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222AL2O3 Percent
222AL2O3 Percent
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.
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
90
10
–
–
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
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
95
–
5
–
–
–
5
–
–
–
–
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
–
–
–
–
–
–
˚ 12 nm SiO2
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
A JXA-840A scanning electron microscope (SEM) was used to Fig. 4. Effect of diameter and mass fraction of Al2 O3 particles on tensile and flexural
evaluate the fractograph of tensile testing specimens. The fractured 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 impact strength, which increased by 5% and 5.6 times than neat
fracture mechanism PEEK, respectively. However, compressive and flexural strength
would increase as the diameter of Al2 O3 particles rises. Compres-
As is shown in Fig. 3(a) and (b), specimens filled with 15 nm sive and flexural strength of specimen filled with 90 nm Al2 O3
Al2 O3 particles and dispersed by DMM possess maximal tensile and 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- Nanometer particles possess large specific surface area, high
eter of Al2 O3 particles. It can be seen that the flexural modulus surface activity and better interactivity with the polymer chain
monotonically increases with the increase in the diameter of Al2 O3 segment in comparison with normal size particles, so the filling
particles, while the variation of tensile modulus with diameter has of it could improve the toughness, rigidity and strength of com-
no similar trend. 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 the decrease of tensile and impact strength. However, compres-
more microcracks and more absorption to impact energy. In addi- sive and flexural strength would increase with the improvement of
tion, inorganic particles could interrupt and delay the spread of material rigidity.
microcrack or stop its transformation to the fracture crack. With Representative SEM micrographs of the tensile fracture surface
the increase of diameter, the specific surface area of inorganic par- of D000, D121 and D221 at various magnifications are all shown
ticles would decrease, then lead to the weakening of interaction in Fig. 5. Dimples are distinctly visible in the micrograph of D000
between inorganic particles and polymer, finally would result in (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- eration of ductile interface layer between the surface of particles
ple appears smooth but some distinctly visible radial striae can be and coupling agents improves the absorption to impact energy. But
found on the edge (see Fig. 5(b) and (c)). The fractograph of D121 there is no analogous trend in the others mechanical properties,
appears rough multilayer structure with distinct edges like mica which is possible due to the weakening of strength and rigidity of
(see Fig. 5(d) and (e)). The multilayer structure could increase the composites for the generation of ductile interface.
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-
3.6. Effect of dispersing methods of nanoparticles in PEEK on
dant of smooth grains in high magnification micrograph as shown
mechanical properties
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
Four kind of dispersing methods: DMM, LSMD, UD and BMD
(see Fig. 5(g) and (h)), which indicates that tensile strength would
were used to disperse fillers in PEEK matrix. Fig. 9(a) and (b) give
not increase as the diameter of Al2 O3 particles rises.
the variation of mechanical properties with these different dispers-
ing methods. It is seen that the compressive, flexural and impact
3.4. Effect of filler content on mechanical properties and fracture
strength of L121 have improved by 14.8%, 10.4% and 15.7%, respec-
mechanism
tively, compared with that of D121. But the tensile strength and ball
indentation hardness of L121 are slightly greater than that of D121.
Tensile, impact, compressive, flexural strength and ball inden-
As far as methods of LSMD, UD and BMD are concerned, the vari-
tation hardness as the function of content of inorganic nanometer
ation of mechanical properties with various dispersing methods is
particles are all shown in Fig. 6(a) and (b). All mechanical properties
slightly. Among the three kinds of specimens, the tensile and com-
of specimens L121 and L131 which dispersed by LSMD are supe-
pressive strength of B141 are superior, while the flexural strength
rior to that of D000, except that tensile strength of L131 is lower
and ball indentation hardness of U141 are best.
than that of D000. Furthermore, tensile, compressive and impact
Fig. 10 shows the SEM micrographs with different magnification
strength of L121 are optimal of all and the impact strength of L121
of tensile fracture surface for PEEK composites by different dispers-
is even eight times that of D000. But the higher flexural strength and
ing methods. From Fig. 10(a), it can be seen that there are abundant
ball indentation hardness of L131 are also presented compared with
of layers on the fractograph of L141, and Fig. 10(b) also displays the
L121. In addition, all the mechanical properties of nanometer SiO2
obviously tough fracture characteristic. But Fig. 10(c) shows that
reinforced PEEK are superior to that of D000 except for the tensile
there are large numbers of grains about 100 nm in diameter, which
strength of L424 and L434, but the improvement of it is worse than
would be Al2 O3 conglomeration or fragments of PEEK resin. Accord-
that of nanometer Al2 O3 reinforced PEEK. Analogous with speci-
ing to Fig. 10(d), the fractograph also displays abundant of layers.
mens filled with nanometer Al2 O3 particles, tensile, compressive
But it is seen that there are some great conglomeration with diam-
and impact strength of L424 are superior to that of L434, except
eter above 2 m from Fig. 10(e) and (f), which reveal that method
that other two mechanical properties of L434 are better than that
of ultrasonic cannot smash the larger grains of Al2 O3 . Fig. 10(g) and
of L424, even the ball indentation hardness of specimen L434 is the
(h) show that the surface of fracture is smoother than above two
highest of all. As is shown in above Fig. 4, the flexural modulus also
and there are little layers, but there are more homogeneous dis-
monotonically increases with the increase in mass fraction of filled
persed grains with more little diameter than others, which prove
Al2 O3 particles. But for tensile modulus, when the content adds to
that ball milling dispersing method can better comminute the con-
10% tensile modulus decreases. It can be found that the variation of
glomeration and disperse it.
modulus is almost in correspondence with that of strength in this
test.
Representative SEM micrographs of the tensile fracture surface 4. Conclusion
of L121, L131 and L424 at various magnifications are all shown in
Fig. 7, respectively. The micrograph of L121 also appears multilayer (1) The filling of Al2 O3 nanometer particles results in a decrease of
structure but the drop in level is greater than that of D121, which crystallinity compared with neat PEEK. This is possibly due to
would account for the higher strength in tensile test (see Fig. 7(a)). the increase of rigidity of PEEK chain for the filling, which could
The edge of one of the layer shown in Fig. 7(a) is composed of encumber the rearrange of PEEK chain in space. In addition,
smooth grains, which are less than 100 nm in diameter (see Fig. 7(b) the glass transition temperature of nanometer Al2 O3 parti-
and (c). However, there is a big smooth area in the middle of the cles reinforced PEEK has increased about 20 ◦ C, however there
micrograph of L131 as shown in Fig. 7(d), which indicates more is a slight reduction in melting point compared with neat
brittle fracture characteristic than other specimens. Clear plastic PEEK.
deformation in the edge of the smooth area could be found at higher (2) AFM micrographs of specimen D121, L121 and L131 could con-
magnification as shown in Fig. 7(e) and (f). And lots of holes could be firm that nanometer Al2 O3 particles are dispersed in PEEK
found in the micrograph of L424 as shown in Fig. 7(g), which indi- with nanometer size. And dispersing homogenization of 5 wt.%
cates that the compatibility of PEEK matrix and SiO2 is not good inorganic particles in specimen is superior to that of 10 wt.% par-
and account for its lowest tensile strength of all specimens. ticles. In addition, liquid-solid mechanical dispersing method is
better than dry powder direct mechanical mixing method.
3.5. Effect of coupling agents for nanoparticle treatment on (3) Tensile strength, ball indentation hardness and impact strength
mechanical properties 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-
As is shown in Fig. 8(a) and (b), tensile, the flexural and impact ter exhibits better performance in flexural and compressive
strength of specimens which filled with coupling agents treated strength but has lowest value of ball indentation hardness of
nanometer Al2 O3 particles are higher than that of neat PEEK, which all.
implies the well interaction between the nanometer Al2 O3 particles (4) PEEK filled with 5 wt.% Al2 O3 represents better performance
and polymer segment chain. Furthermore, the impact strength of than that filled with 10 wt.% Al2 O3 in tensile, compressive and
specimens filled with coupling agents treated Al2 O3 is higher than impact strength, but the latter exhibits better performance in
that of L120 filled with untreated Al2 O3 . It is possible that the gen- flexural strength and ball indentation hardness. In addition,
P. Guoliang et al. / Materials Science and Engineering A 492 (2008) 383–391 391