Advantages of Nanocomposites

Based on
Polyvinylchloride/Organoclay
A. Kalendova, L. Kovarova,
J . Malac, J . Simonik
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Zln
Brno
Ostrava
Praha
http://ft.utb.cz
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Content
Content
!
Introduction
Introduction
!
!
Experimental Conditions
Experimental Conditions
!
!
Results
Results
-
-
Mechanical properties
Mechanical properties
-
-
Abrasion resistance
Abrasion resistance
-
-
Flame resistance
Flame resistance
-
-
Barrier properties
Barrier properties
-
-
Migration
Migration
!
!
Conclusion
Conclusion
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Nanocomposites:
Nanocomposites:
Organic/(in)organic heterogeneous
Organic/(in)organic heterogeneous
materials
materials
with
with
nanometer sized structure elements at least in one
nanometer sized structure elements at least in one
dimension
dimension
(
(
nano
nano
-
-
fibers,
fibers,
nano
nano
-
-
sheets,
sheets,
nano
nano
-
-
spheres).
spheres).
The most developed directions with a real potential in
The most developed directions with a real potential in
polymer processing industry:
polymer processing industry:
! ! Carbon Carbon nanotubes nanotubes- - conductive composites with low filler conductive composites with low filler
loading (<1%) loading (<1%)
! ! Polymer/clay nanocomposites ( Polymer/clay nanocomposites (nano nano- -sheets dispersed in sheets dispersed in
the polymer matrix) the polymer matrix)
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Montmorillonite
Montmorillonite
!
!
2:1 type of layer structured clay mineral
2:1 type of layer structured clay mineral
!
!
Platelet thickness: 1nm
Platelet thickness: 1nm
!
!
Surface area: 750 m
Surface area: 750 m
2 2
/g
/g
!
!
High aspect ratio
High aspect ratio
(
(
MMT: 500
MMT: 500
-
-
1000 versus Kaolin: 10
1000 versus Kaolin: 10

30
30
)
)
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
1 m
SEM Structure
Cloisite
Cloisite
Na
Na
+ +
Intercalation
Intercalation
1 m
SEM
Cloisite
Na+
1 m
SEM
Cloisite
30B
interkalovan
!
!
C
C
hemical
hemical
modification of the clay surface to convert it from
modification of the clay surface to convert it from
hydrophilic to
hydrophilic to
organophilic
organophilic
!
!
T
T
he result = larger distance of
he result = larger distance of
montmorillonite
montmorillonite
layers
layers
!
!
Alkylammonium ions are the most widely used intercalants
Alkylammonium ions are the most widely used intercalants
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Co
Co
-
-
i
i
ntercalation
ntercalation
!
!
C
C
hemical
hemical
modification of the clay surface
modification of the clay surface
by
by
two or
two or
more
more
intercalats
intercalats
!
!
Co
Co
-
-
intercalant agents
intercalant agents
do not
do not
work oneself
work oneself
as
as
intercalant
intercalant
Why use co-intercalation?
!
!
Amine
Amine
group of intercalant could be the source of
group of intercalant could be the source of
degradation of any polymers
degradation of any polymers
(e.g. PVC)
(e.g. PVC)
!
!
Co
Co
-
-
intercalation allows us decreasing the amount of
intercalation allows us decreasing the amount of
amine
amine
in the composition and therefore lowers the
in the composition and therefore lowers the
degradation process
degradation process
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Intercalation technology for
Intercalation technology for
montmorillonite
montmorillonite
Ion exchange method
Ion exchange method
!
!
Wet route
Wet route
!
!
Commercial types
Commercial types
organoclays
organoclays
(e.g. (e.g. Cloisites Cloisites from SCP) from SCP)
Ion
Ion
-
-
dipole method
dipole method
!
!
Dry route
Dry route
!
!
Great versatility
Great versatility
!
!
Simple
Simple
=>
=>
cheap
cheap
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Advantages of Nanocomposites
Advantages of Nanocomposites
!
!
Greater
Greater
tensile and flexural
tensile and flexural
strength
strength
for the same
for the same
dimension of plastic part
dimension of plastic part
!
!
Reduced weight
Reduced weight
for the same performance
for the same performance
!
!
Increased dimensional
Increased dimensional
stability
stability
!
!
Improved
Improved
gas barrier
gas barrier
properties
properties
for the same film
for the same film
thickness
thickness
!
!
Flame retardant properties
Flame retardant properties
!
!
Higher chemical resistance
Higher chemical resistance
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Overview of
Overview of
nanocomposite
nanocomposite
properties improvements
properties improvements
polymer
matrix PE PP PMMA PET PC PVC PS PA BIO
++ ++ ++ ++ ++
80-100 % 30-60% 70-100% 40% 70-100%
++ ++ + ++
50-100K 70K 30-100K 130K (HDT)
++ ++
54-70%
70%
+/-
++ ++
+ + +/- +
+/- ++
+ + +/- +/-
+/-
Colouring
++ ++
Flame retardant +
-
+/- +/-
+/-
+
+
++ ++ -
+/-
+/- ++
Transparency
Slow release
+/- +/- +/-
+/- ++
++ ++ ++ ++ ++
+
Permeability
decrease
+ ++
+/-
Mechanical
strenght increase
+ ++ ++
++ ++ ++
+
Thermal stability
increase
Experimental
Experimental
Experimental conditions
Experimental conditions
1.
1.
Materials:
Materials:
!
!
Suspen
Suspen
s
s
ion type of PVC
ion type of PVC
-
-
Spolana
Spolana
Neratovice
Neratovice
,
,
!R
!R
,
,
Neralit
Neralit
652 (K = 65)
652 (K = 65)
!
!
PVC
PVC
plasticizers
plasticizers
-
-
Deza
Deza
Valask Mezi!", #R
Valask Mezi!", #R
-
-
D
D
ioctylphtalate
ioctylphtalate
(DOP)
(DOP)
-
-
D
D
ioktyladipate
ioktyladipate
(DOA)
(DOA)
-
-
P
P
olyester
olyester
Lankroflex
Lankroflex
(PLA)
(PLA)
!
!
Nanofillers
Nanofillers

Southern Clay Products

Southern Clay Products
, USA
, USA
-
-
Cloisite
Cloisite
Na
Na
+ +
-
-
nature
nature
type
type
of montmorillonite
of montmorillonite
-
-
Cloisite
Cloisite
30B
30B
-
-
intercalated
intercalated
type
type
of
of
montmorillonite
montmorillonite
Clays:
Clays:
1,85
1,85
nm
nm
1,2
1,2
nm
nm d-spacing
90
90
meq
meq
/100 g
/100 g
-
-
Modifier Concentration
methyl,
methyl,
tallow
tallow
, bis
, bis
-
-
2
2
-
-
hydroxyethyl
hydroxyethyl
,
,
quaternary
quaternary
ammonium
ammonium
chlorid
chlorid
-
-
Organic Modifier
30B Na
+
Cloisite
CH
2
CH
2
OH
CH
3
N
+
T
CH
2
CH
2
OH
Cloisite 30B Organic Modifier
Intercalation Model
",85 nm
Surface
Treatment
2.
2.
Equipment:
Equipment:
!
!
L
L
aboratory
aboratory
mixer (T=80
mixer (T=80
o o
C, 2000 rpm)
C, 2000 rpm)
!
!
Buss KO
Buss KO
-
-
kneader
kneader
MKS 30
MKS 30
(T=
(T=
130
130
-
-
160
160
o o
C
C
,
,
L/ D=18 mm, D= 30 mm
L/ D=18 mm, D= 30 mm
,
,
5
5
0 rpm)
0 rpm)
!
!
L
L
aboratory calander
aboratory calander
!
!
X
X
-
-
ray
ray
di
di
ff
ff
raktometer
raktometer
-
- URD 6 difraktometr
!
!
M
M
icroscopy
icroscopy

SEM, TEM, AFM

!
!
DMA
DMA
DX04T
DX04T
Experimental conditions
Experimental conditions
Tomas Bata University in Zlin , Faculty of technology, Czech Republic
Results
XRD, SEM, TEM, DMA, ABRASION,
FLAME RESISTANCE, BARRIER
PROPERTIES AND MIGRATION
Mechanical properties:
Mechanical properties:
0
40
80
120
160
P
V
C

+

D
O
P
P
V
C
/

(
3
0
B

5
%

+

D
O
P
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
P
)
P
V
C
/

(
N
a
+

5
%

+

D
O
P
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
P
)
P
V
C

+

D
O
A
P
V
C
/

(
3
0
B

5
%

+

D
O
A
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
A
)
P
V
C
/

(
N
a
+

5
%

+

D
O
A
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
A
)
P
V
C
/

P
L
A
P
V
C
/

(
3
0
B

5
%

+

P
L
A
)
P
V
C
/

(
N
a
+

5
%

+

P
L
A
)
/
E
*
/


(
M
P
a
)
,

5
0
o
C
XRD patterns:
XRD patterns:
0
100
200
300
400
1 3 5 7 9 11 13 15
2

(deg)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
PVC/DOP
PVC/(30B 5%+ DOP)
PVC/(30B 10% + DOP)
3
,
4
8

n
m
1
,
2
2

n
m
1
,
7
3

n
m
XRD patterns:
XRD patterns:
0
50
100
150
200
250
300
1 3 5 7 9 11 13 15
2 (deg)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
PVC/PLA
PVC/(30B 5%+ PLA)
PVC/(Na5%+ PLA)
4
,
1
6

n
m
1
,
9
3

n
m
1
,
4
1

n
m
2. Cut, 20 000x
2. Cut, 20 000x 1. Cut, 440x
1. Cut, 440x
50 m
1
1 1 1 1 m
2
3. Cut vertical, etching O
2
, 20 000x
3. Cut vertical, etching O
2
, 20 000x
1 1 1 1 m
3
1 1 1 1 m
4. Cut horizontal, etching O
2
, 20 000x
4. Cut horizontal, etching O
2
, 20 000x
4
SEM:
SEM: PVC/ (30B 5% + DOP)
AFM
AFM
PVC/ (30B 5% + DOP)
1
4
8
4

n
m
1
4
8
4

n
m
310
nm
1. SEM, cut, etching O
2
, 20 000x
1. SEM, cut, etching O
2
, 20 000x
1 1 1 1 m
1
2. AFM, cut, etching O
2
2. AFM, cut, etching O
2
742 nm
2
TEM:
TEM: PVC/ (Closisite 30B 5% + DOP)
3 nm
4 nm
Abrasion resistance:
Abrasion resistance:
0,00
0,05
0,10
0,15
0,20
P
V
C

+

D
O
P
P
V
C
/

(
3
0
B

5
%

+

D
O
P
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
P
)
P
V
C
/

(
N
a
+

5
%

+

D
O
P
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
P
)
P
V
C

+

D
O
A
P
V
C
/

(
3
0
B

5
%

+

D
O
A
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
A
)
P
V
C
/

(
N
a
+

5
%

+

D
O
A
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
A
)
P
V
C
/

P
L
A
P
V
C
/

N
a
+

5
%

+

P
L
A
A
b
r
a
s
i
o
n

(
m
m
)
Flame resistance:
Flame resistance:
0
3
6
9
12
15
P
V
C

+

D
O
P
P
V
C
/

(
3
0
B

5
%

+

D
O
P
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
P
)
P
V
C
/

(
N
a
+

5
%

+

D
O
P
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
P
)
P
V
C

+

D
O
A
P
V
C
/

(
3
0
B

5
%

+

D
O
A
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
A
)
P
V
C
/

(
N
a
+

5
%

+

D
O
A
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
A
)
P
V
C
/

P
L
A
P
V
C
/

(
3
0
B

5
%

+

P
L
A
)
P
V
C
/

(
N
a
+

5
%

+

P
L
A
)
A
f
t
e
r
f
l
a
m
e

t
i
m
e

(
s
)
Flame resistance:
Flame resistance:
SEM pictures
SEM pictures
50 m 5 m
1. PVC/DOP, 440x
1. PVC/DOP, 440x
2. PVC/DOP, 4 400x
2. PVC/DOP, 4 400x
1
2
50 m 5 m
3. PVC/(30B 5% + DOP), 440x
3. PVC/(30B 5% + DOP), 440x
4. PVC/(30B 5% + DOP), 4 400x
4. PVC/(30B 5% + DOP), 4 400x
3 4
Barrier properties
Barrier properties
(after 1 day)
(after 1 day)
0,0
0,5
1,0
1,5
2,0
2,5
3,0
P
V
C

+

D
O
P
P
V
C
/

(
3
0
B

5
%

+

D
O
P
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
P
)
P
V
C
/

(
N
a
+

5
%

+

D
O
P
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
P
)
P
V
C

+

D
O
A
P
V
C
/

(
3
0
B

5
%

+

D
O
A
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
A
)
P
V
C
/

(
N
a
+

5
%

+

D
O
A
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
A
)
P
V
C
+

P
L
A
P
V
C
/

(
3
0
B

5
%
+

P
L
A
)

P
V
C
/

(
N
a
+

5
%

+

P
L
A
)
W
V
T

(
g
/
h
m
2
)
Migration of plasticizers
Migration of plasticizers
(after 1 day)
(after 1 day)
0,00
0,02
0,04
0,06
0,08
0,10
P
V
C

+

D
O
P
P
V
C
/

(
3
0
B

5
%

+

D
O
P
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
P
)
P
V
C
/

(
N
a
+

5
%

+

D
O
P
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
P
)
P
V
C

+

D
O
A
P
V
C
/

(
3
0
B

5
%

+

D
O
A
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
A
)
P
V
C
/

(
N
a
+

5
%

+

D
O
A
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
A
)
P
V
C
+

P
L
A
P
V
C
/

(
3
0
B

5
%
+

P
L
A
)

P
V
C
/

(
N
a
+

5
%

+

P
L
A
)

w

(
g
)

0% 11%
3%
8%
5%
24%
6%
0%
-11%
6%
2% -3% 0%
Migration of plasticizers
Migration of plasticizers
(after 30 days)
(after 30 days)
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
P
V
C

+

D
O
P
P
V
C
/

(
3
0
B

5
%

+

D
O
P
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
P
)
P
V
C
/

(
N
a
+

5
%

+

D
O
P
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
P
)
P
V
C

+

D
O
A
P
V
C
/

(
3
0
B

5
%

+

D
O
A
)
P
V
C
/

(
3
0
B

1
0
%

+

D
O
A
)
P
V
C
/

(
N
a
+

5
%

+

D
O
A
)
P
V
C
/

(
N
a
+

1
0
%

+

D
O
A
)
P
V
C
+

P
L
A
P
V
C
/

(
3
0
B

5
%
+

P
L
A
)

P
V
C
/

(
N
a
+

5
%

+

P
L
A
)

m

v
z
o
r
k
u

(
g
)
14%
2%
0%
0%
0%
1%
3% -3%
7% 6% 18%
5% -10%
Results:
Results:
! I n the case of barrier properties the improvement
around 30% is common. It is likely caused by the
longer tortuous path. The migration was not
improved dramatically (5 - 10% after 1 day).
!
!
The mechanical properties have been increased
The mechanical properties have been increased
and they strongly depend
and they strongly depend
on
on
the level of
the level of
exfoliation
exfoliation
.
.
!
!
The abrasion resistance degreases. This fact
The abrasion resistance degreases. This fact
indicates that the
indicates that the
nanoclay
nanoclay
particles function as
particles function as
plastici
plastici
z
z
er
er
carrier.
carrier.
! The flame resistance was improved. The effect is
based probably on the creation the insulating layer
which inhibit the oxygen access.
Thank you
for your attention!
Thank you
for your attention!