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1. Preparation of Cellulose nanowhiskers and Their
Reinforcement Effect in Polylactide
Present By : Miss.Chanigarn Bureepukdee ID 56402201
Date Room
Advisor : Mr.
Influence of chemical surface modification of cellulose
nanowhisker on thermal, mechanical, and barrier
properties of polylactide based bionanocomposite
Vs
Department of Materials Science and Engineering
Faculty of Engineering and Industrial Technology, Silpakorn University

2. Outline
Introduction
Objectives
Experimental
Results and Discussion
Conclusions

3. Introduction
Polylactide or PLA
Polylactide (PLA) is a biodegradable
thermoplastic polyester that can be
derived from renewable resources such
as starch. It is used in many application,
including biomedical product, food
packaging, and automotive materials.
Advantages
- Good biodegradable properties.
- Easy to process.
Disadvantages
- Poor mechanical properties.
- Low thermal resistant

4. Cellulose nanowhiskers
Introduction
Cellulose nanowhiskers are defined as crystalline rod-like
nanoparticles which are obtained by acid hydrolysis of cellulose fibers

5. Introduction

6. Introduction
The advantage of cellulose nanowhiskers
 Good mechanical properties
 Can modified with chemical group
 High aspect ratio
 Low density
 Low energy consumption

7. To study the preparation of cellulose
nanowhiskers from microcrystalline cellulose.
To investigate the effects of CNW and ICN-
CNW on thermal and mechanical properties of
Polylactide composites.
Objectives

8. Polylactide or PLA
Microcrystalline cellulose (MCC)
Sulfuric acid
N-octadecyl isocyanate
Experimental
Materials

9. Experimental
Preparation of cellulose nanowhiskers
Preparation of
PLA/CNW composites
Chemical modification
of CNW
Preparation of
PLA/CNW-ICN
composites
Characterization

10. Experimental
Preparation of cellulose nanowhiskers
Deionization water Stirred at 0 Sulfuric was added
drop by drop
Continuous stirring at 45
for 1ontin20-130 min
Centrifuged at 3000 rpm
for 10-15 min

11. Experimental
Chemical modification of cellulose nanowhiskers
CNW was dispersed in
dry toluene
Grafted with ICN
10 equivalents according to
the hydroxyl group available
at surface of cellulose
nanoparticles
Washed by
centrifugation/redispersation
for amine unreacted isocyanate
removal.

12. Experimental
Preparation of composites
PLA in chloroform CNW/CNW-ICN in
chloroform
The solution was
homoginized for 3 min at
3000 rpm
Degas and Cast into
Teflon mold.

13. Experimental
Characterization
•Wide angle x-ray diffraction
•TEM
•Rheological properties
•UV-visible spectroscopy
•Thermal analysis
•Mechanical properties
•ATR-FTIR
•X-ray analysis
•Dynamic contact angle
•FE-SEM
•Thermal analysis (DSC)
•Thermo mechanical properties
•Mechanical properties

14. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Figure 1. X-Ray diffraction patterns of MCC and CNW isolated
by acid hydrolysis

15. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Figure 2. TEM images of (a) microcrystalline cellulose, (b) CNW

16. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Figure 2. TEM images of (c)
histograms of length and
diameter for the CNW

17. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Figure 3. (a) Complex viscosity of PLA/CNW composites as a
function of frequency and (b) complex viscosity vs. CNW content
at different frequencies

18. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Figure 4. Storage modulus G'
of PLA/CNW composites as a
function of frequency.
Figure 5. Tan δ curves of PLA/CNW
composites as a function of
frequency.

19. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Figure 6. Relative transmittance curves of PLA/CNW composite films.

20. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Figure 7. TGA thermograms of the PLA/CNW composite films

21. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Figure 9. The second DSC heating scans
of the PLA/CNW composite films.
Table II. Thermal Data for the
PLA/CNW Composite Films
Calculated from DSC 2nd Heating
Scan

22. Results and Discussion
Preparation of Cellulose nanowhiskers and Their Reinforcement Effect in Polylactide
Table III. The Mechanical
Properties of the PLA/CNW
Composite Films
Figure 10. Theoretically predicted values
and the experimental
results for the tensile modulus of the
PLA/CNW composite films

23. Results and Discussion
Influence of chemical surface modification of cellulose nanowhiskers on thermal,
mechanical, and barrier properties of Polylactide based bionanocomposites.
Fig. 1. (a) Birefringence behavior of cellulose nanowhiskers, field emission
scanning electron microscopy of (b) unmodified and (c) modified cellulose
nanowhiskers
a b c

24. Results and Discussion
Influence of chemical surface modification of cellulose nanowhisker on thermal,
mechanical, and barrier properties of polylactide based bionanocomposite.
Fig. 2. (a) Dispersion of (a) unmodified and (b) modified cellulose
nanowhiskers in chloroform, (b) FTIR spectrum for (a) unmodified and
(b) modified cellulose nanowhiskers.

25. Results and Discussion
Influence of chemical surface modification of cellulose nanowhisker on thermal,
mechanical, and barrier properties of polylactide based bionanocomposite.
Fig. 3. Images of (a) neat PLA film compare with those of
bionanocomposites reinforced in 3(a) with CNW at (b) 2.5 wt%,
(c) 7.5 wt% and (d) 15 wt%, and in
3(b) with CNW-ICN at (e) 2.5 wt%, (f) 7.5 wt% and (g) 15 wt%.

26. Results and Discussion
Influence of chemical surface modification of cellulose nanowhisker on thermal,
mechanical, and barrier properties of polylactide based bionanocomposite.
Table 1 Thermal properties of PLA and PLA bionanocomposites obtained from
DSC at the first and second heating scan

27. Results and Discussion
Influence of chemical surface modification of cellulose nanowhisker on thermal,
mechanical, and barrier properties of polylactide based bionanocomposite.
Fig. 5. Second heating run thermograms for (a) neat PLA and PLA
reinforced with CNW at (b) 2.5 wt%, (c) 7.5 wt% and (d) 15 wt%, and CNWICN
at (e) 2.5 wt%, (f) 7.5 wt% and (g) 15 wt%.

28. Results and Discussion
Influence of chemical surface modification of cellulose nanowhisker on thermal,
mechanical, and barrier properties of polylactide based bionanocomposite.
Fig. 6. Comparison of the crystallization half times dertermined by DSC
for different annealing conditions for PLA and bionanocomposite films.
Lines are drawn to guide the eye.

29. Results and Discussion
Influence of chemical surface modification of cellulose nanowhisker on thermal,
mechanical, and barrier properties of polylactide based bionanocomposite.
Table 3 Dynamic mechanical analysis, oxygen permeability and water vapour
transmission rate coefficients for PLA and PLA bionanocomposites

30. Results and Discussion
Influence of chemical surface modification of cellulose nanowhisker on thermal,
mechanical, and barrier properties of polylactide based bionanocomposite.
Fig. 7. Logarithm of the storage tensile modulus (E0) for neat PLA and
bionanocomposites reinforced with (a) CNW and (b) CNW-ICN at 2.5, 7.5
and 15 wt%.

31. Conclusions

32. Thank you for your attention.