Tensile Properties and Morphology of PP/EPDM/Glass Bead Ternary Composites

J. 2.

R.K.Y.LI,' d S . C.TJONG'

'Department o f Physics and Materials Science City University o f Hong Kong Kowloon, Hong Kong 2Depczrtmento f Chemical Machinery South China University o f Technology Guangzhou510641, P. R. China
The tensile properties of three types of injection molded glass bead (GB) filled polypropylene (PP)/ethylene-propylene-diene monomer (EPDM) ternary composites have been determined at room temperature by using an Instron materials testing machine. The effects of the filler surface treatment, the glass bead (GB1)pretreated with a silane coupling agent and the EPDM (EPDM-MA)modified with a maleic anhydride, and the filler content on the tensile mechanical properties of the ternary PP composites have been investigated. The Young's modulus (E,) increases while the yield stress (uYJand tensile fracture strength (uk) of the composites decrease with increasing the volume fraction of glass beads (41~1 when the volume fraction of EPDM is constant (+e = 1 O O h ) .The E, values of PP/EPDM/GBl and uk for PP/ EPDM-MA/GB2 (no surface pretreated) systems are the highest at the same +g The tensile fracture energy (Ek) and tensile fracture strain ( E ~ of ) PP/EPDM/GBl and PP/EPDM/GB2 systems appear to peak at +g = 25%. However, the Ebc and E~ of PP/EPDM-MA/GB2 system show little changes with increasing +g The fracture surfaces of ternary composites have been examined in a scanning electron microscope. The correlation between the tensile properties and morphologies of these materials have been discussed.
1 . INTRODUCTION

oughness and strength are important parameters that characterize the performances of structural materials, particularly for the polymeric materials. It is generally known that the toughness of thermoplastic materials can be improved dramatically by modification with rubber particles. However, their stiffness and strength are reduced sigmficantly due to the rubber addition. On the other hand, the stiffness of polymeric materials can be enhanced via the incorporation of rigid inorganic particles but the toughness is decreased substantidly. Therefore, the research topics on the improvements of toughness and stiffness performances of brittle or quasi-ductile polymeric materials have attracted considerable attention of the materials scientists. In the past decade, there have been a number of studies on the structure and mechanical properties of polymer/rubber/rigid particle ternary composites (1-13). In the case of particulate-filled polymeric composites, their mechanical properties are closely related to the morphological structure of the filler/matrix interface.
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The results of the stress analysis by means of the finite element method (FEM) on the particulate filled polymers showed that the formation of a soft and elastic layer near the rigid inorganic particles (i.e. core-shell structure) is beneficial in improving the toughness and strength of such composites owing to the development of a suitable stress distribution in that region (14). pukanszky, et aL (1. 2, 4) have analyzed the formation of phase structures in polypropylene (PP)/elastomer/filler composites, and assumed that two kinds of phase structures tend to develop in such composites: (1) elastomer and rigid particles are dispersed separately: (2) elastomer tends to encapsulate the particles by modifying elastomer with maleic anhydride (MA) or acrylic acid. The former case depends on the reversible work of adhesion, and on the filler size, while the latter depends on the viscosity and shear rate. Composites with core-shell particles generally have lower yield stress but higher impact strength than the composites with functionalized matrix (4).The interfacial adhesion between the inclusion and matrix is another important factor affecting the
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J.2 .L i a q , R. K. Y.L i and S . C. gong

mechanical properties of composites in addition to the morphological structure. Chiang et aL (3)pointed out that the mutual wettability and adhesion of the components play a crucial role on the structure and properties of PP/elastomer/filler systems. Furthermore, impact modification can be achieved effectively through the incorporation of elastomers of sufficient miscibility (3). Zhang and Berglund (5)found that the addition of glass bead compensated the loss in modulus but had little effect on the yield stress of epoxy/CTBN-rubber composites. However, it contributed significantly to the fracture toughness by providmg an additional mechanism for toughening of both the unmodified and rubber-modified epoxy. For PP ternary composites filled with inorganic filler (CaCO, or Mg(OH)J and ethylenepropylene elastomer (EPFQ,similar results in tensile properties were observed (7). More recently, Strider and Mulhaupt (10)indicated that the elastomer interlayer and in situ encapsulation of glass beads in PP/elastomer/glass bead composites impaired filler reinforcement to result in a lower modulus but afforded a significant improvement in the notched Izod impact strength. The objective of this article is to iden* the i nfluence of the filler content and the filler surface pretreatments (including glass beads and rubber particles) on the tensile properties and morphologies of PP/elastomer/glass bead ternary composites.
2 . EXPERIMENTAL 2 . 1 Materms

Chemical Company, using the twin screw extruder in temperatures from 180 to 220C to formed masterbatch EPDM-MA. The blending weight ratio (EPDM/ MA/DCP) was kept at 89.7/10/0.3. Subsequently, it was blended with PP and glass beads in the t w i n screw extruder again at temperatures varied from 180C to 230C. The extrudates of the composites consisted of 10% volume fraction of the masterbatch and various glass bead contents were granulized by a pelletizer. Finally, a l l composite pellets were molded into tensile bars by using an injection molding machine within temperatures at 180C 230C. The relationship among the volume fraction (+J, density (pJ and weight fraction (wi) of composite components is given by:

W i Pc 4* = -W T Pi

and
~c

4rn~r-n + 4gPg + 4 e P e

(2)

where wT is the total material weight including the matrix and fillers, the subscripts m, g, and e refer to the matrix, glass beads, and elastomer, respectively.
2 . 3 &paratun and Methodology

PP used as the matrix material in this work was a commercial grade with trade mark of Himont Pro-fax 6331@. The solid state density and melt flow rate (2.16 kg, 230C) of PP were 0.9 g/cm3 and 12 g/(lO min), respectively. Two types of glass beads (Spheriglass@, A-GLASS, Potters Industries Inc) with same mean diameter of 35 pm were selected as the filler; one was surface pretreated with a silane coupling agent CP-03 (GB1) and the other received no surface treatment (GB2).They were solid spherical particles with a density of 2.5 g/cm3. The elastomer filler was ethylene-propylene-diene monomer (EPDM, grade 2470, Nordel@, W o n t Co.), which had a na~uw molecular dishibution. The Mooney viscosity and density were ( M L ~ ~ $ 68 , and ) 0.87 g/cm3, respectively.
2 . 2 Sample Preparation
Two blending routes were adopted for the fabrica-

The tensile mechanical properties were measured by using an Instron materials testing machine (model 4206) at room temperature. The tests were conducted according to ASTM D638-91 standard. The width and thickness of the specimens were 13.0 mm and 3.20 mm, respectively. The cross head speed of 50 mm/ min was employed in order to observe the tensile fracture behaviour. On the other hand, to measure the Youngs modulus of the materials an extensometer was used with a tensile rate of 1 mm/min. The morphological study was carried out by means of a scanning electron microscope (SEM, Jeol JSM820). to observe the fractural surface of the specimens, and the interfacial structure between the mat r i x and filler, and the dispersion or distribution of the fillers in the matrix. These specimens were taken from the fracture section and were coated gold before SEM observation.
3 . RESULTS AND DISCUSSION 3 . 1 Tensile Curves

tion of ternary composites. For the PP/EPDM/GBl and PP/EPDM/GB2 systems, PP pellets and the fillers were blended directly by using a t w i n screw extruder (Brabender PL2000) at temperatures from 180 to 230C. The volume fraction of EPDM in composites was fixed at loohbut the concentration of glass beads was varied. For t h e PP/EPDM-MA/GB2 system, EPDM was initially functionalized using maleic anhydride (MA) and dicumyl peroxide (DCP), which were respectively supplied by Fluka Chemie and Aldrich
414

Figure 1 shows the typical tensile curves of PP/ EPDM/GB2 system. It can be seen that the maximum tensile stresses of the samples decrease with increasing the volume fraction of glass beads, +g as the volume fraction of EPDM, is fixed at 10 O h . When +g is smaller than 30%. the tensile elongation increases with the increase of +g and it reaches a maximum at +g = 25%. It indicates that the ductility of PP can be improved by addition with glass beads under the applied test conditions.

+ ,

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25
"/

15

a . E
W

c[J

10

5
..

"

50

100
&

150

200

(%)

Flg. 1 . Tensile curves o f PP/EPDM GB2.

3 . 2Y o u n g ' .

Modulus

Figure 2 displays the relationship between the Young's modulus of the composites, E,. and the filler content for 4=being fixed at 10%. With an increase of 4g, the E, of PP/EPDM/GBl and PP/EPDM-MA/GBZ systems increases significantly, while the E, of PP/ EPDM/GBP system increases slowly with increasing 4g when 4g is higher than 25Oh. It means that the improvement in the interfacial adhesion between the matrix and inclusion is beneficial to enhance the stiffness of composites. Such an improvement can be achieved through the appropriate modification of filler surfaces, i.e., glass beads or elastomer particles, with silane coupling agent and MA, respectively. In previous work (15).we have presented an equation for predicting the Young's modulus of rigid inorganic particulate filled thermoplastic composites,

The theoretical prediction for E, of the composites based on Eq 3 is shown in FYg. 2 (solid line). It can be seen that the predicted values basically correlate well with the measured E, data of the composites under these applied test conditions. In this article, h = 1.5, u = 0.33, Ef- E, = 68.966 GPa, and Em = 1.578 GPa. 3 . 3 Tensile Streu Among the mechanical properties, the tensile yield stress of composites is of primary importance, because it gives information on the maximum allowable load without considerable plastic deformation. The correlation between the tensile yield stress, uw of the materials and glass bead concentration is shown in Rg. 3. I t can be seen that uyc decreases nonlinearly with an increase of 4g,and the difference in uycamong the three filled systems is relatively small. It suggests that the effect of the surface treatment for the fillers on the tensile yield stress of the composites is insignificant under the test conditions applied. In previous work, the authors proposed an expression describing the relationship between u , , and the volume fraction of fillers, the parameters of filler geometry and the interfacial adhesion between the matrix and inclusions (16).The mathematical equation is given as follows by assuming the debonding angle being 65":
uyc = uym(1-0.99 f$f2 ' 3 )

and
s=-

7- 5 v 15(1-V)

(4)

9j= 9 ,+ 9 e

(5)

where m = Ef/E,,,. Eris the Young's modulus of f i l l e r .v is the Poisson's ratio of the matrix, A is a constant related to the particle geometry and interfacial adhesion.

(6)

where up is the tensile yield stress of the matrix.

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J. 2 .LiQng, R. K. Y.Li, and S. C.gong

PP / EPDM / GBI PP / EPDM / GB2 PP / EPDM-MA / GB2

m c3

a .
I I I

LU"
1.0

0.5

The comparison between the cry, calculated from Eq 6 and the measured cry, from the experiments is shown in Fig. 3. It can be seen that the predicted values are close to the measured data of the samples.

7 1 ,proposed an equation based Nicolais and Narkis ( 1 on the hypothesis that no or very poor interfacial adhesion exists between the matrix and spherical particles:

24
rn

21%

PP I / EPDM / GBI PP / EPDM / GB2 PP / EPDM-MA / GB2

$Ie= 10%

a .
2
W

12 -

b h

9-

Equation (7)

t
0

10

15

20

25

30

Flg. 3. uyc as afunction o f c+~.

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Tensile Properties and Morphology

uyc =

uym(l-l.21+J2/3)

(53

It is apparent from R g . 3 that Eq 7 deviates signifivalues. It implies cantly from the experimental uyc that a good interfacial bonding exists between the mat r i x and the fillers. Figure 4 displays the relationship between the tensile fracture stress, uk, of the composites and glass bead contents. It is evident that uk decreases nonlinearly with increasing +g Furthermore, PP/EPDM-MA/ GB2 system exhibits the highest ubc.It indicates that the tensile fracture strength of the composites can be enhanced by modification on EPDM with MA and DCP. In other words, a strong interfacial bonding between the maleated EPDM and glass beads leads to the formation of a core-shell structure, that is, glass bead is encapsulated by elastomer. In this case, the stress distribution on the surface of glass bead is improved due to the development of a s o f t and elastic layer around the rigid particles. Thus the tensile fracture strength of the composites increases correspondingly.
3.4 Tenmile Toughne~ and Ductility

for PP/EPDM-MA/GB2 system. It suggests that the plastic yielding of the matrix around the glass bead is the main mechanism for tensile toughening of these composites. When the sample is loaded under the tensile stress, the matrix layer around the rigid particle produces a n obvious plastic deformation and first yield owing to the aistence of stress concentration to absorb a number of plastic deformation energies. Hence, the tensile toughness of the composites increases correspondingly. The tensile strain at break generally reflects ductility of materials. Figure 6 shows the dependence of the tensile fracture strain, E ~ of . the samples on glass bead concentration. It can be observed that the trend of E~~ versus +g curves are similar to those of Ebc against as shown in Fig. 5. It indicates that the ductility and toughness of the PP/EPDM blends can be improved by adding with glass beads whether the glass bead surface is pretreated or not; while the effect of glass bead content on these properties is insignificant for filled PP/EPDM-MA system.

+ ,

3 . 5 Morphology
Figures 7, 8, 9, 10, and 11 are the scanning electron microphotographs of the tensile fracture surfaces of the binary PP/EPDM blends and ternary composites. It can be observed from Figs. 7 and 8 that cavitation occurs in the PP matrix around the elastomer particle, i.e., low interfacial adhesion between the PP matrix and EPDM. In this case, the interfacial debonding occurs initially between the matrix and rub-

Tensile fracture energy is an important parameter characterizing the tensile toughness of materials. The dependence of the tensile fracture energy, Ebc, of the composites on the glass bead contents is illustrated in Fig. 5. This figure reveals that the Ek of PP/EPDM/ GB1 and PP/EPDM/GBB systems increases with increasing and reaches an apparent peak at = 25%. However, Ebc essentially shows little changes with 4,

+ ,

+ ,

24
20 16

o
A

PP I EPDM I GBI PP I EPDM I GB2 PP I EPDM-MA I GB2

12

0' 0

10

15

20

25

30

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J. 2 . Liang, R. K. Y. Li, and S. C.lJong

70
+ PP / EPDM / GBI

+ PP / EPDM / GB2

40

501
t t
t
10
0

PP / EPDM-MA / GB2
I I I

$,=lo%

30
LU
c\r\

10

15

20

25

30

Fig. 5. Dependence o f Ebc on +T

ber particle thereby leading to cavitation under the application of tensile stress. It could be the cause of lower tensile fracture toughness and tensile ductility

of the blends and the composites (see Figs. 5 and 6). For PP/EPDM/GB 1 and PP/EPDM/GB2 systems, there are some ribbon-like matter around glass beads

+ PP / EPDM / GBI
-o-

PP / EPDM / GB2 PP / EPDM-MA / GB2

T I T
f T

s
W

120

1
I I I I

0'

10

15

20

25

30

Rg. 6. Dependence o f Ebc on +q

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Tensile Properties and Morphology

Flg. 7. SEM photograph of tensilefracturesection of PP/EPDM.

(see Figs. 9 and 10). These ribbon-like matter are formed when the matrix layer around the rigid particles occurs plastic deformation of the matrix owing to stress concentration under tensile load. Consequently, they absorb a considerable amount of plastic deformation energies. Hence the tensile fracture toughness and ductility of the materials are enhanced significantly (seeFigs. 1 , 5 and 6).It can be observed from Fig. 1 1 that no ribbon-like matter near the glass beads is formed, that is, the tensile fracture cross-section is relatively smooth. It suggests that the tensile fracture is brittle break. This leads to low tensile ductility as shown in Figs. 5 and 6. Finally, it can be seen in Fig. 1 1 that the glass beads are covered by a t h i n white layer of EPDM. This is because the interfacial bonding

between glass beads and the elastomer is enhanced through modification of EPDM with MA and DCP. The glass beads, therefore, are encapsulated by maleated EPDM to form a so-called core-shell structure during mixing in the compounder. In this case, the stress distribution is somewhat improved, leading to an increase of the tensile fracture strength (see Fig. 4). On the basis of SEM examination, the microstructures of the interfacial layer between the filler and the matrix of the ternary composites could be divided into three types: (i) the elastomer particles and glass beads are dispersed separately in the PP matrix (e.g. PP/EPDM/GB2 system, see Fig. 12 a);(ii) some glass beads are encapsulated by the PP matrix and the rubber particles are dispersed in the matrix

Ffg. 8. SEMphotosmph o f tensilefracture section of PP/EPDMMA.

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J. Z. Liang,R. K. Y.L i andS. C . qong

Fig. 9. SEMphotogTaph of tensilefracture section of PP/EDPM/GBl($,, = 20%).

(e.g. PP/EPDM/GBl system, see Rg. 12 b); (iii) glass beads are firstly encapsulated by EPDM to form a core-shell model, and then disperse in the PP matrix (e.g. PP/EPDM-MA/GB2, see Rg. 12 c). For models (i) and (ii), the rigid inorganic particles directly contact with the resin matrix, the matrix layer around the particle yield first and produces an obvious plastic deformation owing to the stress concentration under a given tensile load: this plastic deformation absorbs a considerable amount of plastic deformation energy to produce briffle-ductile transition, thus the tensile toughness of the material is increased. In other words, tensile yield is the main toughening mechanism for these filled systems. For model (iii), the glass beads are encapsulated by a t h i n layer of s o f t and elastic rubber, because the stress on the bead is transferred though

this s o f t and elastic layer, the stress distribution on the particle is improved, which is obvious different from that of the former models. In this case, the tensile stress at break of the material is increased, but the tensile toughness and ductility show liffle changes. In addition, core-shell structure is beneficial to increase the Young's modulus (see Rg. 2).
4. CONCLUSION

For particulate filled polymer composites, the mechanical properties depend, to much extent, upon the interfacial morphology and structure between the inclusions and matrix. To i d e n e the effects of filler surface treatment on the tensile properties of filled PP composites, three filled systems were made. They

Fig. 10. SEMphot5graph of tensilefmcture section of PP/EDPM/GB2 [ $ g = 20%).

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Tensile Properties and Morphology

F @ . 11. SEMphotograph o f tensilefrarhve section o f PP/EDPM-MA/GBZ ( + g

= 2096).

were: (i) PP/EPDM/GBl (glassbeads were coated with a silane coupling agent), where some glass beads were covered by PP and rubber particles disperse in the PP matrix, (ii) PP/EPDM/GB2 ( a l l fillers were untreated), where glass bead and rubber particles separately dispersed in the PP matrix, and (iii) PP/EPDM-MA/GB2 (EPDM modified by a maleic anhydride), where glass beads were encapsulated by elastomer, and then dispersed in the PP matrix. The results showed that the Youngs modulus, E,, increases but the yield stress, uyc,and tensile fracture strength, ubC. of the composites decrease with increasing the volume fraction of glass beads, +a, when the volume fraction of EPDM is = 10%); at the Same conditions the kept constant

values of E, of system (i)and ubC for system (iii)are the highest. The tensile fracture energy, EbC. and tensile fractum strain, E~ of system (i)and system (ii)increase with the increase of +q and an apparent maximum is reached at +g = 25%. However, the dependence of EbC and E~ for system (iii)on +g is not obvious. It suggests that the brittle-ductile transition in tension is mainly attributable to the absorption of plastic deformation energy owing to the existence of stress concentration of the matrix around the glass beads for systems (i) and (ii), and the tensile strength can be enhanced by improving the morphological structure (i.e. core-shell model) and adhesion of the interface between the filler and the matrix for system (iii).

PP

&

bb /o Glass bead
Glass bead

0I-L
Glass bead

4
I

0
0 0
PP

Ftg. 12. Diagram o f morphological strurture o f the oomposites.

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J.Z.Liang, R . K . Y.L i

a d s . C. gong
8. J. Jancar and A. T. Dibenedetto, J. M a t e r . Sci., 30,

ACKNOWLEDGMENT
The first author was the recipient of a research studentship from the City University of Hong Kong during the course of this work.

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