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EUROPEAN
POLYMER
European Polymer Journal 44 (2008) 755–768
JOURNAL
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Polymer toughening using residue of recycled windshields:

PVB film as impact modifier
Ticiane Sanches Valera, Nicole Raymonde Demarquette *
University of São Paulo, Materials and Metallurgical Engineering Department, Av. Prof. Mello Moraes, 2463, 05508-900 São Paulo, Brazil

Received 24 August 2007; received in revised form 12 December 2007; accepted 13 December 2007
Available online 8 January 2008

Abstract

In this work, poly(vinyl butyral) (PVB) film originated from the mechanical separation of windshields was tested as an
impact modifier of Polyamide-6 (PA-6). The changes undergone by PVB film during the recycling process and the blend
manufacturing were evaluated by thermal analyses, infrared spectroscopy and loss on ignition. Blends of PA-6/original
PVB film and PA-6/recovered PVB film were obtained in concentrations ranging from 90/10 to 60/40. The mechanical
properties of the blends were investigated and explained in light of the blends morphologies, which in turns were correlated
to the changes undergone by the PVB film during the recycling process. The original film presented a plasticizer content of
33 wt.%, which decreased to as low as 20 wt.% after the recycling and blend preparation processes. The PA-6/PVB film
blends presented lower values of tensile strength and Young’s modulus than Polyamide-6, but all blends presented a dra-
matic increase in their toughness, with a special feature for the 40 wt.% blend, which resulted in a super toughened material
(impact strength exceeding 500 J/m). Similar results were obtained with recovered PVB film and super tough blends were
also obtained. The use of recovered PVB resulted in a smaller improvement of the impact strength due to the loss of plas-
ticizer undergone during the recycling process. The morphological observations showed that if the interparticle distance is
smaller than around 0.2 lm (critical value), the notched Izod impact strength values increase considerably and the fracture
surface of blends exhibit characteristics of tough failure.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Recycled windshield; Recovered PVB film; Toughening agent; Polyamide-6

1. Introduction and vinyl acetate whose properties can be tailored

Windshields or laminated safety glasses consist of
a ‘‘sandwich” of a film of poly(vinyl butyral), PVB,
between two sheets of glass. PVB is a random amor-
phous copolymer of vinyl butyral, vinyl alcohol,
*
Corresponding author. Tel.: +55 11 3091 5693; fax: +55 11
3091 5243.
E-mail address: nick@usp.br (N.R. Demarquette).
by the percentage of each monomer within the chain
[1]: the hydrophobic vinyl butyral units provide
elasticity, toughness and compatibility with various
plasticizers and the hydrophilic vinyl alcohol units
confer high adhesion to inorganic materials such
as glass. In order to be used in laminated safety
glasses PVB is normally blended to around
30 wt.% of a plasticizer such as alkyl phthalates [2]
or dibutyl sebacates [3]. Due to its structure and

0014-3057/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2007.12.012
756 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768
presence of plasticizer, PVB film possesses similar
properties to rubber [4]. In spite of the high price
of PVB film (about US$15/m2) and the large quan-
tity of windshields that are annually discarded in
landfields (100 thousand tons per year of which
7% consist of PVB film, in the USA alone [5]) very
little work has been conducted on finding alterna-
tives to disposal of laminated glass residues to land-
fields. Cha et al. [4,6,7] showed that it was possible
to use uncontaminated scrapped PVB film collected
from windshield production as an impact modifier
of Polyamide-6 (Nylon-6). Polyamides are pseudo-
ductile polymers often blended to rubbers [8] to
enhance their low notched impact strength [9]. The
PVB film used by Cha et al. [4,6,7] was very similar
to virgin PVB film as it corresponded to the indus-
trial residues that could not be used in the wind-
shields. However, during the production of
windshields and the recycling process, the properties
of PVB film may change: the plasticizer may be
eliminated and the PVB may suffer degradation
[2,3,10]. It is therefore of interest to study the
changes undergone by PVB film during the manu-
facturing of the windshields and recycling process
and the possibility of using the PVB film residue
as impact modifier.
Polymer toughening has drawn a lot of attention
from academics and plastic industry [4,6,7,9,11–37]
as impact strength is one of the most important
mechanical properties of plastics. It is well known
that pseudo-ductile matrixes, such as Polyamides
toughened with rubber material, present higher duc-
tility, crack resistance and mainly greater impact
strength, when compared to the one of the pure
matrix [23]. Various theories have been proposed
to explain toughening mechanism, including stress
relief by cavitation of rubber particles, matrix craz-
ing and shear yielding. More details can be found in
different monographs on the subject [8,9,22,23,25–
28].
Wu [22,26] proposed that interparticle distance
(between the nodules of the dispersed phase) is the
most important parameter that controls the brit-
tle-to-tough transition of rubber/polymer blends.
If the interparticle distance, given by Eq. (1) is smal-
ler than a critical value (called critical interparticle
distance) the blend will be tough, otherwise, the
blend will be brittle:
" 13 #
p and lab-scale process, was sieved (ASTM #10, sieve
s¼d 1
6/
where s is the interparticle distance between the sur-
faces of two nearest neighboring particles, d is the
particle diameter and / is the rubber volume
fraction.
The critical interparticle distance is independent
of rubber volume fraction and particle size and is
characteristic of a given matrix. This parameter
alone can explain the effects of rubber volume frac-
tion, particle size, polydispersity, coalescence of
rubbery phase and morphology on toughness [22].
Since Wu proposed the interparticle distance model,
many authors worked on the subject [27–34,36,37]
and it was found that the critical interparticle dis-
tance can be affected by different parameters, such
as temperature and speed of impact tests, notch
radius of samples for impact test, interfacial tension
between blend components and other properties of
the rubbery and matrix phases [29,30,32,33,36,37].
In the present work, PVB film originated from the
mechanical separation of windshields, either from
industrial fabrication waste or from post-consump-
tion products was tested as an impact modifier for
Polyamide-6 (PA-6). The changes undergone by the
PVB film during windshield manufacture and recy-
cling process were evaluated. Blends of PA-6/origi-
nal PVB film/ and PA-6/recovered PVB film were
obtained. Their mechanical properties were com-
pared and explained in light of blend morphology
and of the changes undergone by the PVB film during
the blend manufacturing and the recycling process.
2. Experimental
2.1. Materials
The properties of the polymers used in this work
are listed in Table 1. Three types of PVB were used
in this work: original PVB film corresponding to
the material used in the production of windshields
(Solutia, Saflex RB41), recovered PVB film origi-
nated from the grinding of windshields rejected in
the production line or post-consumption, and pure
PVB without plasticizer to quantify the loss of plas-
ticizer from the PVB film during the recycling pro-
cess. Two types of recovered PVB film were used:
one was originated from an industrial recycling com-
pany (R2) and the other (R1) was ground using a
modified blade grinder, in our laboratories. The
ground material, originated from both the industrial
ð1Þ opening 2 mm) and the passing material was blended
to Polyamide-6 by extrusion. The PVB plasticizer
 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768 757

Table 1 film and quantify the amount of plasticizer within

Characteristics of the studied materials the PVB films before and after recycling process.
Materials Property Values In order to quantify the amount of plasticizer within
PVB film Melt flow index (g/10 min) 2.88 (235 °C, 2.16 kg) the different PVB film samples, a calibration curve
Refractive index 1.478 (23 °C) was obtained using 6 blends of pure PVB with 0–
Density (g/cm3) 1.066 (23 °C) 40 wt.% plasticizer. The samples were dissolved in
Tensile strength (MPa) 22.2
Elongation (%) 190
chloroform, in a concentration of 10 mg/mL. The
Tensile modulus (MPa) 6.4 solutions were placed in a cell with KBr window,
and subsequently analyzed. The absorbance of the
Plasticizer Molecular formula C22H42O6
Molecular weight 402.6 carbonyl band at 1730 cm1 was used to quantify
Density (g/cm3) 0.95 the plasticizer content and a calibration curve with
Flash point (°C) 207 carbonyl band area versus weight fraction of plasti-
PA-6 Melt flow index (g/10 min) 27.5 (235 °C, 2.16 kg) cizer was obtained. This curve was used to deter-
Density (g/cm3) 1.14 (23 °C) mine the plasticizer content in samples of original
Tensile strength (MPa) 57.4 PVB film, recovered PVB film, and the films submit-
Elongation (%) 259 ted to one and two extrusions, and injected. Fig. 1
Tensile modulus (MPa) 2471
shows the calibration curve obtained. It can be seen
that the absorbance of –OH group (area of –OH
present in commercial PVB film used in this work group peak) increases linearly with the concentra-
was triethylene glycol di-2-ethylhexanoate. tion of plasticizer present in the blends of PVB
and plasticizer, following Beer–Lambert’s law.
2.2. Blending and sample preparation However, there was a non-zero intercept because
the PVB copolymer presents vinyl acetate units in
Two types of blends were prepared in this work: its structure.

1. PA-6/original PVB film with concentrations of

PVB film ranging from 0 to 40 wt.%.
2. PA-6/recovered PVB film (obtained from the
grinding process) with concentrations of PVB
film of 20 and 40 wt.%. – those two concentra-
tions were chosen as a function of the results
obtained when studying the PA-6/original PVB
film blends.
The blends were prepared using a Laboratory
twin-screw extruder (Haake Rheomex PTW16) with
four heating zones with temperatures ranging from
230 to 250 °C, and then injected to form samples for
impact and tensile tests using a Demag Ergotech
2.3.2. Differential scanning calorimetry (DSC) and
thermogravimetrical analysis (TGA)
The blends were analyzed using a DSC Q10 (TA
Instruments). Approximately 5 mg of material was
used for each experiment. The sample was heated
at a heating rate of 10 °C/min, then cooled at a rate
of 10 °C/min to 40 °C and finally reheated at a
rate of 10 °C/min to 250 °C. The experimental
14 y = 0.275x + 0.839
R2 = 0.990
Carbonyl band area (at 1730 cm-1)

12

Injection molding machine with a diameter of

10
25 mm and L/D of 20. The processing temperatures
along the injection barrel ranged from 220 to 250 °C. 8
The blends with virgin PVB film and recovered
PVB film using an industrial grinder were extruded 6

once and twice in order to study the reprocessing 4

(recycling) of the blends.
2

2.3. Characterization 0
0 10 20 30 40 50

2.3.1. Infrared spectroscopy Plasticizer content (wt%)

A Nicolet 560 IR – Magna infrared spectrometer Fig. 1. Calibration curve used to determine the plasticizer
was used to access the possible degradation of PVB content.
758 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768
procedures were based on ASTM3417 and
ASTM3418. Thermogravimetric analyses were
carried out in a DTA/TG STA409 (Netzch) to
determine the loss mass from PVB films and blends,
from ambient temperature to 300 °C, in flowing syn-
thetic air, at 20 °C/min heating rates.
All the samples were dried under vacuum at a
temperature of 60 °C for at least 48 h prior to ther-
mal analyses.
2.3.3. LOI – loss on ignition
The fragments of ground PVB film were burned
in a laboratory electric oven at 600 °C for 3 h to
determine the residual amount of glass. The values
reported represent the average of three tests.
2.3.4. Mechanical properties
They were measured using an EMIC DL-2000
universal testing machine. The Young‘s modulus
was determined using testing velocity of 1 mm/min
and the others tensile properties were obtained
using a testing velocity of 50 mm/min. Notched
Izod impact strength was measured using a CEAST
impact testing machine. The radius of notch used in
the specimens was of 0.25 ± 0.05 mm and angle of
45 ± 1° (ASTM D256, specimen type 3). The results
of mechanical properties reported in this work
correspond to the average of at least 15
measurements.
2.3.5. Morphology
The morphology of all the blends was character-
ized by scanning electron microscopy. To obtain a
good contrast between the phases, the PVB film
was dissolved with ethanol. Quantitative analysis
of the morphology was performed using Carl Zeiss
Vision KS-300 software. The impact strength speci-
mens after testing were used for qualitative analyses
of the fracture surface. In the case of the quantita-
tive morphological analyses, Saltikov’s correction
[38] was used.
2.3.6. Rheological characterization
The shear viscosity of the polymers as a function
of shear rate was evaluated using a capillary rheom-
eter Instron 4467 at a temperature of 250 °C. The
die used had a diameter of 0.76 mm and L/D of
34. Rabinowitsh correction was applied to the
experimental results. All the samples were dried
under vacuum at a temperature of 60 °C for 48 h
prior to rheological measurements.
3. Results and discussion
3.1. Mechanical separation process
The windshields were recycled and two types of
wastes were obtained, scrapped PVB film and par-
ticulate glass. The PVB films were ground. The
mean values of the LOI tests for ground PVB films
were: 99.2 wt.% and 99.3 wt.% for R1 (recovered
films obtained in laboratorial scale) and R2 (recov-
ered films obtained using industrial grinder), respec-
tively, showing that the fragments of films are
almost glass-free.
3.2. Changes undergone by the PVB film during the
blend manufacturing and the recycling process
Fig. 2 presents the infrared spectra of original
and recovered PVB films, and of films that have
been submitted to extrusion and injection molding
processes. Fig. 2a–d shows four different film spec-
tra regions: the band at 3489 cm1, corresponding
to –OH group (Fig. 2a), together with the band rel-
ative to C–H stretching at 2970 cm1 (Fig. 2b), the
band at 1140 cm1 relative to C–C(@O)–O stretch-
ing of vinyl acetate units (Fig. 2c), and the band at
1730 cm1 of C@O group (Fig. 2d). It can be seen
from Fig. 2a–c, that the featured regions the spec-
tra of the original and recovered PVB films are sim-
ilar, showing no changes in absorbance, indicating
that the PVB chain did not undergo any modifica-
tions in the vinyl alcohol and vinyl acetate struc-
tures and therefore did not suffer thermal
degradation. According to El-Din et al. [2] the ini-
tial point of thermal degradation of PVB is the
vinyl acetate unit, the weakest unit of the PVB
structure, which gets detached from the main chain.
In subsequent steps, the molecule suffers scission
and the ring of the vinyl butyral unit opens, leading
to the formation of chains with C@C double bonds.
These changes involve a reduction in the absor-
bance of –OH, C–H stretching and C@O bands
and disappearance of band corresponding to PVB
vinyl acetate unit. None of these changes were
observed in the spectra presented in Fig. 2a–c. It
can be seen from Fig. 2d that the only band that
was changed is the one related to ester units, pres-
ent in the PVB and in the plasticizer. Once the PVB
unit bands did not change, the variation in absor-
bance of the C@O band was attributed only to
the plasticizer. The plasticizer is most likely exuding
– or degrading – during the manufacturing of the
 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768 759

a c
Intensity (a.u.)

Intensity (a.u.)
8
8
7 7
6
5
6
4 5
3
4
2 3
2
1 1

4000 3500 1300 1200 1100 1000 900

Wavenumber (cm-1) Wavenumber (cm-1)

b d
Intensity (a.u.)

Intensity (a.u.)

6
5

8 4
7
6 3
5 2
4
3
2 1
1

3200 3150 3100 3050 3000 2950 2900 2850 2800 2750 2700 2000 1500
Wavenumber (cm-1) Wavenumber (cm-1)

Fig. 2. Infrared spectra of the PVB films. 1 = original PVB film; 2 = R2 recovered PVB film; 3 = R1 recovered PVB film; 4 = original
PVB film (1 extrusion step); 5 = original PVB film (2 extrusion steps); 6 = R1 recovered PVB film (1 extrusion step); 7 = R2 recovered
PVB film (2 extrusion steps); 8 = R2 recovered PVB film (1 extrusion step). (a) The band at 3489 cm1, corresponding to –OH group; (b)
together with the band relative to C–H stretching at 2970 cm1; (c) the band at 1140 cm1 relative to C–C(@O)–O stretching of vinyl
acetate units; and (d) the band at 1730 cm1 of C@O group.

windshields, recycling process and/or blend prepa- Table 2

ration. Table 2 presents the plasticizer contents of PVB film plasticizer content obtained using a calibration curve
the PVB films evaluated using the calibration curve Sample Weight fraction (%)
presented in Fig. 1. It can be seen that the original Original PVB film 33
film presents a plasticizer content of 33 wt.%, cor- R1 recovered PVB film 27
roborating values of the literature [1]. The plasti- R2 recovered PVB film 26
Original PVB film (1 extrusion step) 28
cizer content decreases to as low as 26 wt.% Original PVB film (2 extrusion steps) 24
during the recycling process (R1 and R2 films). R1 recovered PVB film (1 extrusion step) 21
When the films are extruded only once, the plasti- R2 recovered PVB film (1 extrusion step) 20
cizer content of the original and the recovered films R2 recovered PVB film (2 extrusion steps) 19
are reduced in about 15% and 23%, respectively.
The double extrusion leads to a decrease in plasti-
cizer content of 27% for both original and recov- PVB films. The authors showed that from 200 to
ered PVB film. These results are in good 250 °C (maximum process temperature used in this
agreement with the ones of Dhaliwal and Hay [3] work), the only changes of PVB films was loss of
who studied the degradation process of recovered plasticizer.
760 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768

Table 3 Table 4
Glass transition temperature (Tg) of PVB copolymer and PVB Thermogravimetric analyses of PA-6, PVB copolymer, PVB
films, and the melting temperatures of blends films, and blends
Samples Glass Melt Samples Weight
temperature temperature loss (%)
(°C) (°C) Original PVB film 4.1
PVB copolymer 71 R1 recovered PVB film 2.8
Original PVB film 4 R2 recovered PVB film 2.1
R1 recovered PVB film 11 PA-6 0.7
R2 recovered PVB film 13 PA-6/original PVB film (90/10) – single extrusion 2.5
PA-6 222 PA-6/original PVB film (80/20) – single extrusion 3.3
PA-6/original PVB film (90/10) – 222 PA-6/original PVB film (70/30) – single extrusion 3.5
single extrusion PA-6/original PVB film (60/40) – single extrusion 3.8
PA-6/original PVB film (80/20) – 222 PA-6/original PVB film (80/20) – double extrusion 2.6
single extrusion PA-6/R1 PVB film (80/20) – single extrusion 2.0
PA-6/original PVB film (70/30) – 222 PA-6/R2 PVB film (80/20) – single extrusion 1.5
single extrusion PA-6/R2 PVB film (80/20) – double extrusion 1.2
PA-6/original PVB film (60/40) – 221 PA-6/original PVB film (60/40) – double extrusion 2.7
single extrusion PA-6/R1 PVB film (60/40) – single extrusion 2.2
PA-6/original PVB film (80/20) – 220 PA-6/R2 PVB film (60/40) – single extrusion 2.0
double extrusion PA-6/R2 PVB film (60/40) – double extrusion 1.6
PA-6/R1 PVB film (80/20) – 219
single extrusion
PA-6/R2 PVB film (80/20) – 220 film maintains the thermal properties of the matrix,
single extrusion
PA-6/R2 PVB film (80/20) – 220
one of requirements for an efficient toughness agent,
double extrusion besides the improvement in impact properties [8]. It
PA-6/original PVB film (60/40) – 220 can also be noticed in Table 4 that the blends with
double extrusion higher PVB film content present the greatest weight
PA-6/R1 PVB film (60/40) – 221 losses. These results are in good agreement with the
single extrusion
PA-6/R2 PVB film (60/40) – 220
ones presented in Table 2 since the PVB film weight
single extrusion loss is attributed to loss of plasticizer, the loss is
PA-6/R2 PVB film (60/40) – 220 greater for the blends containing higher plasticizer
double extrusion concentrations in the films.

3.3. Rheological characterization

Table 3 shows the glass transition temperature
(Tg) of PVB copolymer and PVB films, and the
melting temperatures of blends. It can be seen that
the Tg of the pure copolymer is higher than the ones
of the films, due to the presence of plasticizer in the
films. The values found in this work corroborate the
ones obtained by Cascone et al. [21] and Dhaliwal
and Hay [3]. It can also be seen from Table 3 that
the melting temperature of the Polyamide-6 matrix
is not affected, within experimental error, by the
addition of PVB film. These results indicate that
the plasticizer did not migrate to PA-6 phase.
Table 4 presents a summary of thermogravimet-
ric analyses of PA-6, PVB, and blends. In Table 4,
it is shown the weight loss of the samples for tem-
peratures ranging from 25 to 250 °C. The results
presented in Table 4 show that the thermal degrada-
tion of the matrix is only slightly affected by the
presence of PVB film, since the weight loss of the
blends is always less than 4 wt.%. Hence, the PVB
Fig. 3 presents the viscosity of pure phases as a
function of shear rate. The vertical lines in Fig. 3
correspond to the applied shear rate during extru-
sion and injection molding processes (around 1000
and 10,000 s1, respectively [39]). The curves in
Fig. 3 show that the original PVB films present
the smallest viscosity values, and the viscosity of
the recovered films are of the same order of magni-
tude, within experimental error. The original films
present the largest reductions in viscosity, due to
the higher concentration of plasticizer in their com-
positions. Table 5 presents the dispersed phase/
matrix viscosity ratio for all studied binary systems
at a shear rate that corresponds to the injection
molding shear rate. For comparison purposes, the
plasticizer content of PVB films presented in Table
2 is shown again. It can be seen that the viscosity
ratio increases with decreasing amount of
plasticizer.
 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768 761

PA-6 (single extrusion)

PA-6 (double extrusion)
R2 Recovered PVB film (single extrusion)
R2 Recovered PVB film (double extrusion)
100 R1 Recovered PVB film (single extrusion)
Original PVB film (double extrusion)
Original PVB film (single extrusion)
Viscosity (Pa.s)

10

1000 10000

Shear rate (s-1)

Fig. 3. Viscosity of pure phases as a function of shear rate.

Table 5
Dispersed phase/matrix viscosity ratio for all studied binary systems at a shear rate that corresponds to the injection molding shear rate
(10,000 s1)
Sample Viscosity ratio Weight fraction of plasticizer (%)
Original PVB film (single extrusion)/PA-6 (single extrusion) 0.36 28
Original PVB film (double extrusion)/PA-6 (double extrusion) 0.56 24
R1 recovered PVB film (single extrusion)/PA-6 (single extrusion) 0.51 21
R2 recovered PVB film (single extrusion)/PA-6 (single extrusion) 0.53 20
R2 recovered PVB film (double extrusion)/PA-6 (double extrusion) 0.58 19
For comparison purposes, the plasticizer content of PVB films presented in Table 4 is shown again.

3.4. Blend morphology
Fig. 4 presents typical morphologies of the
blends studied here. Fig. 4a and b shows PA-6/ori-
ginal PVB film (60/40) blend, submitted to, respec-
tively, one and two extrusion steps, Fig. 4c and d
shows PA-6/R2 recovered PVB film (60/40), after
one and two step extrusions, respectively. Table 6
summarizes the quantitative experimental results
of morphological observations. For comparison
purposes, the notched Izod impact strength values
obtained for the blends are also presented. It can
be seen that all blends studied present particle sizes
greater than 0.1 lm and below 1 lm, and exhibit
low polydispersity (dv/dn < 2), which are favorable
conditions for a successful rubber toughening
[8,23]. It can be also seen from Table 6 that dn
increases with increasing PVB film concentration
due to dispersed phase coalescence. It can be also
seen from Table 6 that dn of PA-6/original PVB film
(1E) blend is larger than the one of PA-6/R1 recov-
ered PVB film (1E) and PA-6/R2 recovered PVB
film (1E) blends, and that dn of PA-6/original PVB
film (1E) blend is larger than dn of PA-6/original
PVB film (2E) blend. These results can be explained
in light of viscosity ratio that increases during the
recycling process or after the second extrusion.
These results are in good agreement with the results
of Wu [40] who suggested that the finest morphol-
ogy is reached when the viscosity ratio is close to
one.
3.5. Mechanical properties of the blends
3.5.1. Original PVB film/PA-6 blends
Figs. 5 and 6 present the tensile strength and
Young’s modulus of the blends as a function of
the original PVB film content (wt.%), respectively.
The results show that both the tensile strength and
modulus decreased when the PVB content
increased. A reduction in those two mechanical
properties is a common observation in rubber
toughened polymers because of the lower strength
and modulus of the dispersed phase [9,22–28].
Fig. 7 presents the notched Izod impact strength
of the blends using original PVB films. It can be seen
from Fig. 7 that the notched Izod impact strength
increases when the PVB film content increases,
762 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768

Fig. 4. Typical morphologies of the blends. 1E = one extrusion step and 2E = two extrusion steps. (a) PA-6/original PVB film (60/40), 1E,
after ethanol etching. (b) PA-6/original PVB film (60/40), 2E, after ethanol etching. (c) PA-6/recovered PVB film (60/40), 1E, after ethanol
etching. (d) PA-6/recovered PVB film (60/40), 2E, after ethanol etching.

Table 6
Quantitative results of the morphology of studied blends: dv = volume average diameter and dn = number average diameter
Sample dn dv Polydispersity (dv/dn) Notched Izod impact strength (kJ/m2)
PA-6/original PVB (90:10), 1E 0.53 1.04 1.9 166 ± 12
PA-6/original PVB (80:20), 1E 0.68 1.06 1.6 233 ± 48
PA-6/original PVB (70:30), 1E 0.86 1.40 1.6 326 ± 49
PA-6/original PVB (60:40), 1E 1.05 1.79 1.7 1590 ± 39
PA-6/original PVB (80:20), 2E 0.53 0.97 1.8 215 ± 23
PA-6/original PVB (60:40), 2E 0.60 0.86 1.4 1279 ± 69
PA-6/R1 recovered PVB – (80:20), 1E 0.44 0.71 1.6 202 ± 18
PA-6/R2 recovered PVB – (80:20), 1E 0.48 0.91 1.9 202 ± 26
PA-6/R2 recovered PVB – (80:20), 2E 0.57 1.02 1.8 196 ± 26
PA-6/R1 recovered PVB – (60:40), 1E 0.61 0.99 1.6 1289 ± 46
PA-6/R2 recovered PVB – (60:40), 1E 0.51 0.97 1.9 1239 ± 72
PA-6/R2 recovered PVB – (60:40), 2E 0.59 0.92 1.6 1108 ± 40
1E = one extrusion step and 2E = two extrusion steps. For comparison purposes, the notched Izod impact strength values of the blends
are also presented here.

and that the PA-6/original PVB film blends can be
considered tough (for PVB film concentrations up
to 30%) and super tough (for PVB film concentra-
tion of 40%) [8]. The results obtained in this work
partially corroborate the results reported by Cha
et al. [4], who used scrapped PVB films, very similar
to original PVB film, as an impact modifier for Poly-
amide-6. The greatest difference between the values
reported by the authors and the results obtained
in this work is in the impact strength values of the
 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768 763

70 2000

60

Notched Izod Impact Strength (J/m )

1600
50
Tensile Strength (MPa)

40 1200

30
800

20

400
10

0
0 10 20 30 40 0
PVB Film content (wt.%) 0 10 20 30 40
PVB Film content (wt.%)
Fig. 5. Tensile strength versus original PVB film content (wt.%).
Fig. 7. Notched Izod impact strength (J/m) as a function of
dispersed phase content (wt.%).

2300
Original PVB film (1E)
2100 Original PVB film (2E) Interparticle distance
Average particle diameter
1900 1800
Young's Modulus (MPa)

Notched Izod Impact Strength (J/m)

1700 1600 60/40 Blends

60/40 Blends
1500 1400

1200
1300
1000
1100
800
900
600
700 70/30 Blend 70/30 Blend
400
80/20 Blends
500 200
0 5 10 15 20 25 30 35 40 45 80/20 Blends
90/10 Blends
PVB Film Content (wt.%) 0
0.01 0.1 1 10
Fig. 6. Young’s modulus versus original PVB film content Interparticle distance (μm) or Average particle diameter (μm)
(wt.%). 1E = material extruded once, 2E = material extruded
twice. Fig. 8. Notched Izod impact strength versus interparticle dis-
tance and average particle size.

higher PVB film content blends. In the case of the

60/40 PA-6/PVB film blend, Cha et al. [4] obtained by Wu [22,26]. The results for the recovered PVB
an impact strength value of about 42 kJ/m2, film/PA-6 blends are also included in this graph
whereas in this work, 157 kJ/m2 was obtained. although the effect of recycling will be discussed
These differences can be due to the type of PVB film later in the paper. When the Izod impact strength
used, the processing conditions, and the test condi- is plotted as a function of the interparticle distance,
tions [8,23] that are different in both studies. a single curve can be fitted to the experimental data.
The results presented in Table 6 indicate that the This curve suggests that there is a particular single
finest morphology does not correspond to the best interparticle distance for which a sudden change in
improvement in impact strength, since the samples impact strength is observed. The same conclusion
with original PVB film present the greatest average cannot be drawn if the average particle size is con-
radius and the best impact strength indicating that sidered. It can be seen in Fig. 8 that the critical inter-
there is no straight correlation between the dis- particle distance is around 0.2 lm since that in this
persed phase particle size and the impact strength. region there was a sudden change in the Izod impact
Fig. 8 shows the notched Izod impact strength for strength values corroborating the results of Borgg-
all blends versus the average particle diameter, dn, reve et al. [27]. It can be noticed from Fig. 8 that
and the interparticle distance parameter proposed the blends with PVB film contents higher than
764 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768

Fig. 9. Micrograph of the notched Izod impact fracture of (a) PA-6, (b) PA-6/original PVB film (80/20) blend, (c) PA-6/original PVB film
(60/40) blend, (d) a magnification of 60/40 blend micrograph, after etching.

20 wt.% present an interparticle distance greater
than the critical. The interparticle distance of all
blends seem to be dependent only on their PVB con-
tent, regardless the kind of PVB film used (original
or recovered), or the number of extrusion steps (sin-
gle or double).
Fig. 9 shows typical fracture surfaces of notched
Izod impact strength specimens of PA-6 and PA-6/
PVB film (80/20 and 60/40) blends. The fracture
surfaces show the presence of two different regions
in the PA-6 and 80/20 blend specimens (Fig. 9a
and b). The inside region of the circles presented
in Fig. 9a and b features a mirror zone, which is
commonly observed in samples for which fracture
is preceded by craze formation. The outside circle
region, called hackle region [41], presents rough sur-
faces, with divergent lines pointing towards the
crack propagation directions. The 60/40 blends pre-
 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768 765

70

PA-6/PVB film (80/20)

60
PA-6/PVB film (60/40)

50
Tensile Strength (MPa)

40
62
60

30

44
43
42

42

41

41
20

37
36

36
24

10

0
PA-6 (1 and 2E) PVB O (1E) PVB O (2E) PVB R2 (1E) PVB R2 (2E) PVB R1 (1E)

Fig. 10. Tensile strength versus recovered and original PVB film content. The specimens were extruded once or twice. 1E = material
extruded once, 2E = material extruded twice, R1 = recovered film using lab-scale grinder; R2 = recovered film using an industrial grinder;
O = original film.

2500
PA-6/PVB film (80/20)
PA-6/PVB film (60/40)

2000
Young’s Modulus (MPa)

1500
2093
2075

1000
1695

1698
1596

1600
1259

1136

1139
1100

1091

500
793

0
PA-6 (1 and 2E) PVB O (1E) PVB O (2E) PVB R2 (1E) PVBR2(2E) PVB R1 (1E)

Fig. 11. Young’s modulus of the blends with recovered and virgin PVB film. 1E = material extruded once; 2E = material extruded twice;
R1 = recovered film using lab-scale grinder; R2 = recovered film using an industrial grinder; O = original film.

sented in Fig. 9c show an extensive matrix yielding, present greater fracture energy than 80/20
characteristic deformation of tough failure. The blends. These observations are in good agreement
tough fracture proceeds entirely within the PA-6 with the interparticle distance parameter since the
matrix, without exposing the PVB film particles (see 60/40 blends exhibit values of interparticle distance
Fig. 9d). Since the shear yielding of the matrix is smaller than the critical value (around 0.2 lm),
more effective to improve the impact strength whereas 80/20 blends presented values above the
than crazing, it is expected that the 60/40 blends critical.
766 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768

3.5.2. Recovered PVB film/PA-6 blends (2) The notched Izod impact strength values of the
The PVB concentrations that resulted in best blends containing recovered films are higher
combination of impact strength and tensile proper- than the ones for pure PA-6. However, the
ties were found to be 20 and 40 wt.% of PVB film. blends containing recovered films show a lower
Adding 40 wt.% PVB film to PA-6 resulted in an impact strength value than the ones containing
increase of impact strength of about 1400% when the original PVB film, except in the case of the
compared to the one for pure PA-6, although pre- 60/40 original PVB blend extruded twice.
senting the smallest tensile strength and modulus. (3) Independently of the type of PVB film used,
Adding 20 wt.% PVB film to PA-6 resulted in a super tough blends were obtained when
reduction in the tensile strength values of at least 40 wt.% of PVB film is added to PA-6.
50% smaller than the ones for the 40 wt.% PVB film (4) The tensile strength and Young’s modulus of
blend, but the improvement in impact strength was the blends obtained using recovered PVB are
not as significant. Hence, the 80/20 and 60/40 com- of the same order of magnitude as the ones
positions were chosen for studying the substitution of the blends obtained using pure PVB films
of original PVB film from recovered PVB film. processed twice; the specimens with original
Figs. 10–12 present a comparison of the tensile PVB film as toughening agent, submitted to
strength, Young’s modulus and notched Izod only one extrusion presented the smallest ten-
impact strength of the blends obtained with original sile strength and modulus.
PVB and with recovered PVB (for both processes (5) The tensile strength of the 80/20 blends sub-
R1 and R2). All those mechanical properties were mitted to one or two extrusions are of the
determined for samples extruded once (1E) and same order of magnitude within experimental
twice (2E). The following observations can be done error. In the particular case of the 60/40 origi-
when analyzing those three figures. nal PVB blend, a large increase of tensile
strength was observed when the blend was
(1) Both recycling processes (industrial R2 or lab processed twice (see Fig. 10). The tensile
scale R1) result in blends with similar mechan- strength increased in about 83% when the
ical properties within experimental error. blend was reprocessed.

1600 PA-6/PVB film (80/20)

PA-6/PVB film (60/40)

1400
Notched Izod Impact Strength (J/m)

1200

1000
1590

800
1289
1279

1239

600
1108

400

200
233

215

202

202
196
104
95

0
PA-6 (1 and 2E) PVB O (1E) PVB O (2E) PVB R2 (1E) PVB R2 (2E) PVB R1 (1E)

Fig. 12. Notched Izod impact strength of the blends with original and recovered PVB film as impact modifier. 1E = material extruded
once; 2E = material extruded twice; R1 = recovered film using lab-scale grinder; R2 = recovered film using an industrial grinder;
O = original film.
 T.S. Valera, N.R. Demarquette / European Polymer Journal 44 (2008) 755–768
1650
PA-6/PVB film (80/20)
Notched Izod Impact Strength(J/m)
1450
PA-6/PVB film (60/40)
1250
1050
850
650
450
250
50
0 5 10
Plasticizer content (wt.%)
Fig. 13. Notched Izod impact strength of the blends as a function
of plasticizer content. 1E = material extruded once; 2E = mate-
rial extruded twice; R1 = recovered film using lab-scale grinder;
R2 = recovered film using an industrial grinder; O = original
film.
(6) When comparing the 80/20 and 60/40 blends it
can be seen, as expected, that the tensile
strength and Young’s modulus of the 80/20
blends (for every kind of PVB film used) are
larger than the ones of 60/40 blends. An oppo-
site trend is observed for the notched impact
strength.
Fig. 13 presents the notched Izod impact strength
of the blends studied in this work as a function of
plasticizer content. It can be seen that the notched
Izod impact strength decreases almost linearly with
decreasing concentrations of plasticizer, mainly in
the blends with high concentration of dispersed
phase. Theses results indicate that the PVB film
plasticizer content is a factor that needs to be con-
trolled of one wants to use recovered PVB film as
an impact modifier.
4. Conclusions
In this paper, an alternative to use the PVB film
from recycled windshields as a toughening agent or
an impact modifier for Polyamide-6 was presented.
The results showed that the original PVB film pre-
sents a plasticizer content of 33 wt.%, which
decreased to as low as 20 wt.% after the recycling
and blend preparation processes. The PA-6/original
and recovered PVB film blends showed a reduction
in their tensile strength and Young’s modulus val-
ues, when compared to the ones for PA-6 matrix,
but all blends presented a dramatic increase in their
toughness, with a special feature for the 40 wt.%
767
blend, which resulted in a super toughened material.
The use of recovered PVB film as impact modifier is
conditioned to the quantification of the loss of plas-
ticizer undergone during the windshield recycling
process and blend preparation since the amount of
plasticizer controls the viscosity ratio of the dis-
persed and matrix phases, which in turns controls
the morphology of the blends and their properties.
The morphological observations showed that if the
interparticle distance is smaller than around
0.2 lm (critical value), the notched Izod impact
15 20 25 30
strength values increase considerably. Conse-
quently, the fracture surface of these blends exhib-
ited characteristics of tough failure.
Acknowledgments
The authors would like to thank FAPESP,
CAPES and CNPq for financial support. Saint-
Gobain Sekurit, Celanese Chemical Europe and
Solutia do Brasil for providing the materials used
in this study.
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