filled with various diameters Al2 O3 particles. (a), (b) and (c)
D000; (d), (e) and (f) D121; (g) and (h) D221.

3.3. Effect of filler nanoparticle size on mechanical properties and
fracture mechanism
As is shown in Fig. 3(a) and (b), specimens filled with 15 nm
Al2 O3 particles and dispersed by DMM possess maximal tensile and
impact strength, which increased by 5% and 5.6 times than neat
PEEK, respectively. However, compressive and flexural strength
would increase as the diameter of Al2 O3 particles rises. Compres-
sive and flexural strength of specimen filled with 90 nm Al2 O3
increased by 21% and 17% than that of neat PEEK, respectively. Fig. 4

Fig. 6. Effect of content of various nanometer particles on the mechanical properties. (a) tensile, compressive and flexural strength; (b) impact strength and ball indentation
hardness.
388 P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391

Fig. 7. SEM micrographs with different magnification of tensile fracture surface for PEEK composites filled with various contents Al2 O3 or SiO2 . (a), (b) and (c) L121; (d), (e)
and (f) L131; (g) L424.

shows the variation of tensile and flexural modulus with diam-
eter of Al2 O3 particles. It can be seen that the flexural modulus
monotonically increases with the increase in the diameter of Al2 O3
particles, while the variation of tensile modulus with diameter has
no similar trend.
Nanometer particles possess large specific surface area, high
surface activity and better interactivity with the polymer chain
segment in comparison with normal size particles, so the filling
of it could improve the toughness, rigidity and strength of com-
posites [18]. Meanwhile the rigid inorganic particles in polymer

Fig. 8. Comparison of mechanical properties of composites filled with various coupling agents treated Al2 O3 particles: (a) tensile and flexural strength; (b) impact strength
and ball indentation hardness.
 P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391 389

Fig. 9. Variation of mechanical properties of PEEK composites with different dispersing methods. (a) tensile, compressive and flexural strength; (b) impact strength and ball
indentation hardness.

would lead to the concentration of stress, then easily resulting in
more microcracks and more absorption to impact energy. In addi-
tion, inorganic particles could interrupt and delay the spread of
microcrack or stop its transformation to the fracture crack. With
the increase of diameter, the specific surface area of inorganic par-
ticles would decrease, then lead to the weakening of interaction
between inorganic particles and polymer, finally would result in
the decrease of tensile and impact strength. However, compres-
sive and flexural strength would increase with the improvement of
material rigidity.
Representative SEM micrographs of the tensile fracture surface
of D000, D121 and D221 at various magnifications are all shown
in Fig. 5. Dimples are distinctly visible in the micrograph of D000
(see Fig. 5(a)). The high magnification micrograph of one of the

Fig. 10. SEM micrographs with different magnification of tensile fracture surface for PEEK composites prepared by different dispersing methods. (a), (b) and (c) L141; (d), (e)
and (f) U141; (g), (h) and (i) B141.
390 P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391
dimples in Fig. 5(a) is shown in Fig. 5(b). The bottom of the dim-
ple appears smooth but some distinctly visible radial striae can be
found on the edge (see Fig. 5(b) and (c)). The fractograph of D121
appears rough multilayer structure with distinct edges like mica
(see Fig. 5(d) and (e)). The multilayer structure could increase the
area on which the tensile force acts, which could account for the
raise of tensile strength. And one of the layers is composed of abun-
dant of smooth grains in high magnification micrograph as shown
in Fig. 5(f). The micrograph of D221 also appears multilayer struc-
ture analogous to that of D121, but the number of layers is fewer
(see Fig. 5(g) and (h)), which indicates that tensile strength would
not increase as the diameter of Al2 O3 particles rises.
3.4. Effect of filler content on mechanical properties and fracture
mechanism
Tensile, impact, compressive, flexural strength and ball inden-
tation hardness as the function of content of inorganic nanometer
particles are all shown in Fig. 6(a) and (b). All mechanical properties
of specimens L121 and L131 which dispersed by LSMD are supe-
rior to that of D000, except that tensile strength of L131 is lower
than that of D000. Furthermore, tensile, compressive and impact
strength of L121 are optimal of all and the impact strength of L121
is even eight times that of D000. But the higher flexural strength and
ball indentation hardness of L131 are also presented compared with
L121. In addition, all the mechanical properties of nanometer SiO2
reinforced PEEK are superior to that of D000 except for the tensile
strength of L424 and L434, but the improvement of it is worse than
that of nanometer Al2 O3 reinforced PEEK. Analogous with speci-
mens filled with nanometer Al2 O3 particles, tensile, compressive
and impact strength of L424 are superior to that of L434, except
that other two mechanical properties of L434 are better than that
of L424, even the ball indentation hardness of specimen L434 is the
highest of all. As is shown in above Fig. 4, the flexural modulus also
monotonically increases with the increase in mass fraction of filled
Al2 O3 particles. But for tensile modulus, when the content adds to
10% tensile modulus decreases. It can be found that the variation of
modulus is almost in correspondence with that of strength in this
test.
Representative SEM micrographs of the tensile fracture surface
of L121, L131 and L424 at various magnifications are all shown in
Fig. 7, respectively. The micrograph of L121 also appears multilayer
structure but the drop in level is greater than that of D121, which
would account for the higher strength in tensile test (see Fig. 7(a)).
The edge of one of the layer shown in Fig. 7(a) is composed of
smooth grains, which are less than 100 nm in diameter (see Fig. 7(b)
and (c). However, there is a big smooth area in the middle of the
micrograph of L131 as shown in Fig. 7(d), which indicates more
brittle fracture characteristic than other specimens. Clear plastic
deformation in the edge of the smooth area could be found at higher
magnification as shown in Fig. 7(e) and (f). And lots of holes could be
found in the micrograph of L424 as shown in Fig. 7(g), which indi-
cates that the compatibility of PEEK matrix and SiO2 is not good
and account for its lowest tensile strength of all specimens.
3.5. Effect of coupling agents for nanoparticle treatment on
mechanical properties
As is shown in Fig. 8(a) and (b), tensile, the flexural and impact
strength of specimens which filled with coupling agents treated
nanometer Al2 O3 particles are higher than that of neat PEEK, which
implies the well interaction between the nanometer Al2 O3 particles
and polymer segment chain. Furthermore, the impact strength of
specimens filled with coupling agents treated Al2 O3 is higher than
that of L120 filled with untreated Al2 O3 . It is possible that the gen-
eration of ductile interface layer between the surface of particles
and coupling agents improves the absorption to impact energy. But
there is no analogous trend in the others mechanical properties,
which is possible due to the weakening of strength and rigidity of
composites for the generation of ductile interface.
3.6. Effect of dispersing methods of nanoparticles in PEEK on
mechanical properties
Four kind of dispersing methods: DMM, LSMD, UD and BMD
were used to disperse fillers in PEEK matrix. Fig. 9(a) and (b) give
the variation of mechanical properties with these different dispers-
ing methods. It is seen that the compressive, flexural and impact
strength of L121 have improved by 14.8%, 10.4% and 15.7%, respec-
tively, compared with that of D121. But the tensile strength and ball
indentation hardness of L121 are slightly greater than that of D121.
As far as methods of LSMD, UD and BMD are concerned, the vari-
ation of mechanical properties with various dispersing methods is
slightly. Among the three kinds of specimens, the tensile and com-
pressive strength of B141 are superior, while the flexural strength
and ball indentation hardness of U141 are best.
Fig. 10 shows the SEM micrographs with different magnification
of tensile fracture surface for PEEK composites by different dispers-
ing methods. From Fig. 10(a), it can be seen that there are abundant
of layers on the fractograph of L141, and Fig. 10(b) also displays the
obviously tough fracture characteristic. But Fig. 10(c) shows that
there are large numbers of grains about 100 nm in diameter, which
would be Al2 O3 conglomeration or fragments of PEEK resin. Accord-
ing to Fig. 10(d), the fractograph also displays abundant of layers.
But it is seen that there are some great conglomeration with diam-
eter above 2 ␮m from Fig. 10(e) and (f), which reveal that method
of ultrasonic cannot smash the larger grains of Al2 O3 . Fig. 10(g) and
(h) show that the surface of fracture is smoother than above two
and there are little layers, but there are more homogeneous dis-
persed grains with more little diameter than others, which prove
that ball milling dispersing method can better comminute the con-
glomeration and disperse it.
4. Conclusion
(1) The filling of Al2 O3 nanometer particles results in a decrease of
crystallinity compared with neat PEEK. This is possibly due to
the increase of rigidity of PEEK chain for the filling, which could
encumber the rearrange of PEEK chain in space. In addition,
the glass transition temperature of nanometer Al2 O3 parti-
cles reinforced PEEK has increased about 20 ◦ C, however there
is a slight reduction in melting point compared with neat
PEEK.
(2) AFM micrographs of specimen D121, L121 and L131 could con-
firm that nanometer Al2 O3 particles are dispersed in PEEK
with nanometer size. And dispersing homogenization of 5 wt.%
inorganic particles in specimen is superior to that of 10 wt.% par-
ticles. In addition, liquid-solid mechanical dispersing method is
better than dry powder direct mechanical mixing method.
(3) Tensile strength, ball indentation hardness and impact strength
of PEEK filled with 15 nm Al2 O3 particles are better than those
of PEEK filled with 90 nm Al2 O3 particles, however, the lat-
ter exhibits better performance in flexural and compressive
strength but has lowest value of ball indentation hardness of
all.
(4) PEEK filled with 5 wt.% Al2 O3 represents better performance
than that filled with 10 wt.% Al2 O3 in tensile, compressive and
impact strength, but the latter exhibits better performance in
flexural strength and ball indentation hardness. In addition,
 P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391 391

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