advances in the characterization of functional rubber .... sabu-nanoscale... · nanosize range...

Sabu Thomas International and Interuniversity Center for Nanoscience

and Nanotechnology,School of Chemical Sciences Mahatma Gandhi UniversityKottayam, Kerala,India

www.iiucnn.com, www.sabuthomas.com

Advances in the Characterization of Functional Rubber Composites and

Nanocomposites

Potential Nanocomposite Materials

Nano tubes

Graphitic platelets

Nano talc

Meta oxides

Synthetic and natural clays

Bio fibres (flax, hemp…)

Single walled carbon nanotube

RUBBER NANOCOMPOSITES

Polymers comprising particles at least one dimension in the

nanosize range (1-100 nm)

Class of materials that have properties with significant commercial

potential

Attractive features identified with nanocomposites are Efficient reinforcement without loss of ductility and even

improvement in impact strength

Excellent optical and altered electronic properties

Heat Stability

Flame resistance

Improved gas barrier properties

Improved abrasion resistance

Reduced shrinkage and residual stress

Effect of Aspects Ratio- Spherical vs Platy

Aspect ratio 1 10-20 100-200

Viscosity increase Low Low-moderate High

Mechanical

reinforcement

Low Moderate High

Barrier improvement Low Moderate-high High

Dispersibility Moderate-easy Easy Difficult

Structure of layered silicates

Si-tetrahedron

Si-tetrahedron

Mg,Li-Octahedron

1nm

200-

3000nm

High in-plane stiffness

(178 GPa) and strength

High layer aspect ratio

Gallery space 0.96nm

Criteria for Nanocomposites –Structure Influence

Best Properties

8

Typical applications:

• Improving mechanical properties

• Increasing the electrical conductivity

• Increasing thermal conductivity

• Biocide / antibacterial

• UV-absorption

[Gray circles in

the pristine clay scheme

represent the

organomodificant

molecules]

Schematic of

theWAXD

patterns yielded

by different filler

morphologies.

Rubber Nanocomposites, Edited by S.Thomas & R.Stephen

Rubber–Mineral Interface

Lowering the surface energy of the inorganic

silicate

Improvement of the wetting characteristics with the

polymer

Treatment of the silicate surfaces (alkyl

ammonium,..)

Addition of block or graft copolymers as

compatibilizer

In-situ reactive extrusion

Chemical Modification of Clay

Need of chemical modification?

Dispersing layered silicates in a polymer is like trying to mix oil in water

It is for compatibilizing the polymer and the layered silicate

Compatibilizing agents consists of

Hydrophilic function (like polar media

such as water or layered silicates)

Organophilic function (like

organic molecules such as oil

or polymer

Role of compatibilizing agents are similar to detergent

Commonly Used Compatibilizing Agents

Amino acids

Alkylamines

Polyetheramines

Dihydroimidazolines

Silanes

Most widely used are alkylammonium ions- why?

They can easily exchange the inorganic ions situated between the layers

Due to the non-polar nature of their chain, lower the surface energy of the

layered silicate

Reduce the electrostatic interaction between the silicate layers and allow

molecules to diffuse between the layers

Organic Modification and Shift in d-spacing of Clay

WAXs of MMT clays

12ALA- 12-aminolauric acid –

1°alkylammonium

DOA-dioctylamine-2°alkylammonium

TOA- trioctylamine-3°alkylammonium

Cloisite Na+- Natural MMT

Cloisite 30B and Cloisite 20A- Organic treated MMT

14

All loading show intercalated

morphology but the (002) peak

in CIIRN10 is higher than other

loading which indicates an

agglomerated morphology.

These results are confirmed

by the HRTEM images of CIIR

and NR nanocomposites

WAXD pattern of NR/nanoclay and Chlorobutyl nanoclay composites

15

XRD pattern of 50/50 NR/NBR rubber blends with different clay loading

Higher filler loaded samples indicate the presence of intercalated

aggregate structure

Maria, H.J., Lyczko, N., Nzihou, A., Joseph, K., Mathew, C. and Thomas, S., 2014. Applied Clay Science, 87, pp.120-128.

16

2D SAXS images of EVA/clay nanocomposites. (a) 7 wt % Cloisite20A clay loading, C7 sample (b) 7 wt % Cloisite25A

clay loading, D7 sample. (c) azimuthal plot I(u) versus u for C7 (solid line) and D7

2D – SAXS imaging of EVA clay Nanocomposite

Wilson, R., Plivelic, T.S., Aprem, A.S., Ranganathaiagh, C., Kumar, S.A. and Thomas, S., 2012. Journal of applied polymer

science, 123(6), pp.3806-3818

Influence of nanoclay loading on the Storage modulus (G’)

of (a) natural rubber nanocomposites and (b) chlorobutyl

rubber nanocomposites at 160 C.

Rheological behaviour of clay incorporated natural rubber and chlorobutyl

rubber nanocomposites

Zachariah, A.K., Geethamma, V.G., Chandra, A.K., Mohammed, P.K. and Thomas, S., 2014. Rheological behaviour of clay incorporated natural

rubber and chlorobutyl rubber nanocomposites. RSC Advances, 4(101), pp.58047-58058.

17

The effect of amplitude dependence on the dynamic viscoelastic properties

of filled rubbers is referred to as the Payne Effect. (Payne, A. R. J. Polym.

Sci. 1962, 6, 57).There is a decrease in dynamic storage modulus of filled

elastomers with increasing deformation amplitude. (Fletcher and Gent,

1953)

Payne Effect

Payne Effect (Schematic representation)

Kraus (1984) proposed an empirical model based on the agglomeration/deagglomeration kinetics of filler aggregates,assuming a van der waal’s type interaction between the particles

Schematic representation of filled elastomeric network

Payne Effect

Yves Grohens et al Nonlinear Viscoelastic Behavior of Silica-Filled Natural Rubber Nanocomposites

J. Phys. Chem. C 2009, 113, 17997–18002

19

2.2

2.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6G

' (

MP

a )

0.12 4 6 8

12 4 6 8

102

g (%)Liquid-like

Strongly

aggregated

Weakly aggregated

Particles arrangement

20

Comparison of tan δ, hysteresis property and rolling resistance between a

carbon black

and a silica filled rubber for tire application. (A: temperature dependence

of tan δ, B: strain

dependence of G", the Payne effect)

Comparison of hysteresis property and rolling

resistance

Nanocomposites in Tyre industry

MAGIC TRIANGLE OF TYRE

PERFORMANCE

Traction avoid slippage while running on the road,

Abrasion resistance low wear and good durability,

Rolling resistance affects fuel consumption.

Nanofillers enable the best balance of these three parameters.

Cross-linker Particles/polymer

anchoring

Filled Rubber

Polymer chains

Colloidal particles

Schematic representation at low and high filler loading.

NR/Silica nanocomposites

Strain dependence of the storage modulus

(E0-E∞) increases with increase in

silica content

24

1E-3 0.01 0.1 1 10 100

0.4

0.8

1.2

1.6

2.0

2.4

2.8

% Strain

E' (

MP

a)

NR

NRS5

NRS10

NRS15

NRS20

AP Meera, S Said, Y Grohens, S Thomas J. Phys. Chem. C 2009, 113, 17997–18002

1E-3 0.01 0.1 1 10 100

0.04

0.08

0.12

0.16

% Strain

E''

(M

Pa)

NR

NRS5

NRS10

NRS20

Strain dependence of loss modulus

Strain

Rubber chain segments

Silica aggregate

(a)

(b)

Schematic representation of (a) the breakdown of aggregates and desorption of rubber chain

segments from the filler surface in silica filled NR system (b) multiple points of attachments of

rubber chains at the silica surface converting to the single points of attachments on straining.

25

AFM height image of NR filled with 20 phr

nanosilica

AP Meera, S Said, Y Grohens, S Thomas J. Phys. Chem. C 2009, 113, 17997–18002

Effect of temperature on the Payne effect

1E-3 0.01 0.1 1 10 100

0

1

2

3

4

5

E

' x 2

73/T

(MP

a)

% Strain

248 K

263 K

303 K

373 K

NR/Silica composites

The amplitude of the Payne effect decreases dramatically

with temperature 26 AP Meera, S Said, Y Grohens, S Thomas J. Phys. Chem. C 2009, 113, 17997–18002

Effect of Temperature

0.01 0.1 1 10 100

0

1

2

3

4

5

% Strain

E'x

273

/T (

MP

a)

● 248 K ▲263 K ▼303 K 373

K

NR/Silica

composites

The solid lines represent the curve fits according to the model 27

28

Strain dependence of the storage modulus (fitted with the Maier and Göritz model) for a) neat PU, b) PG0.5, c) PG1.5 and d) PG3 at

different temperatures of 298 K, 323 K and 348 K.

Payne effect analysis of polyurethane / Graphene oxide composites

Ponnamma, D., Sadasivuni, K.K., Strankowski, M., Moldenaers, P., Thomas, S. and Grohens, Y., 2013.Rsc Advances, 3(36), pp.16068-16079.

Dynamic Mechanical Characteristics of Ionic Liquid Modified MWCNT -SBR

Composites

Abraham, J.; Thomas, J.; Kalarikkal, N.; George, S. C.; Thomas, S.. J. Phys. Chem. B 2018, 122 (4), 1525–1536 29

Viscoelastic Behavior and Reinforcement Mechanism in Rubber Nanocomposites in the Vicinity of Spherical Nanoparticles , P. Bindu and Sabu

Thomas J. Phys. Chem. B 2013, 117, 12632-12648

.

(a) Schematic of the core-shell morphology of rubber-

nano ZnO nanocomposites. (b) Schematic of the

distribution of spherical nanofiller (nano ZnO) in the

rubber matrix Plot of Cv vs nano ZnO content (wt %).

Rubber-nano Zno Nanocomposites.

30

a

b

SEM images of the (a) 70/30 and (b) 50/50 NR/NBR blend with dispersed and co- continuous morphology.

Morphology – Scanning Electron Microscopy

Result & discussion

50/50 NR/NBR blend with 0 clay

70/30 NR/NBR blend with 0 clay

Dispersed phase of

NBR NBR phase with co-

continous and

dispersed phase

morphology.

31

c)

b) a)

e)

The change in morphology of 50/50

NR/NBR nanocomposites with

increase in nanoclay loading

a),b),c) &d) corresponding to the

blend nanocomposites with 0,2,5 and

10phr clay respectively.

Morphology – Scanning Electron

Microscopy

Result & discussion

e) Schematic showing the change in

morphology of 50/50(0) from cocontnious

into dispersed morphology on adding clay.

The decrease in

phase size with the

addition of

(O1MT) Cloisite

10 A clay

1phr clay 2phr clay

5phr

clay

10 phr clay

D D

D D

32

33

TEM images of Carbon Black distribution in NR /SBR rubber

blend

34

CB distribution in NR /SSBR rubber blends

Henning et.al ,MICROMECHANICS OF POLYMERS 25th Polychar 2017

AFM phase image of 50XNBR-50NR blend with 8 phr of

Cloisite 15A

AFM phase image of 50XNBR-50NR blend (b) AFM-Raman spectra of

NR phase (red colour) and XNBR phase (blue colour) in 50XNBR-50NR

blend

Satyanarayana, M.S., Bhowmick, A.K. and Kumar, K.D., 2016 Polymer, 99, pp.21-43. 35

Raman Imaging of XNBR – NR blends

Air Permeability

-1 0 1 2 3 4 5 6 7 8 9 10 11

0

10

20

30

40

50

60

70

80

90

100

110

GT

RX

10

2(c

c/m

2xdayxatm

)

Amount of filler (phr)

100 CIIR

70 CIIR

Nitrogen Impermeability

Comparison of Nitrogen Permeability of 70Chlorobutyl Rubber /30 Natural Rubber nanocomposites with Chlorobutyl Rubber

Nanocomposites with Nanomer I.44P

Absolute Values of Nitrogen Permeability in

Nanocomposites with Closite 10A

• CIIR neat - 73.73

• NR Neat- 210.67

• CIIR/2.5 Closite 10A- 56.43

• CIIR/5.0 Closite 10A- 61.47

• CIIR/7.5 Closite 10A-91.45

• CIIR/10 Closite 10A-79.21

• 70CIIR/30 NR- 100.43

• 70CIIR/30NR 5Closite10A- 50.23

• 70CIIR/30NR 7.5 Closite 10A- 53.29

• 70CIIR/30NR 10 Closite 10A- 74.78

CNT/NR Nanocomposites

Compo.Stru., 75, 2006, 496

By increasing the amount of CNT, the orientation become more randomize

The storage modulus vs. strain amplitiude for MWCNT-filled NR films

Measured at room temperature

S Bhattacharyyaa, C.Sinturela, O. Bahloula, M.Saboungia,S. Thomas, J. Salvetata , C arbon 4 6 ( 2 0 0 8 ) 1 0 3 7

TEM images of activated CNTs

Resistivity vs. CNT volume fraction, showing

an electrical percolation behavior due to CNT

network formation.

NRL/Carbon Nanotube Composites

(Electrical Conductivity )

S. Thomas et al. Carbon 46 (2008) 1037-1045

Part-I Part-II Part-III Part-IV Conclusions

42

Reinforcement Of Natural Rubber By Networking of Activated

Carbon Nanotubes

Improving reinforcement of natural rubber by networking of activated carbon nanotubes Sanjib Bhattacharyyaa, Christophe

Sinturela…..Sabu Thomasb, Jean-Paul Salvetat Carbon Volume 46, Issue 7, June 2008, Pages 1037–1045 43

http://www.sciencedirect.com/science/article/pii/S0008622308001474

















http://www.sciencedirect.com/science/journal/00086223

http://www.sciencedirect.com/science/journal/00086223/46/7

Stress-strain curves of SBR/ CNT nanocomposites with Stress-strain curves of SBR nanocomposites with various ionic

liquid concentration

Stress-strain relationship

Abraham, J., Xavier, P., Bose, S., George, S.C., Kalarikkal, N. and Thomas, S., 2017. Polymer, 112, pp.102-115.

44

Well-organized interconnected RGO networks throughout the

NR matrix, which played an important role in determining the

properties of composites Effective Interfacial Stress Transfer From

NR Matrix To RGO Sheets Imparted By

Gelatin.The Composites Exhibited An

Excellent Stretchability Without Rapid

Fracture.

RGO nanosheets were wrapped around

NRL particles to form an interconnected

weblike networks.

Dong, B., Wu, S., Zhang, L., & Wu, Y. (2016). Industrial & Engineering Chemistry Research, 55(17), 4919-4929.

Ionic liquid Modified MWCNT SBR Soft Nanocomposites for EMI shielding

Transmission microscopy images of

unmodified and modified

composites(A) T3 IL0 (B) T3 IL1 (C)

TEM image of modified MWCNT

Thomas et al. J. Mater. Chem,,in

Press, RSC Advnces, PCCP

RSC Advances, 2016, PCCP, 2016

(A) Total shielding effectiveness as a function of frequency for composites with different MWCNT loadings

(B) with IL loading (C) Electrical conductivity at 1 KHz and the average SET at different bands vs. concentration

of f-MWCNTs. Thomas et al. J. Mater. Chem,, in Press, RSC Advances, 2016, PCCP, 2016

Nano Sized Biofillers (Agro waste)

Sources of biofillers

Wood

coir

PALF

Banana

Oil Palm

Transmission electron micrographs from a dilute suspension

of hydrolyzed (a) tunicin, (b) wheat straw, (c) cotton, (d)

sugar-beet pulp, (e) squid pen, (f) Riftia tubes, (g) crab shell,

and (h) waxy maize.

Courtesy: Alain Dufresne, ICBC 2005, M.G University, Kottayam

SPM – Acid Hydrolysed fibrils,

Banana fiber

Phase SPMs by Multimode SPM with a Nanoscope IV

controller in tapping mode , Thomas et al. Biomacromolecules

51

SEM

Characterizations nanowhiskers (wood)

I. Cellulose

Macro to Nano

AFM

50 nm

ESEM image of acid treated

PALF fibre

Carbohydrate Polymers 86,

no. 4 (2011): 1790-1798.

The drop in pressure facilitates the increase in the fibrillation process of the PALF fibers whose size ranges in nanometers

Tensile tests performed at room temperature on pure P(S-BuA) rubber

matrix and related cellulose filled composites

Logarithm of the normalized storage shear modulus (log G'T/G'200, where

G'200 corresponds to the experimental value measured at 200 K) vs.

temperature at 1 Hz for tunicin whiskers reinforced poly(S-co-BuA)

rubber nanocomposite films.

Mechanical test

Carbohydrate Polymers 86, no. 4 (2011): 1790-1798

56

Nano Mechanical Analysis

Load – Displacement curves of PDMS – clay composites

Charitidis, C.A. and Koumoulos, E.P., 2012. Plastics, Rubber and Composites, 41(2), pp.88-93.

Application of loads from 1 to 10

000 mn and the recording of

penetration depths as a function of

applied loads with a high load

resolution (1nN) and a high

displacement resolution (0.04 nm).

International and Inter University Centre for Nanoscience and Nanotechnology

Pressure Tactile Sensor:

In a pressure tactile sensor, the pressure applied on the surface of the sensor changes either the electric property (piezoelectricity) or resistance of the material, thereby exhibiting the touch characteristics.

Materials used-

Polymer- poly(isobutylene-co-isoprene) (IIR)

Fillers- RGO and expanded graphite (EG)

Weight %- 5

Method- Solution mixing

Kishor Kumar Sadasivuni et al Materials Letters 96 (2013) 109–112

International and Inter University Centre for Nanoscience and Nanotechnology 58

-0.05 -0.06 -0.07 -0.08 -0.09 -0.10

-0.1

-0.2

-0.3

-0.4

-0.5

Max R

ela

tive R

esis

tan

ce (

AR M

ax)

Force (kN)

IIRRGO

IIREG

Linear Fit

Pressure Sensing

+

-

The resistivity change is explained by construction and destruction of conductive networks. The relative resistance AR of IIR-RGO composite changes linearly with pressure unlike IIR- EG IIR–RGO has potentiality as flexible force sensor.

Kishor Kumar Sadasivuni et al Materials Letters 96 (2013) 109–112


Thomas et a.l Materials Letters 96 (2013) 109–112, Progress in

Polymer Sci, 2015

0 100 200 300 400-0.12

-0.10

-0.08

-0.06

-0.04

-0.02

0.00

Fore

ce

(kN

)

A

R

Time (sec)

AR -0.08

-0.06

-0.04

-0.02

0.00a)

Force (kN) 0 100 200 300 400-0.5

-0.4

-0.3

-0.2

-0.1

0.0

Fo

rce

(k

N)

AR

Time (sec)

AR -0.08

-0.06

-0.04

-0.02

0.00b)

Force (kN)

AR of the samples decrease with pressure at successive double cycles

of measurements (negative pressure coefficient of resistance).

The electrical resistance of RGO filled rubber composite changes

regularly with uniaxial pressure due to the large number of contacts

between RGOs (nano-confinement).

IIR/EG IIR /RGO

Pressure Sensing….


Organic Solvent Sensing

•The solvent sensitivity of NR composite samples were noted from the sudden variation in electrical

conductivity which was due to the breakdown of the filler networks during swelling in different

solvents.

•It is concluded that the polarity induced by RGO addition reduces the interactions between CNTs and

ultimately results in the solvent sensitivity.

Materials used-

Polymer- Natural Rubber (NR)

Fillers-CNT, RGO sheets (thermally reduced at temperatures of 200

and 600 0C )

Weight %- 5

Method- Solution mixing

Deepalekshmi Ponnamma et al Soft Matter, 2013, 10.1039/C3SM51978C


Organic Solvent Sensing….

Deepalekshmi Ponnamma et al Soft Matter, 2013, 10.1039/C3SM51978C

•The experimental set up for the tests reveals solvent injection on the film surface.

•It was found that the synergy between CNTs and RGO exfoliated at 200° C imparts maximum sensitivity to NR in recognizing the usually used aromatic laboratory solvents.

•The electrical resistance is found to vary for the organic solvents used, toluene, p-xylene and benzene.

Experimental setup for solvent sensing in a closed chamber (a) and the electrical

resistance variation with solvents toluene (b) p-xylene (c) and benzene (d) for

composites.


Dual Phase Sensing

Kishor Kumar Sadasivuni et al Material Chemistry and Physics, 10.1016/j.matchemphys.2014.06.055

Materials used-

Polymer- poly(styrene-isoprene-styrene) (SIS)

block copolymer

Fillers-PANI

Weight %- 5- Method- in situ polymerization

in the presence of doping agent

•Here we propose oil sensors made of polyaniline (PANI) filled

SIS composite films

•The changes in resistivity of the samples in presence of both

oil and water media reveal good sensing ability of SIS-PANI

films towards oil in water (dual phase).


Dual Phase Sensing….

•The relative resistance of the SIS-PANI thin film

sensors increases slowly when exposed to oil,

and then reaches towards a constant value with

time.

•The relative resistance of the SIS-PANI sensors

varies upon the exposure to water medium

where the change is drastic and the resistance

value shows a decrease trend different from the

previous case.

•For oil in water medium, the relative resistance

first decreases and then increases.

Kishor Kumar Sadasivuni et al Material Chemistry and Physics, 10.1016/j.matchemphys.2014.06.055

Relative resistances (DR/R0) vs time (min) for SIS-PANI composite

films in different media a) oil b) water and c) oil in water.

CNT@CNC/NR Strain sensor

• CNT@CNC (1/1 wt%)

nanohybrid suspension.

• 1.2, 2.0, 2.8, 3.5 and 4.2

S. Wang et.al Soft Matter, 2016, 12, 845--852


CNC CNT CNT/C

NC

CNT/CN

C-NR

CNT-

NR

Z-Potential SEM

• CNT@CNC/NR percolation

threshold (1.6 vol%)

• 4-fold lower than that of the

CNT/NR (7vol%)

• CNT@CNC/NR-2.8 is 9

orders magnitude of

CNT/NR


Electrical conductivity

No significant effect on aspect ratio of CNC

RGO@CNC/NR Chemical sensor

• 1, 2, 3, 4 and 5 phr of

RGO

RGO RGO/C

NC RGO/C

NC RGO

J. Cao et al. Carbohydrate Polymers 140 (2016)

88–95

• RGO@CNC/NR nanocomposites is

only 0.66 vol %

• RGO /NR 1.7 vol%

Electrical conductivity Tensile Properties

J. Cao et al. Carbohydrate Polymers 140

(2016) 88–95

Responsivity–Time relationship

Exposed to toluene During five immersion drying runs

RGO@CNC/NR RGO/NR

J. Cao et al. Carbohydrate Polymers 140

(2016) 88–95

RGO@CNC/NR2.

08

CONCLUSON MULTIPLE TECHNIQUES

-Rheometery(rotational/capillary)

-Microscopy(OM, SEM, TEM, AFM)

-Spectroscopy(NMR, FTIR, Raman,FS, UV..)

-X-ray-WAX/SAXS

-DMA, TMA, DSC, TGA

-Dielectric measurements

-Mechanical measurements (static and dyamic)

-Zeata potential

-Flammability

-Permeability

-EMI shielding

Acknowledgements

PhD Students/Post Docs

Siby, Deepa, Kishore, Ajesh, Rani, Visak, Jiji, Hanna, Eldhow,

Runcy,Visak,Meera, Bindu, Srinivas

Government Funding

DST, Nanomission (Prof. CNR Rao)

ISRO, CSIR, DBT, AICTE, UGC, DRDO, DIT, TWAS,BRNS

Industrial Funding

Du Pont, USA, General Cables, USA, Surface treat, Czech

MRF Tyres, Apollo Tyres, India

Collaborators

Dr.Jurgen Pionteck, Dresden, Germany

Plivelic, T.S., Italy

Aji P Mathew, University of Stockholm. Sweden

Prof. Paula Mouldnaers. KUL, Belgium

Prof. Yves Grohens, Uni of South Brittany, France

71

72

Thank you for Your Attention

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Nano Group

School of Chemical Sciences

Centre for Nanoscience

“The aim of University education should be to turn out true servants of the people, who would live and die for the country’s freedom” – Mahatma Gandhi

Books Edited

Welcome to

INTERNATIONAL CONFERENCE ON NATURAL POLYMERS

Venue :MAHATMA GANDHI UNIVRSITY CAMPUS.

Kottayam, KERALA,INDIA

Date: December 7-9, 2018

Website: [email protected]

mailto:[email protected]

advances in the characterization of functional rubber .... sabu-nanoscale... · nanosize range...

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