1302 Workshop

STRENGTHENING OF PLA FILMS BY

CHEMICALLY MODIFIED CELLULOSE
MICROFIBRILS

Mohammad Mahbubul Hassan

Food & Bio-based Products Group, AgResearch Limited,

Lincoln, Canterbury.
 Background
• A cellulose microfibril is a very fine fibre-like strand made of cellulose

• Cellulose microfibrils are synthesized at the cell surface by large enzyme

complexes having hexagonal symmetry

• Micro to nanoparticles and micro-whiskers uniformly dispersed in a polymer

matrix and also properly compatibilised to the matrix polymer can increase
tensile strength of the matrix polymer

• Cellulose are hydrophilic and PLA is a hydrophobic thermoplastic polymer

Arrangement of cellulose macro
and microfibrils in a plant
Cellulose fibre
Cellulose macrofibrils
Cellulose microfibrils
 Methodology
• Cellulose microfibrils were modified by reacting with dodecyltriethoxysilane
to make them hydrophobic (CMF-1)

• Cellulose microfibrils were modified by reacting with Sodium p-[(4,6-

dichloro-1,3,5-triazin-2-yl)amino] naphthalene sulphonate (CMF-2) to
improve dispersibility

• They were blended with PLA (Ingeo 2060D) at 1, 2, 3, and 5 weight%

• Thermal and mechanical properties of the PLA/cellulose microfibril

composites were characterised by TGA, DSC and DMTA
 Results

CMF -1

CMF -2

Optical microscopic images of CMF-1 and CM-2

• Microscopic images show that in the case of 100 CMF-1 CMF-2

90
CMF-1, microfibrils are bundled but in the 80

Transmittance (%)
case of CMF-2, microfibrils are fragmented 70
60

• FTIR spectrum of CMF-1 shows no hydroxyl 50

40
peak but the spectrum of CMF-2 shows a 30
large hydroxyl peak 20
10
0
• FTIR spectra shows double peaks at 1020

1158
1335
1512
1689
1866
2043
2220
2397
2574
2751
2928
3105
3282
3459
3636
3813
3990
4167
4344
450
627
804
981
and 1110 cm-1 (CMF-1) for Si-O-Si and a
Wavenumber (cm-1)
peak at 1040 cm-1 (CMF-2) due to sulphonate
groups FTIR spectra of CMF-1 and CMF-2
 Thermal properties
120 120

100 100

Weight loss (%)

Weight loss (%)

80 80
PLA control
60 PLA Control 60 1% CMF-2
1% CMF-1 2% CMF-2
40 40
2% CMF-1 3% CMF-2
20 3% CMF-1 20

0 0

71
43

100
129
159
188
218
247
276
306
335
365
394
423
453
482
512
541
570
43
62
84

275

508
105
126
147
169
190
211
232
254
296
317
339
360
381
402
424
445
466
487
530
551
572
593
Temperature (°C) Temperature (°C)

Thermo-gravimetric curves of PLA containing various weight% of CMF-1and CMF-2

• The addition of both cellulose microfibrils to PLA reduced its thermal stability

• Thermal stability decreased with an increase in weight% of cellulose

microfibrils

• The addition of CMF-1 to PLA had larger effect on its thermal stability
compared to the addition of CMF-2
 Mechanical properties
1.5
Tensile strength (MPa)

Elongation at break
60
50
40 1

(%)
30
20 0.5
10
0 0
0 1 2 3 4 5 0 1 2 3 4 5
Weight% of CMF-1
Weight% of CMF-1
Tensile strength

Elongation at break
60 1.5
(MPa)

40 1

(%)
20
0.5
0
0 1 2 3 0
0 1 2 3
Weight% of CMF-2
Weight% of CMF-2

• The addition of CMF-1 to PLA increased the tensile strength and elongation
at break of the PLA/CMF-1 composites up to the applied 3 weight%, after
which strength and elongation both decreased with an increase in the
weight% of CMF-1

• In the case of CMF-2, the tensile strength of the PLA/CMF-2 composites

decreased and the elongation at break increased with an increase in
weight% of CMF-2
 Water absorption and surface
morphologies
Control 1% CMF1 2% CMF1

• The addition of CMF-1 to PLA 2.5 3% CMF1 5% CMF1

decreased the maximum water 2

Water absorption (%)

absorption capacity of PLA.
1.5

• The water absorption by PLA 1

decreased with an increase in
0.5
CMF-1 weight% up to 3%, after
which the water absorption 0
1 2 3 4 5 6 7
capacity again started to Time (day)

decrease
Control 1% CMF2
• The addition of CMF-2 PLA
3 2% CMF2 3% CMF2
increased the water absorption
capacity of PLA, which 2.5
Water absorption (%)

increased with an increase in 2

weight% of CMF-2. 1.5

1
• CMF-1 agglomerated in the PLA
0.5
matrix but CMF-2 dispersed in
0
the PLA matrix 1 2 3 4 5 6 7
Time (day)
 Conclusion
• The addition of silane modified CMF-1 increased the tensile strength of PLA
and the highest tensile strength was shown by the PLA composite with 3
weight% CMF-1.

• The addition of CMF-2 decreased the mechanical properties of PLA and the
lowest tensile strength was shown by PLA with 3 weight% of CMF-1.

• The addition of both types of CMF showed an increase in elongation at break

but decreased thermal stability.

• Silane modified CMF-1 produced aggregation but dispersed well in the PLA
matrix. CMF-2 also dispersed well in the polymer matrix.

• The hydrophobicised cellulose microfibrils could be used in PLA foams to

improve their mechanical properties.

• The developed composites can be used wherever PLA can be used.

 1302 Workshop

BARRIER COATINGS FOR POTATO

STRACH FOAM PLATES

Mohammad Mahbubul Hassan

Food & Bio-based Products Group, AgResearch Limited,

Lincoln, Canterbury.
Methodology
• Potato starch plates were made by the method developed by Nick Tucker
(PFR)

• Plates were sandwiched between two double layers of PLA by hot press
mould

• Films made from different grades (Ingeo 2060D, 2500HP and (4060D) of
PLA were used

• Films of different thicknesses (20 and 30 µm) were used

• Moulding carried out at 110, 115, 120, 125 and 130°C

Characterisation

• Screening of different grades of PLA films

• Hot water stability was tested by pouring boiling water ion plates for 4
times and each time kept for 5 minutes

• Any dimensional change was visually observed and any stiffness change
of the plate was tested by hand

• Stability in high moisture environment was tested by placing beef and

lamb meat in two separate plates and kept them in a fridge at 4°C for 5
days

• Any dimensional change was visually observed and any stiffness change
was observed by hanging the plates on two supports
Thermal stability

• Uncoated control plate lost its dimensional stability within 5 minutes of

the pouring of boiling water and became soft gel-like

• PLA coated plate shoed excellent stability as no change in dimensional

and stiffness of the plate occurred
Stability at high moisture

• Beef released juice (left) after five days of storing but no change in
dimension and stiffness was observed

• Lamb meat (right) released very small quantity of juice but no change in
dimension and stiffness was observed

• The PLA-coated plates showed excellent moisture barrier properties

 Conclusion
• The addition of silane modified CMF-1 increased the tensile strength of PLA
and the highest tensile strength was shown by the PLA composite with 3
weight% CMF-1.

• The addition of CMF-2 decreased the mechanical properties of PLA and the
lowest tensile strength was shown by PLA with 3 weight% of CMF-1.

• The addition of both types of CMF showed an increase in elongation at break

but decreased thermal stability.

• Silane modified CMF-1 produced aggregation but dispersed well in the PLA
matrix. CMF-2 also dispersed well in the polymer matrix.

• The hydrophobicised cellulose microfibrils could be used in PLA foams to

improve their mechanical properties.