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MODIFICATION DE KAOLINITES SUBMICRONIQUES EN VUE DE

LEUR INCORPORATION DANS DES MATRICES POLYMRES

SURFACE MODIFICATION OF ULTRA FINE KAOLINITES AND

THEIR INCORPORATION INTO POLYMER MATRICES
MARCOS BATISTELLA
M. Jos-Marie LOPEZ-CUESTA
M. Carlos PETTER
M. Belkacem OTAZAGHINE
Mme. Anne-Sophie CARO-BRETELLE

Directeur de thse
Co-directeur de thse
Encadrant
Encadrante

Introduo
L

o Caolinita

L 50 nm - 5 m
h 30 - 100 nm

001
h

Al2Si2O5(OH)4

o Compsitos
o Propriedades Mecnicas & Modificao da Superficie
Buggy, M., et al. (2005). Composites Part A: Applied Science and Manufacturing,
36(4), 437442.

Itagaki, T., Matsumuraet al. (2001). Journal of Materials Science Letters, 20(16),
14831484.
Gardolinski, et al. (2000). Journal of Materials Science, 35(12), 31133119.
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Introduo
o Reao ao fogo
o Uso de cargas minerais
o Tryhydroxyde daluminium
2 Al(OH)3
Al2O3 + 3 H2O (1051 J/g)
o Montmorillonitas (argilas)

o Outros Estudos: Caolinitas

Wang, et al. Pol. Deg. Stab., 95(4), 572578 (2010).
Vahabi et al., Applied Clay Science, 70, 58-66 (2012).
Shehata et al. J. Appl. Pol. Sci. 92, 3119-3125 (2004).

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Objetivos
Reao ao
fogo
Carga
Funcional
Propriedades
Mecnicas

Objetivos

Mecanismos

Modificao
de superfcie

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Materiais
Cargas

Modificao
de Superfcie

Matrizes

Mean Diameter Specific surface

H

Aspect Ratio

(m)
Area (m2.g-1)
(l/h)
3-aminopropyl
Reference
Density Kaolinites
Applications
O
K1, K2,
K3
O
A
trymetoxysilane
Kaolinite K1
0,8
12,2
12
O
S i
O Paralux
S i
O
O
Ethylene-vinyl
Ethylene-vinyl
Talc
TA
O
Glycidoxypropyl
acetate
Kaolinite
K2(28%
0,2 0,95
19
Alcudia
PA440O
CablesEVA 6
acetate
G
3 - A m vinyl
i n o p r acetate)
o p y l ) t r i t h o x y s i l a n e 3 - g l y c i d o x y p r o p y l t r i m t h trimetoxysilane
o x y s ila n e
Trisilanol
Isooctyl
Polyamide
PA 19
Aluminium
Kaolinite K3
Paraplate
3
76
POSS
ATH
Polyamide 6
Rhodia C206
1,14
Automotive
Trisilanol
Polypropylene
trihydroxyde
Talc
Jetfine 0.7
0,7
19,9isooctyyl PP Polypropylene
Sabic PP505P
0,905
Automotive P
POSS
Magnesium
ATH
Apyral OP22
12,1
4
4
MgOH
Dihydrohyde
MDH
MH-10
1
2

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Mtodos
o Extruso/Injeo

o Cone Calorimtrico
o pHRR
o TTI
o THR
o THE

-2

HRR (kW.m )

pHRR

o Epiradiador

o Reologia
o Dynamical mode
o Parallel Plates

THR

Time (s)

TTI

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Cone Calorimtrico
1500

1500

1250
1000

HRR (kW/m)

1250

EVA
A20
A35
A50
A60

750

1000
750

500

500

250

250

0
0

200

400

EVA
K20
K35
K50
K60
A50

600

Time (s)

800 0

200

400

600

800

1000

Time (s)

Irr: 50kW*m-2
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Cone Calorimeter
1504

602

596

500

TTI (s)

Kaolinite
ATH

1032

1000

50
40

411
262

Kaolinite
ATH

60

-2

pHRR (KW*m )

1500

10

20

30

40

282
192

199

50

60

10

20

30

40

50

60

% Filler

% Filler

40

30

35

EHC (kJ/g)

30
25

o Decrease in pHRR

20
15

o Increase in TTI

ATH
Kaolinite

10
5
0
0

10

20

30

40

50

60

% Filler

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10

Reao ao fogo vs. Reologia

105

20 %

103
102
105

G' (Pa-s)

Regime 1

0,1

10

100

60 %

104

EVA
EVA-ATH
EVA-K1
EVA-K2
EVA-K3

103
102
0,1

20 %

10

10

10

Regime
Regime11

0,8
0,8
3

10

EVA

pHRRc/pHHR
G' (Pa-s)
pHRR
/pHHREVAG' (Pa-s)

1,0
1,0

0,6
0,6
10

20

10

0,1

5010
% 20
20 20

0,4
0,4
10

0,2
0,2
3

10

0,0
2

10

00

0,1

20

0,4

20

20

0,2

35

Regime 2
50
35

35

60
50

35

50

50

0,0
0

EVA-ATH
EVA-K1
EVA-K2
EVA-ATH
EVA-K3
EVA-K1
MDH
EVA-K2
Bohmite
EVA-K3
ATH-2

10

G'c/G'EVA

100

20

3520
35
20 10 20
30
50
30
50 50
35
60 35 50 35
35
35
35
50 50

0,0
10

20

0,6

100

(rad/s)

20

EVA-ATH
EVA-K1
EVA-K2
EVA-K3

0,8

pHRRc/pHHREVA

G' (Pa-s)

1,0
104

10
1

Regime
Regime 2
40
60 55
50

G'c/G'EVA

61020

50

EVA
EVA-ATH
50
EVA-K1
50
60
50
EVA-K2
EVA-K3

100

Temperature: 160 C
Strain: 5 %
Parallel Plates

30
10

/G'EVA
G'(rad/s)
c

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11

Estabilidade Trmica
100

100

-20

-20

80

80

Weight (%)

-15

-15

-6
-4

60

60

-10

-10

-4

40

40

-2

-5

-5

-2

20

20

0
250

0
0

Derivative Weight (%)

-20

450
100

300

500
300

200

350
400

400

450

550
500

600

600
0

700

300

450 200

100

350

500400

300

400

550600

500

EVA
EVA-K1-20
EVA-K1-35
EVA-K1-50
EVA-K1-60

EVA
EVA-ATH-20
EVA-ATH-35
EVA-ATH-50
EVA-ATH-60

-15

0
250

-10

0
600
700

450

-20
-15
-10

-5

-5

0
0

Under air; 10C/min.

200

400

600

Temperature (C)

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200
400
600
Temperature (C)

12

Concluses
o A qdio de caolinita no EVA apresenta vantagens em relao
formulaes EVA+ATH:
o Melhora na reao ao fogo pela formao de uma barreira protetora
o
o

Reduo do pHRR
Aumento do TTI

o Reologia
o G x pHRR
o Efeito catalitico na perda da parte acetato

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Modificao da Superfcie
BJT-Atrao de Jovens Talentos

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Caracterizao

100

K1
K1-ODPA
K1-G
K1-ODPA/G

90
2

85

Adsorbance

Masse (%)

95

80

K1
K1-G
K1-ODPA
K1-ODPA/G

-1

dTG (%.min )

-1.6
-1.2
-0.8

3000

2950

2900

2850

2800

2750

-0.4
0

0.0
0

200

400

600

800

4000

3500

3000

2500

2000

1500

1000

500

-1

Longueur d'onde (cm )

Temprature (C)

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Misturas PP/PA

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16

Perspectivas
Modificao da Superficie

PP

PP

Nodules
de PA

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Nodules
de PA

17

Perspectivas
Exfoliao/Modificao Seletiva
DMSO

Dodecylamine

MMA/AIBN
T = 80C

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Thank you for your attention!

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PCFC
Small amounts (1-4mg)
Coupling between condensed and gas phase
Complete combustion

Scrubbers

Analy
zer

Flowmeter

O2

O2
Combustor
Pyrolysys
chamber
Solid

Pyrolyzer

N2

Gas release

D
A
Q

HHR (W/g)
pHRR
HRC

Sample

R. Sonnier, et al. Predicting the flammability parameters of a

polymer: Application to some phosphonate groups.
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