Polypropylene Based Nanocomposites Containing Various Organoclay

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Polypropylene Based Nanocomposites Containing Various Organoclay

Polypropylene Based Nanocomposites

Containing Various Organoclay

J. Li and L. A. Utracki

Polymer Composites Group Industrial Materials Institute National Research Council Canada

The 6th _{PNC-Tech Meeting}

2

Outline

Objective

Experimental details

Results

3

Work objectives

Evaluation of dispersion and mechanical

properties of polypropylene based

nanocomposites containing organoclays

– especially synthetic clays.

Comparison of relative merits of natural

and synthetic clays.

4

Clay Properties

Specifications of synthetic and (for comparison) mineral clays

The

highlighted clays are at IMI

Company Organoclay Intercalant Wt. loss (%) Aspect ratio d_{001 (nm)} CEC (meq/g)

Synthetic clays

CO-OP Somasif ME-100 none 5000 0.95 1.1- 1.2

Somasif MAE 2M2HT 30-40 5000 3.1

Somasif MTE M3O 25-35 5000 2.4

Somasif MEE M2EtOHC 20-30 5000 2.3

Somasif MPE M2E-PPOH 60-70 5000 5..3

Lucentite SWN none < 10 ~50 1.27 0.65

Lucentite SAN 2M2HT 30-40 ~50 1.79 1.2

Lucentite SPN M2E-PPOH 55-65 ~50 4.37

Lucentite SEN M2EtOHC 30-40 ~50 2.39

Lucentite STN M3O 22-32 ~50 2.44

Topy Ind. Topy-4CTs 3MOD ~27 1000-5000 2.32 0.827

Topy-4CDTs 2M2OD ~32 1000-5000 3.18 0.352

Kunimine Sumecton SA none < 10 50 1.3 0.997 - 0.71

Laport Ind. Laponite RD none ~9.5 25 (mono) 0.48

Laport Ind. Laponite B none < 10 ~25

Süd Chemie Optigel SH none < 10 20 – 50

FCC Inc. Suplite-MP none < 10 ~25

Mineral Clays

SCP Na-MMT none 7 ~290 1.23 1.0

10A 2MBHTA 39 ~290 1.93 1.25

20A 2M2HTA 38 ~290 2.47 0.95

30B MT2EtOH 32 ~290 1.86 0.90

Kunimine Kunipia-F none < 10 320 (80-1120) 1.2 1.15

Kunipia-T 3MOD 32.2 ~320 2.07

5

Materials

Trade name Intercalant (wt%) Mw (Kg/mol) Density (g/ml) at 25 o_C T_m (o_{C) Supplier} Profax 1274 250 0.902 161 Basell PB3150 330 0.91 ~164 Crompton Somasif MAE 2M2ODA 40.0  0.0* -- -- -- Unicoop/CBC Co. Ltd Lucentite SAN 2M2ODA 41.0  0.0* -- -- -- Unicoop/CBC Co. Ltd Cloisite 20A 2M2ODA 39.0  0.3* -- -- -- Southern Clay products

6

Sample designation

Designation Loading and organoclay type Loading and compatibilizer PP-PB3150 none 4 wt% PB3150 TMQC20A 2 wt% C20A 4 wt% PB3150 TMQSAN 2 wt% Lucentite SAN 4 wt% PB3150 TMQMAE 2 wt% Somasif MAE 4 wt% PB3150

7

Compounding

Masterbatch: PP + 20 wt% of compatibilizer (Polybond 3150) + 10-wt% of organoclay.

TSE: Leistritz-34mm CORI, L/D = 40 with screw configuration shown above (N = 100 rpm, T = 200°C, Q =10 kg/h), under a blanket of dry nitrogen.

Feeding: Zone 0: PP + compatibilizers;

Zone 5: side feeder for organoclay

PNC by dilution masterbatch with addition of PP (N =200 rpm, T =190o_C,

8

XRD Patterns for

Organoclays

2 Theta (degree) 2 3 4 5 6 7 8 9 10 Inten sity (cps) 0 500 1000 1500 2000 Somasif MAE; d001 = 3.13 nm Lucentite SAN; d001 = 2.17 nm C20A; d001 = 2.50 nm All organoclays contain the same intercalant with

similar loading amount. Somasif MAE has

the largest d001 spacing,

while Lucentite SAN, the smallest.

Somasif MAE has the largest aspect ratio (~5,000).

9

XRD Patterns for

Nanocomposites

2 Theta (degree) 1 2 3 4 5 6 7 8 9 10 In ten sit y ( cp s) 0 5000 10000 15000 20000 25000 TMQC20A190; d001 = 2.99 nm TMQSAN190; d001 = 2.49 nm TMQMAE190; d001 = 3.47nm 2 Theta (degree) 1 2 3 4 5 6 7 8 9 10 In ten sit y ( cp s) 0 2000 4000 6000 8000 10000 12000 14000 TMQC20A220; d001 = 2.80 nm TMQSAN220; d001 = 2.15 nm TMQMAE; d001 = 3.23 nm T = 190 o_C T = 220 o_C

Comparing to organoclays, the d001 spacing of PNC increased indicating

intercalation of organoclays by the matrix.

Shifting peak to higher 2Q position at higher temperature means the

reduction of d001, which might be caused by the Hofmann elimination

reaction of the or the intercalant and/or partial diffusion of it from the organoclay interlayers to the matrix.

10

FEGSEM-TMQC20A

Good dispersion was found for PNC containing C20A. The clay particles slightly increased at the higher processing temperature. 10 mm 10 mm 5 mm 5 mm 190o_C 220o_C

11 T

FEGSEM-TMQSAN

10 mm 10 mm 5 mm 5 mm 190oC 220oC TMQSAN shows two population of clay dispersion. No significant morphology change was observed when processing temperature increased form 190 to 220o_C.

12

FEGSEM- TMQMAE

Two particle populations was observed with higher and lower aspect ratio. The aspect ratio seems to be higher at the higher processing temperature. 190oC 220oC 10 mm 10 mm 5 mm 5 mm

13

DSC

Thermograms-Crystallization

Temperature (oC) 100 110 120 130 140 He at Flow (W /g) -3 -2 -1 0 1 2 PP-PB3150-190 TMQC20A190 TMQSAN190 TMQMAE190 Temperature (oC) 100 110 120 130 140 Heat Flow (W/g) -3 -2 -1 0 1 2 PP-PB3150-220 TMQC20A220 TMQSAN220 TMQMAE220

The order of T_peak: Matrix < TMQC20A < TMQSAN < TMQMAE - high aspect ratio increased the rate of crystallization?

T_{peak of the specimens slightly increases with the increasing}

14

Crystallinity and T

_onset

PP-PB315 0-190 PP-PB315 0-220 TMQC20 A190 TMQC20 A220 TMQSA N190 TMQSA N220 TMQMAE1 90 TMQMAE2 20 To n set ( o C) 120 121 122 123 124 125 126 PP-PB315 0-190 PP-PB315 0-220 TMQC20A19 0 TMQC20A22 0 TMQSAN1 90 TMQSAN2 20 TMQMA E190 TMQMA E220 Cry st allin it y ( % ) 40 42 44 46 48 50

No significant change of crystallinity was observed with addition of the organoclays into PP-PB3150 matrix.

The addition of organoclay increased the onset crystallization temperature (T_onset) of PNC with the order of PP-PB3150

<TMQC20A<TMQSAN<TMQMAE.

15

Mechanical Properties

- Tensile Behavior

PP-PB3150 -190 TMQC20A19 0 TMQSAN1 90 TMQMAE19 0 Tensile str ength (MP a) 30 32 34 36 38 Tensile m odu lus (M P a) 1600 1800 2000 2200 2400 2600 PP-PB31 50-220 TMQC20 A220 TMQSAN22 0 TMQMAE22 0 Te nsile str eng th ( MPa) 30 32 34 36 38 Te nsile m odu lus ( MPa) 1600 1800 2000 2200 2400 2600

TMQMAE demonstrated the highest tensile modulus at both processing temperatures.

All the tensile moduli of PNC decreased with increasing

processing temperature, but the effect was the smallest for specimen of TMQMAE.

16

Mechanical Properties

- Flexural Behavior

PP-PB31 50-190 TMQC20A19 0 TMQSAN 190 TMQMAE19 0 F lexru al s tr en gth ( M Pa) 50 55 60 65 70 F lexur al m od ulu s ( M Pa) 1000 1200 1400 1600 1800 2000 2200 2400 Flexural strength Flexural modulus PP-PB3150-2 20 TMQC20A22 0 TMQSAN2 20 TMQMAE2 20 Flex rual strength (M Pa) 50 55 60 65 70 Flex

ural modulus (MPa)

1000 1200 1400 1600 1800 2000 2200 2400 Flexural strength. Flexural modulus

Generally, flexural behavior of the samples was insensitive

to the processing temperature from 190 to 220o_C.

Only TMQMAE showed flexural modulus increase at higher processing temperature.

17

Mechanical Properties

- Impact Strength

PP-PB315 0-220 TMQC20A22 0 TMQSAN2 20 TMQMA E220 Imp ac t st ren g th ( J/m) 20 22 24 26 28 30 32 34 PP-PB315 0-190 TMQC20A19 0 TMQSAN1 90 TMQMA E190 Imp ac t st ren g th ( J/m) 20 22 24 26 28 30 32 34

No significant impact behavior difference was found at the lower processing temperature, but it was at the higher

processing temperature.

TMQMAE and TMQC20A displayed better performance at higher processing temperature.

18

Conclusion

All organoclays in the PP matrix were intercalated by compatibilizer or PP

compared increasing the d₀₀₁ spacing of pristine organoclay and by

compounding.

Good dispersion on micro-scale of TMQC20A was observed by FEGSEM. The dispersion of synthetic clay appeared to have two populations. Stacks with high length (high aspect ratio) is the feature of TMQMAE.

TEM revealed that

The addition of organoclays did not alter significantly the crystallinity of PNC,

however, the T_onset’s of the PNC changed. The clay particle acts as a

nucleating agent and accelerates the crystallization process. The order is: TMQMAE>TMQSAN>TMQC20A.

The tensile and flexural moduli of nanocomposite containing synthetic clay -Somasif MAE - are superior to the one with mineral clays possibly due to the high aspect ratio.

19

Future work

Improving the dispersion of synthetic clay in PNC by

addition of compatibilizer mixture.

Investigating the relationship between dispersion,

structure and mechnical behavior.

The compounding should be repeated using SSE +

EFM