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The Effect of Low Levels of Plasticizer on the
Rheological and Mechanical Properties of Polyvinyl

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C hIo rid e/N ewsp r int - Fiber Co mp0s ites

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LAURENT M. MATUANA*

Faculty of Forestry
University of Toronto
Toronto, Ontario, Canada M 5 S 3B3
CHUL B. PARK

Department of Mechanical and Industrial Engineering

University of Toronto
Toronto, Ontario, Canada M 5 S 3G8
and
JOHN J. BALATINECZ

Faculty of Forestry
University of Toronto
Toronto, Ontario, Canada M5S 3B3
Plasticizers play a key role in the formulation of semirigid and flexible PVC and in

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determining their physical properties and processability. This study examines the
effects of the low phr levels of plasticizer (DOP) on the rheological and mechanical
properties of rigid and semi-rigid PVC /newsprint-fiber composites. Mechanical and
rheological properties of unfilled PVC compounds and PVC /newsprint-fiber com-
posites a t 45 phr were compared over the range of 0 to 15 phr of DOP plasticizer.

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Analyses of data using SAS procedures of ANOVA were also conducted to discern
the effects of concentration of plasticizer on these properties. The following conclu-
sions were reached: 1)DOP was relatively ineffective in improving melt flow index of
the composites compared to unfilled PVC. 2) The composites were significantly
inferior in tensile strength a t yield and stiffer than unfilled PVC. The differences
observed were roughly the same over the DOP range studied. 3 )Elongation at break
and toughness (break energy) were lower for the composites and were essentially
independent of DOP level, whereas there was a significant improvement for unfilled
PVC over the DOP range studied. 4) Impact strengths of the composites and unfilled
PVC were essentially comparable u p to about 11.25 phr of DOP. However, a t 15 phr
DOP, impact strength of the composite was far inferior to that of unfilled PVC. 5)The
well-known antiplasticization effect was noted for the unfilled PVC, as well as to
some extent for the filled PVC.

INTRODUCTION Currently, the fiber-reinforced thermoplastic com-

posites markets, which represent one third of all perfor-
composite is any combination of two or more ma-
A terials in any form and for any use. It takes ad-
vantage of the beneficial characteristics of each com-
mance plastics, are dominated by glass fiber (93%of
reinforcement materials) ( 3 )and some other inorganic
filers such as talc, mica, clay, and calcium carbonate
ponent material and often has more useful properties
(4). These high-density conventional fillers offer wide

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than any of the constituents on its own ( 1 , 2).

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property changes in the composites, but on a volumetric
basis, their use is not cost-effective (5).In addition, these
inorganic fillers cause wear of equipment during pro-
* To whom correspondence should he addressed. cessing (6).

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, DECEMBER 1997, Vol. 3, No. 4 265
 Luurent M. Matuana, Chul B. Park a n d John J. Balatinecz

in recent years, natural organic fillers such as dipole bonding therefore decreases the restrictions on
wood-fibers and other lignocellulosic fibers have pen- deformation of the molecules. As a result, the chain
etrated slowly into this market because they possess flexibility increases and flow properties are enhanced.

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many advantages relative to most common mineral Based on this general mechanism, when a plasticizer
fillers. These include high specific stiffness and is incorporated into PVC, the polar groups of plasti-
strength (7);availability; lower density; lower cost on a cizer bond with the polymer dipoles, and the nonpolar
unit-volume basis; low hardness, which minimizes parts act as shields between polymer dipoles, thus
wear of the processing equipment; renewability; recy- resulting in less cohesion overall, with consequent
clability; nonhazardous; biodegradability, and so on increased freedom of molecular movement.
(8, 9). The replacement of inorganic fillers with com- In addition to the melt flow properties, the flexibil-
parable lignocellulosic fibers provides weight savings ity, extensibility, and rigidity of finish products at

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and decreases the cost without reducing the rigidity of room temperature are influenced by the addition of
the composite. plasticizers (17-19). The effects of various concentra-
Most studies on thermoplastic/cellulosic fiber com- tions of plasticizers on the mechanical properties of
posites have centered around the investigation of polymers and copolymers in the high concentration
polyolefins as a polymeric matrix (9-16). Although range have been reported ( 31 , 33-38]. In general, a t a
PVC produced worldwide accounts for almost 30%of higher plasticizer concentration (more than 1 5 2 0 %1,
the total production of thermoplastics, second to a the materials become softer and tougher, with a lower
combined product of all polyolefins (i.e., low/high tensile strength, a lower modulus, and a higher elon-
density polyethylene and polypropylene) (17-19), the gation a t break a n d a higher impact strength. How-
use of cellulosic fibers in PVC is not common a s in ever, it was also discovered that lightly plasticized
polyolefins. Relatively little in-depth examination has compounds are, contrary to the general belief a t the
been performed for PVC /wood-fiber composites in time, more rigid and brittle a t a low temperature than
particular, and most studies on PVC/wood-fiber com- unplasticized ones (37-40) because of the phenome-
posites have focused on the improvement of the fiber non termed antiplasticization. Although the manifes-
and plastic interface, the influence of processing pa- tations of this phenomenon have been reported, their
rameters, the effect of the nature of the fibers, and the mechanism is not fully described in the literature.
mechanical properties (21-29). Relatively few studies According to Horsley (40), the maximum tensile
discussed the influence of PVC formulation on the strength is attributed to the increase in the degree of

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properties of PVC /wood-fiber composites. Yet it is well order, or even of the crystallinity of the system. The
known that the processability of PVC strongly de- orientation of the macromolecules is likely to be ren-,
pends on its formulation. dered easier by the addition of small amounts of plas-
ticizers, and in the region where several straight seg-
ments of PVC chains become parallel, crystallization
Background on the Mechanism of Plasticization
may take place. Inside the crystallites, the cohesion
and Mechanical Properties of Plasticized PVC
forces are always considerably higher than in the
A common industrial practice is to modify PVC com- amorphous region. In this respect, antiplasticization
positions by incorporating a diverse array of additives may be associated with the maximization of PVC crys-
in order to obtain a polymer with satisfactory process- tallinity with a small quantity of plasticizer (33).
ing and end-use performance. The required modifica- Ghersa (38) suggested that antiplasticization may be
tions are more extensive and diversified than those due to the steric hindrance of the plasticizer mole-
practiced with other polymers of major industrial im- cules, which, attached with a polar group to PVC
portance. However, the industrial application of PVC chains, could act as crosslinks. In other words, as
in the form of the resulting materials is more versatile. there are a few plasticizer molecules, they may be
In flexible and semirigid PVC formulations, plasti- almost totally immobilized by attachment to the resin
cizers are key ingredients, although other compound- (bound plasticizer) by various forces including hydro-
ing ingredients are also extremely important (e.g., sta- gen bonding. This tends to restrict the freedom of

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bilizers). Plasticizers impart flexibility and play a n small proportions of the polymer molecule-side, i.e.,
important role in heat processing by reducing the vis- chains and segments. Therefore, it results in a more
cosity of the molten material to insure good flow prop- rigid resin with a higher tensile strength than the base
erties. A particularly wide review of the theory of plas- polymer itself (32).
ticization h a s been presented by many investigators
(30-33).According to Matthews (311, PVC has a repet-
itive head-to-tail arrangement of vinyl chloride units, Problem Statement
with variable amounts of chain-branching, and only a Despite the well-known effects of plasticizer on the

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small amount of crystallinity. The highly electronega- processability and properties of PVC, research has not
tive nature of chlorine leads to dipoles along the poly- been carried out to examine the effects of plasticizer
mer molecules, resulting in high concentrations of on the properties of wood-fiber filled PVC composites.

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secondary valence forces, which reduce the flexibility In this context, the main objective of this study is to
of individual molecules, and consequently, increase evaluate the effect of low levels of incorporated plasti-
the rigidity of unplasticized PVC. Reduction in the cizer on the melt flow index, the tensile properties, and

266 JOURNAL OF VINYL &ADDITIVE TECHNOLOGY, DECEMBER 1997, Vol. 3, No. 4

 zyxwvut Effect of Low Levels of Plasticizer

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the notched Izod impact properties of PVC/newsprint-
fiber composites. This research also investigates how
the antiplasticization phenomenon observed in un-
filled PVC affects the physical and mechanical prop-
erties of the PVC /newsprint-fiber composites.

Materials
EXPERIMENTAL
circulating cold water in the press. From these panels,
the dogbone-shaped specimens (Type I tensile speci-
mens of an ASTM standard D638) were made for ten-
sile testing. Rectangular samples of 12.7 mm x 63.5
mm were cut from the panel sheets for impact testing.

Property Testing
Tensile testing was carried out according to the
The polymer matrix used in this study was PVC ASTM standard D638 on a Instron Universal Testing

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(Geon 103EPF761, supplied by Royal Plastics Limited. Machine Sintech (Model 20) equipped with Testwork
Dioctyl phthalate (DOP) was used as the plasticizer. program (Version 2.10, Sintech Inc.) for statistical cal-
Lubricant (calcium stearate) and stabilizer (antimony culations. The cross-head displacement rate was 12.5
type) were also used as ingredients in the formula- mmlmin. Four tensile properties were determined
tions. A ground waste inked newsprint-fiber was used from the stress-strain curves: 1) the stress a t break, 2)
as the filler. Fibers from waste newsprint were dry- the modulus, 3 ) the elongation at break, and 4) the
shredded into feedstock in a standard hammer mill energy to break. The tensile strength was determined
as the yield load divided by the initial section area of
(American Pulverizer Type MI. The machine was
the specimen. The initial tangent modulus was deter-
equipped with a shift screen of openings 1 mm in
mined from the slope of the load-deformation curves.
diameter. After defibrating, the fibers were sieved to
The deformations were measured by a strain gage

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mesh size 60 mixture: 60% mesh 60, 20% mesh 80,
extensometer (Sintech, Model 632) and the elongation
15% mesh 100, and 5% mesh 200, with a Granu
at break of a tensile test bar was recorded as percent
Grinder (C. W. Brabender Instruments Inc.). All ma-
elongation. All evaluations were made a t the room

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terials were used a s received from the manufacturers.
temperature (21"C). Before testing, the samples were
Compounding and Compression Molding conditioned a t the room temperature and 50% relative
humidity for more than 48 hours in accordance with
The compounding of PVC and PVC /newsprint-fiber Procedure A of ASTM D618. At least five specimens
composites was carried out in a high intensity turbine were tested a t each concentration of DOP.
mixer (Werner-Pfleiderer Gelimat G- 1). The rotating The notched Izod impact property (measure of frac-
speed was set such that the tip of the blade ran at a ture energy) of the samples was determined using a
speed of 22.8 m / s . The initial mixing temperature was Tinius Olsen Izod impact tester. Notched samples
100°C, and the compounded materials were automat- were tested a t the room temperature according to the
ically discharged from the turbine mixer a t the pre-set procedure outlined in ASTM D256. The statistical av-
temperature of 190°C. Once mixed, the melted com- erage of the measurements of at least 10 specimens
pounds were allowed to cool to the room temperature was taken to obtain a reliable average and standard
and then granulated into particles in a Brabender deviation.
granulator (ModelS-10-9).The screen size of the gran- The melt flow index (MFI) was also measured on
ulator was 6 mm. these compounded mixtures. The melt flow index
Two different types of mixture were formed under measurement was performed according to the proce-
the same conditions: (1) PVC alone, and (2)PVC and dure outlined in ASTM D3364 using a n extrusion rhe-
45 phr of newsprint-fiber composites. The concentra- ometer and a specified die. The melt temperature was
tions of plasticizer in these mixtures varied from 0 phr 190°C and a n applied dead load of 21.6 kg (including
to 15 phr, with 3.75 phr increments. The formulations the piston) was employed.

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used in these mixtures are shown in Table 1. The
composites were compression-molded into panels ( 1.5 Statistical Analysis
mm in thickness) in a hydraulic press (Wabash Metal
Analysis of variance (ANOVA)was performed on the
Products Inc., Model 50-1818-2tm) at 190°C for 4
collected data with SAS package (SAS/STAT release
minutes using 30 tons of pressure. The mold was then
6.03).Duncan's multiple range tests were employed to
cooled to a temperature below 50°C under pressure by
distinguish the statistical differences among the vari-
ous concentrations of plasticizer on the mechanical
Table 1. Formulations Used in PVC and WC/Newsprint- properties for both materials.
Fiber Composites.
Formulations RESULTS AND DISCUSSION
Unfilled PVC Filled PVC

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Ingredients (PW (PW
Effect of DOP Concentration on t h e MFI
~~

Resin (Geon 103EPF76) (K value 66) 100 100 Figure 1 illustrates the effect of plasticizer content
Plasticizer (DOP) 0-1 5 0-1 5 on the MFI for PVC and PVC/newsprint-fiber compos-
Stabilizer (antimony) 1.2 1.2 ites. Two distinct observations were made from this
Lubricant (calcium stearate) 1.2 1.2 figure. First, the melt flow index increased with a n
Fillers (newsmint-fibers) 0 45
increase in the DOP concentration for both materials

JOURNAL OF VINYL &ADDITIVE TECHNOLOGY, DECEMBER 1997, Vol. 3, No. 4 267

 zyxwvzyx
zyxwvutsrqponm
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Luurent M. Matuana. Chul B. Park and John J. Balatinecz

20 1

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A Composites
OPVC
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50

--...
___,..__...__,..
-0 phr
.. 7 . 5

.. 15phr
phr

-._.....
:
(4

0 I I I I I I

o! I
0 3.75 7.5 11.25 15 18.75
DOP Content @hr)

Fig. 1 . Eflect ofDOP content on the meltflow index of PVC and

PVClnewsprintjiber composites.

as expected from the theory of plasticization (17). In-

creasing the concentration of plasticizer in PVC en-
hances the chain mobility arising from an increase in
40 t -.7.5phr

. 15phr

free volume or decrease in molecular interaction (30).

Second, the addition of newsprint-fibers affected the
melt flow index of the polymer matrix as expected from
the theory of filled melts (41). The presence of news-
print-fibers in the PVC matrix restricts viscous flow. In
fact, when the PVC and PVC/newsprint-fiber compos-
ites were not plasticized, the materials did not flow
continuously and their MFI values were almost negli-
gible.
0 0 005 0.01
Strain
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0.015

Fig. 2. Stress-strain plots of [a)PVC and (b)PVClnewsprint-

0.02

Effect of DOP Concentration on the Tensile fiber composites with uarious concentrations of DOP.
Properties

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The most interesting features of stress-strain behavior. In this range of plasticizer, the stress-strain
curves of PVC and PVC/newsprint-fiber composites curves had a small slope over a wide range of elonga-
obtained from tensile tests are shown in Fig. 2. The tion.
stress-strain relations for PVC/newsprint-fiber com-
posites were practically linear to the time of fracture Tensile Strength at Yield
(Fig. 2b). To the DOP concentration of 7.5 phr, the The effects of plasticizer concentration on the ten-
stress-strain curves of PVC /newsprint-fiber compos- sile strength at yield for unfilled and 45 phr news-
ites obeyed Hooke’s Law with the strain being directly
proportional to the applied stress. All stress-strain
curves of these composites showed no yield point be- 50
fore fracture, and failed in a brittle mode. -
By contrast, a wide difference in the shape of the
stress-strain curves was observed in the case of un-
filled PVC (Fig. 2a). A well-defined yield point was
observed before fracture in all stress-strain curves,
indicating a ductile behavior for unfilled PVC. Unplas-
ticized PVC also obeyed Hooke’s Law u p to a strain of
0.02. In the case of plasticized PVC, this law was also
obeyed for only a short distance, if a t all. Up to 7.5 phr
DOP, the specimens stretched on a wide range of
strain but no localized neck was formed beyond yield
load, which are typically observed with the toughened
- PVC
..-A-.- Composites

PVC specimens (42). In this range of plasticizer, the o!

slope of the stress-strain curve was very steep and 0 3.75 7.5 11.25 15 18.75
followed by a yield value before fracture a s shown in DOP Content @hr)
Fig. 2a. On the other hand, at 15 phr DOP, the spec- Fig. 3. Dependence of the tensile yield strength on theplasti-
imens yielded with necking exemplifying cold-drawing cuer contents in PVC and PVClnewsprintfiber composites.

268 JOURNAL OF VINYL &ADDITIVE TECHNOLOGY, DECEMBER 1997, Vol. 3, No. 4

print-fibers filled PVC composites are shown in R g . 3 .
The presence of antiplasticization region is clearly ob-
served in this figure in the range of 0 to 3.75 phr and
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Effect of Low Levels of Plasticizer

(up to about 3.75 phr to 7.5 phr) in a PVC compound

led to an increase in the tensile modulus because of
antiplasticization. Duncan’s multiple range tests re-
0 to 7.5 phr of DOP for the base polymer and compos- sults also demonstrated that this increase in modulus
ites, respectively: increasing the DOP content led to a was significant with 95% confidence (Table 2). It is
small increase in the yield strength because of the interesting to note that the maxima in both the yield
antiplasticization phenomenon. However, the yield strength and tensile modulus curves occurred almost
strength significantly decreased as the DOP concen- a t the same plasticizer content around 3.75 phr for
tration increased further beyond the antiplasticization both materials. At higher plasticizer contents, the ten-
region. Duncan’s multiple range tests, listed in Table sile modulus decreased significantly a s a result of the
2, confirmed that the yield strengths of both materials plasticization effect as reported in the literature (37,
plasticized with DOP u p to 3.75 phr were significantly 38).

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higher than the unplasticized ones. Since the mixing The addition of newsprint-fibers into the PVC ma-
behavior, moldability, surface quality of the compos- trix increased the modulus of the composites. The
ites samples were better a t 7.5 phr DOP than a t 3.75 modulus of the composite was almost two times
phr, the optimum plasticizer concentrations (to max- greater than that of pure PVC a t each DOP content.
imize the tensile strength a t yield) seem to be around Based on the rule of mixtures (431, the modulus of

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3.75 phr and 7.5 phr for PVC and PVC/newsprint short-fibers composites (E,) is a strong function of the
composites, respectively. fiber’s modulus and can be estimated by
The decrease in strength may be due, in appreciable
part, to the increased plasticization level of the matrix.
Beyond the plasticization threshold (i.e., the concen-

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tration a t which the strength reaches its original val-
ue), the material becomes progressively softer, more
flexible, extensible and tougher (17), with a lower yield
strength. The SEM micrographs of the fractured PVC
shown in Fig. 4 a-f verify the softening effect of the
DOP plasticizer.
Figure 3 also shows that the addition of newsprint-
fibers in PVC affects the tensile strength adversely for
all plasticizer contents. The poor dispersion of the
where V, is the matrix volume fraction, E, and Emare
the fiber and matrix moduli, respectively, and k& the
efficiency coefficient that varies as a function of the
composites’ microstructural parameters such as dis-
persion, orientation, adhesion, etc. Chtourou et al.
( 11) experimentally determined that in compression
molding (as in this study), k , related to the modulus
of compressed samples is approximately 0.33. During
processing, newsprint-fibers tend to collapse into rib-
fibers and reduced interfacial adhesion to the polymer bons and these ribbons possess a high stiffness in the

z
matrix may explain this reduction (28). range of 10 to 80 GPa (9, 44). Because of the higher
stiffness of newsprint-fiber, the modulus of the com-
Tensile Modulus posites increased significantly. Unlike the tensile
Figure 5 shows the tensile modulus for PVC and strength, the modulus did not seem to be affected by
PVC /newsprint-fiber composites plasticized with var- the adhesion between matrix and fibers. It is reported
ious concentrations of DOP. As in the case of yield that the adhesion has no effect on stiffness a t very low
strength, the incorporation of a small amount of DOP strains (below 0.2 a s in this study), and the effect of

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Table 2. Duncan’s Multiple Range Tests for Tensile and Notched Impact Properties of PVC and PVC/Newsprint-Fiber Composites.
~~

Tensile Strength at
Yield Tensile Modulus Elongation at Break Energy to Break lzod Impact Property
Ducan Mean DOP Ducan Mean DOP Ducan Mean DOP Ducan Mean DOP Ducan Mean DOP
Samples Grp(’) (MPa) (phr) Grp”) (GPa) (phr) Grp(‘) (“10) (phr) Grp(‘) (J) (phr) Grp‘’) (J/m) (phr)
R’ = 0.9505 R’ = 0.9745 R2 = 0.9894 R2 = 0.9760 R’ = 0.9015
Pr = 0.0001 Pr = 0.0001 Pr = 0.0001 Pr = 0.0001 Pr = 0.0001
A 42.40 3.75 A 2.28 3.75 A 74.02 15.00 A 33.53 15.00 A 380.42 15.00
B 38.92 7.50 B 2.08 0.00 B 12.42 11.25 B 5.92 11.25 B 42.97 11.25
PVC B 38.82 0.00 B 2.06 7.50 C 5.06 7.50 CB 3.24 7.50 B 37.62 0.00
C 34.18 11.25 C 1.78 11.25 C 4.00 0.00 C 2.53 0.00 B 37.62 3.75
D 28.92 15.00 D 1.19 15.00 C 3.5 3.75 C 2.00 3.75 B 34.39 7.50

R2 = 0.7927 R‘ = 0.7566 R2 = 0.1921 R2 = 0.5289 R2 = 0.6974

Pr = 0.0001 Pr = 0.0001 Pr = 0.3459 Pr = 0.0034 Pr = 0.0034
A 31.54 7.50 A 3.63 3.75 A 1.21 7.50 A 0.53 7.50 A 39.52 15.00
A 30.48 3.75 A 3.63 7.50 A 1.11 3.75 A 0.50 3.75 BA 36.30 11.25
Composites B 27.40 0.00 A 3.41 0.00 A 1.11 11.25 A 0.41 0.00 B 34.76 7.50
B 24.68 11.25 B 3.05 11.25 A 1.08 15.00 A 0.40 11.25 C 29.17 3.75
C 20.54 15.00 C 2.54 15.00 A 1.04 0.00 B 0.27 15.00 D 23.94 0.00
’Ducan Grp(” stands for Duncan Grouping. The means with the same letter are not significantly different.

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, DECEMBER 1997, Vol. 3, No. 4 269
 zyxwvutsr
zyxwv
Luurent M. Matuana, Chul B. Park and John J. Balatinecz

zyxwvuts
zy
zyxwvuzy
FYg. 4. SEM micrographs of fractured PVC [a to cj and PVC/newsprintrftbercomposites [d tof) with various DOP contents. [a and
0 phr DOP; [b and e): 7.5 phr DOP, and (c andf): 15 phr DOP.

adhesion starts to be apparent a t strains above 0.2 ever, beyond this region, the elongation a t break sig-
ti):

(45). nificantly increased with the plasticizer concentration

for the pure PVC. Second, the plasticization concept of
Elongation at Break increasing the elongation at break was not valid for
The effect of plasticizer concentration on the elon- PVC /newsprint-fiber composites since the elongation
gation a t break is shown in Fig. 6. The contrast be- a t break of the composites was essentially indepen-

z
tween the two materials of PVC and PVC/newsprint- dent of the plasticization of the matrix. This was con-
fiber composites is striking. First, both Fig. 6 and the firmed by Duncan’s tests that showed no significant
results of Duncan’s tests in Table 2 show that the differences for the elongation at break of the compos-

zyxwvutsrqpo
elongation a t break was not significantly affected by ites as the concentration of DOP increased. In addi-
the addition of plasticizer for the base polymer in the tion, the elongation at break of the PVC /newsprint-
antiplasticization region (up to 3.75 phr DOP). How- fiber composites was much lower than that of PVC

270 JOURNAL OF VINYL &ADDITIVE

i TECHNOLOGY, DECEMBER 1997, Vol. 3, No. 4
 zyxwvut
Effect of Low Leuels of Plasticizer

5T---lzyxwvutsrqpo
.$. ....
T
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Fig. 4 . Continued.

f l loo - --A-- Comosites

~

01
t -pvc
0 3.75 7.5 11.25
DOP Content (phr)
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a 15 18.75

Fcg. 5. Dependence of the tensile modulus on the plasticizer

0.1
0 3.75 7.5 11.25
DOP Content (phr)
15 18.75

Fig. 6.Dependence of the elongation at break on the plasti-

contents in PVC and PVC/newsprint$ber composites. cizer contents in PVC and PVClnewsprintTier composites.

regardless of plasticizer content. The decreased elon- of toughness, since this measures the work done or
gation at break may be due to the higher degree of energy used to break the sample. The toughness of
brittleness introduced by the incorporation of news- these materials followed similar trends to the elonga-
print-fibers into the PVC matrix. This was evidenced tion at break.
by the difference in the failure mode for each material The results in Fig. 7 and Duncan’s tests in Table 2
a s shown in Fig. 2. PVC exhibited a more ductile fail- showed that up to 7.5 phr, the toughness of PVC was
ure since a yielded point was observed before fracture not affected much by the DOP concentration because

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while composites experienced a brittle failure, in the elongation at break remained constant in this
which a yield point was not observed. range of plasticizer. However, above this concentra-
tion, the toughness increased significantly with the

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DOP content because of the increased elongation at
Toughness break which caused a n increase in the area under the
Figure 7 shows the effect of plasticizer content on stress-strain curves of PVC. On the other hand, the

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the energy to break (toughness) for PVC and PVC/ increase in DOP concentration had a negligible effect
newsprint-fiber composites. The integrated area un- on the toughness of the PVC /newsprint-fiber compos-
der the stress-strain curve was taken a s one measure ites.

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, DECEMBER 1997, Vol. 3, No. 4 27 1

 h u r e n t M. Matuana, Chul B. Park a n d John J. Balatinecz zyxw
DOP the presence of newsprint-fibers did not affect
the impact value of the matrix polymer. However, the
deleterious effect of the addition of newsprint-fibers to

-
PVC matrix became apparent a t plasticizer concentra-

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tions above 1 1.25 phr. PVC/newsprint-fiber compos-
ites exhibited much lower capability of absorbing im-
pact energy. This is a typical trade-off of improving the
stiffness of the matrix by incorporating newsprint-
fibers into the PVC matrix. This study indicates that
the incorporation of newsprint-fibers caused much
..

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higher degree of brittleness to the PVC matrix. As a
I consequence, ductile deformation of the matrix was

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0.1 inhibited and a n increasing proportion of the fracture
0 3.75 7.5 11.25 15 18.75
energy will arise from fiber debonding and frictional
DOP Content (phr)
pull-out losses as the fiber concentration increased
(46). In addition, each fiber acted a s a discontinuity
f i g . 7. Dependence of the energy Lo break on the plasticizer capable of initiating cracks (45) in the PVC/news-
contents in PVC and PVCI newsprintlftber composites. print-fiber composites.
CONCLUSIONS
This study investigated the effects of plasticizer on
the melt flow index, tensile properties and notched
Izod impact properties of newsprint-fibers filled PVC
composites and unfilled PVC. The formulations were
modified by incorporating various concentrations of
dioctyl phthalate a s a plasticizer. Based on the exper-

0
0 zyxwvutsrqponm
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3 75 75
DOP Contenl (phr)
11 25

Fig. 8. Dependence of notched Izod impact ualues on the DOP

15
imental results, the following conclusions can be
drawn:
1) The melt flow index of PVC and PVC/newsprint-
fiber composites increased linearly a s the concentra-
tion of plasticizer increased due to the plasticization
effect. The addition of newsprint-fibers in the PVC
contents in PVC and PVC / newsprint3ber composites. matrix reduced the melt flow index for all the plasli-
cizer concentrations.
2) The tensile strength at yield of PVC and PVC/
Effect of DOP Concentration on the Notched Izod
newsprint-fiber composites slightly increased by the
Impact Property
addition of a small amount of plasticizer. This seemed
The effects of plasticizer content on the notched Izod to be due to antiplasticization. At higher plasticizer
impact property (fracture energy) of the unfilled and concentrations, the tensile strength a t yield decreased
newsprint-fibers filled PVC are illustrated in Fig. 8 and with a n increase in the plasticizer concentration be-
the results of Duncan’s tests are listed in Table 2. cause of plasticization of the matrix. The addition of
Figure 8 shows a mild increase in the impact values of newsprint-fibers in the PVC matrix reduced the tensile
polymer with the plasticizer content up to 11.25 phr. strength at yield of the composites.
However, Duncan’s tests showed that this increase 3) At low contents of plasticizer, the tensile modulus
was not statistically significant. On the other hand, increased due to the antiplasticization phenomenon,
above this concentration, a significant improvement whereas at higher DOP contents, the tensile modulus
was observed. The notched Izod impact value in- decreased as the plasticizer content increased. The
creased from 44.2 J / m to 380.4 J / m when the DOP addition of newsprint-fibers increased the tensile
content increased from 11.25 phr to 15 phr. This in- modulus of the composites because of the higher mod-
creased impact value of PVC may be explained by the ulus of the fibers.
same plastic deformation mechanism which caused 4) The elongation a t break of PVC remained con-
the increased elongation a t break in the tensile test. I t stant in the antiplasticization region whereas the
should be noted that a t 15 phr DOP, the PVC speci- elongation a t break increased with the plasticizer con-
mens in impact testing deformed without breaking tent beyond the plasticization threshold. The addition
due to the improved ductile behavior of the polymer. of newsprint-fibers in PVC matrix reduced the ductile
The notched Izod impact property of PVC/news- behavior of the matrix by making the composites be-
print-fiber composites was also affected by the DOP have more brittlely. Furthermore, the elongation a t
concentration in the same manner a s the base poly- break of PVC /newsprint-fiber composites was not im-
mer. These observations were revealed by Duncan’s proved by the addition of plasticizer.
tests although they cannot be clearly seen from Fig. 8 5)The effect of plasticizer on the toughness of these
because of the scale. It seemed that u p to 11.25 phr materials followed similar trends to the elongation to

272 JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, DECEMBER 1997, Vol. 3, No. 4
 zyxwvu
zyxwvu
zyxwvutsr
Effect of Low Levels of Plasticizer

break. As the plasticizer concentration increased, the A. K. Mohd Omar, Plast. Rubber Proc. Appl., 21, 225
toughness of PVC increased whereas the toughness of (1994).
PVC/newsprint-fiber composites were not a function 14. R. G. Raj, B. V. Kokta. G. Groleau, and C. Daneault,
of plasticizer content. Plast. Rubber Proc. Appl., 11, 215 (1989).
15. R. G . Raj, B. V. Kokta, and J. D. Nizio, J. Appl. Polym.
6) The notched Izod impact property of PVC was a Sci., 45.. 91 (1992).
.
strong function of plasticizer content: the impact val- 16. S. Dong, S. Sapieha, and H. P. Schreiber, Polym. Eng.
ues increased significantly as the plasticizer concen- Sci., 32, 1734 (1992).
tration increased for both materials. The presence of 17. W. V. Titow, PVC Plastics: Properties, Processing, and
newsprint-fibers did not affect the impact values of the Applications, Ch. 5, Elsevier Applied Science, New York
( 1990).
polymer matrix up to 11.25 phr DOP. However, the 18. W. V. Titow and B. J . Lanham, Reinforced Thermoplas-
deleterious effect of the addition of newsprint-fibers to tics, Applied Science Publishers Ltd., London (1975).
PVC matrix became apparent a t plasticizer concentra- 19. I. L. Gomez, Engineering With Rigid PVC: Processability
tions above 11.25 phr. and Applications, Marcel Dekker Inc., New York (19841.
20. R. G. Raj and B. V. Kokta, “Studies on mechanical prop-
ACKNOWLEDGMENTS erties of PVC-wood fiber composites,” presented a t Cel-
lulon 1988 meeting, Kyoto. Japan (1988).
The authors are grateful for the generous donation 21. B. V. Kokta, D. Maldas. C. Daneault, and P. BCland,
of materials and financial support provided by Royal Polyrn. Plast. Technol. Eng.. 29, 8 7 (1990).
22. B. V. Kokta, D. Maldas, C. Daneault, and P. Beland,
Plastics Limited. Le Fonds pour la Formation de Cher-

zyx
Polym. Compos., 11. 8 4 (1990).
cheurs et 1’Aide a la Recherche (Fonds FCAR) of Que- 23. B. V. Kokta, D. Maldas, C. Daneault, and P. BCland, J.

zyxwvutsrqp
bec and the University of Toronto are also acknowl- Vinyl Technol., 12, 146 (1990).
edged for the scholarships awarded to one of the 24. D. Maldas, B. V. Kokta. and C . Daneault, J. Vinyl Tech-
authors (L.M.M.). Last, the authors would like to nol., 11.90 (1989).
25. D. Maldas and B. V. Kokta, J.Reinf. Plast. Compos., 11.
thank Mr. S. Law for his useful technical advice dur- 1093 (1992).
ing manufacturing and property testing of compos-

zyxwvutsrqp
26. D. Maldas and B. V. Kokta, J. Test. Eual., 21.68 (1993).
ites. 27. L. Matuana-Malanda, C. B. Park, and J . J . Balatinecz, J.

zyx
Cell. Plast., 32, 449 (1996).
NOMENCLATURE 28. L. M. Matuana, C. B. Park, and J . J . Balatinecz. in

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Cellular and Microcellular Materials, MD-Vol. 76, p. 1, V.
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31. G. Matthews, Vinyl and Allied Polymers, Volume 2: Vinyl
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vm Matrix volume fraction, %. Plastics Institute, Illiffe Books, London (1972).
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