Soumyadip Dutta

19RT60R11
M.Tech ( 1st Sem)
Rubber Technology Centre,
IIT Kharagpur
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 Motivation of Work
 Introduction
 Experimental Section
 Results and Discussion
 Conclusion
 References
 Motivation of the work

To develop ECO- Bio-based rubber

FRIENDLY tyres nanocomposites

To study the
possibility of using Performance of
CNC as both nanocomposites from
reinforcing and renewable sources
crosslinking agent
Introduction
 Cellulose Nano-crystals

 Light weight, renewable source

 Very high strength
 Can be modified easily

 Major applications in packaging,

biomedical sectors
 Large specific
surface area
of nano-fillers
CNT

Layered
Silicates

Rubber
Nanocomposites

Reinforcements
Improved from biobased
Performance renewable
sources

CNC
 Literature Survey
Goodyear used corn-starch derived fillers in partial replacement of carbon black
and silica. ( Kim et al., 2015; Wu et al., 2004)

Nanocelluloses including cellulose nanocrystals or nanofibrils were incorporated

as reinforcing filler in a nonvulcanized rubber matrix. ( Pasquini et al., 2010;
Siqueira et al., 2011; Bendahou et al., 2009)

To improve the compatibility between nanocelluloses and rubbery matrix,

Rosilo et al., modified cellulose nanocrystals (CNCs) surfaces with a
hydrocarbon chain with a double bond at the chain end. A bifunctional dithiol
cross-linker was then used with a UV initiator to create covalent bonds at the
interface between modified CNCs and the polybutadiene (PBD) matrix by
means of a thiol−ene reaction triggered by UV radiation. ( Rosilo et al., 2013;
Hoyle et al., 2010)
Experimental Section
 Preparation of m-CNCs Preparation of NR/m-CNCs

Mercaptoundecanoic acid + acetic m-CNCs suspended

anhydride + glacial acetic acid + sulfuric in toluene
acid in a round bottom flask at room
temperature

M-CNCs
suspensions added
CNC added and kept in oil bath for 3 to NR solution in
days at 40⁰ C toluene

Thiol-modified CNCs were precipitated Casted in

and washed with methanol and finally aluminium dish and
solvent exchanged to toluene cured by UV
irradiation
Characterizations

RT-FTIR FESEM

DMA Tensile Testing

 Results and Discussions
 Previously, mercapto group (SH) has been incorporated into
cellulose derivatives by mercaptoethylation with ethylene
sulphides or by esterification with mercaptoacetic acid.

 Cotton cellulose fibers or fabrics that were surface esterified

with mercaptoacetic acid have been used for the synthesis of
cellulose-metal nanoparticle composites.

 In this study, we have covalently incorporated the cross-

linkable mercapto group on the surface of CNCs by
esterification with 11-mercaptoundecanoic acid.
 Fourier Transform Infrared Spectroscopy
PerkinElmer Spectrum 2000

 Peak for –OH stretching at ~3450 cm-1  Change of adsorbance of =C-H out of plane
 Peak for -CH stretching at ~2895 cm-1 bending at 836 cm-1
 Peak for ester carbonyl group at ~1743 cm-1  NR & NR/CNC reached ~16% conversion
after modification  NR/m-CNCs reached ~46% conversion
 Surface Morphology
 Hitachi S-4800 FE-SEM

 Smooth and homogeneous surface

morphology can be seen in case of
NR/m-CNCs-10 nanocomposite film
(Fig-a) which is similar to the pure NR
(Fig-c).

 For the unmodified CNCs/NR NC

films strong phase separation
aggregation is observed (Fig-b).
 Cross-link Density
 A cross-link density of 0.046
mmol/g observed in pure NR

 For the NR/CNCs

nanocomposites, the cross-link
density increased only slightly
as compared to pure NR sample

 NR/m-CNCs nanocomposites
showed a large increase in
crosslink density

oTests done by Swelling Method . Calculated using Flory-Rehner equations

 Uniaxial Tensile Tests

 Instron 5944 UTM ; strain rate 250mm/min

Tensile strength and modulus increased in NR/CNCs-10 by almost 75% and 73%
 while comparing between NR/CNCs-10 and NR/m-CNCs-10 TS increased from 4.2 to 10.2
MPa, Strain-to-failure increased from 750 to 1210% and Work of fracture ( Toughness) increased
almost by 3 times. The modulus almost remained same , But in NR/m-CNCs slight improvement
was found.
 Dynamic Mechanical Thermal Analysis
Q 800 DMA

• Both composites showed higher modulus

• Tan δ was maximum at -51.7⁰ C for neat NR
than neat NR
• Both composites showed transitions at
• The composites showed Tg at -49⁰ C
higher temperature
 Stress Softening Effect

 The stress values at the end of first two

cycles are higher for NR/CNCs sample
but with increased strain the resulting
stress drops below that for the NR sample

 In contrast, for the NR/m-CNCs sample

the resulting stress constantly gives
higher values than neat NR even at high
strain even after several repeated loading
cycles
Structure of Nano composites

 Surface Brush modified CNC

 Less polar , less hydrophilic
 covalent cross-linking at filler-matrix
interface
 Conclusion
 Demonstrated a novel concept of using biobased cellulose nanocrystals, as
reinforcing rod-like nanoparticles, which also have cross-linking sites for covalent
coupling to the natural rubber elastomer network.

 Surface brush-modified m-CNCs bearing crosslinkable mercapto groups were

successfully prepared by a simple esterification reaction on CNCs with 11-
mercaptoundecanoic acid

 Such nanostructure is responsible for the remarkably improved mechanical

properties of the composites. The NR/m-CNCs nanocomposite with 10 wt % of m-
CNCs showed much higher values of engineering tensile strength (10.2 ± 1.3 MPa),
strain-to-failure (1210 ± 110%), and toughness (4.60 ± 0.57 MJ m−3) compared to
pure NR and nanocomposites reinforced with unmodified CNCs

 We foresee the potential application of modified cellulose nanocrystals bearing

thiols in the tire industry and general elastomeric composites

 The present experiments were designed to prove the effect of thiol-functional

CNCs for covalent cross-linking at the NR/CNCs interface
 References
1. Chandra, R.; Soni, R. K. Recent Developments in Thermally Curable and Photocurable Systems.
Prog. Polym. Sci. 1994, 19, 137−169.
2. Kim, H.-Y.; Park, S. S.; Lim, S.-T. Preparation, Characterization and Utilization of Starch
Nanoparticles. Colloids Surf., B 2015, 126, 607−620.
3. Wu,Y. P.; Ji, M. Q.; Qi, Q.; Wang, Y. Q.; Zhang, L. Q. Preparation, Structure, and Properties of
Starch/Rubber Composites Prepared by Co-Coagulating Rubber Latex and Starch Paste.
Macromol. Rapid Commun. 2004, 25, 565−570.
4. Pasquini, D.; Teixeira, E. D.; Curvelo, A. A. D.; Belgacem, M. N.; Dufresne, A. Extraction of Cellulose
whiskers from Cassava Bagasse and Their Applications as Reinforcing Agent in Natural Rubber. Ind.
Crops Prod. 2010, 32, 486−490.
5. Bendahou, A.; Habibi,Y.; Kaddami, H.; Dufresne, A. Physico-Chemical Characterization of Palm from
Phoenix Dactylifera-L, Preparation of Cellulose Whiskers and Natural Rubber-Based
Nanocomposites. J. Biobased Mater. Bioenergy 2009, 3, 81−90.
6. Rosilo, H.; Kontturi, E.; Seitsonen, J.; Kolehmainen, E.; Ikkala, O. Transition to Reinforced State by
Percolating Domains of Intercalated Brush-Modified Cellulose Nanocrystals and Poly-(Butadiene)
in Cross-Linked Composites Based on Thiol-Ene Click Chemistry. Biomacromolecules 2013, 14,
1547−1554.
7. Pei, A. H.; Malho, J. M.; Ruokolainen, J.; Zhou, Q.; Berglund, L. A. Strong Nanocomposite
Reinforcement Effects in Polyurethane Elastomer with Low Volume Fraction of Cellulose
Nanocrystals. Macromolecules 2011, 44, 4422−4427
8. Harwood, J. A. C.; Mullins, L.; Payne, A. R. Stress Softening in Natural Rubber Vulcanizates. Part II.
Stress Softening Effects in Pure Gum and Filler Loaded Rubbers. J. Appl. Polym. Sci. 1965, 9,
3011−3021