Starch/Polyaniline (PANI) Biopolymer Film

as Ammonia Colorimetric Sensor for

Intelligent Food Packaging
Chia Min Rui
Universiti Kebangsaan Malaysia

Supervisor : Prof. Dr. Ishak Ahmad

Co-supervisor : Assoc. Prof. Dr. Phang Sook Wai

1
Plastic Pollution
• Petroleum-based plastic: result in serious
environmental pollution.
• > 250k tons of plastic pieces accumulated
in the ocean.
Food Wastage
• Annual wastage of edible food
Global : 1.3 billion tons
Malaysia : 1.1 million tons
• Confusing food date labelling
• Vague expiry dates
2
 Problems Solutions Results
• Plastic pollution • Biodegradable plastic • Environmental conservation
• Food wastage • Food freshness indicator • Prevent unnecessary food wastage

✓Biopolymer that is biodegradable, capable to indicate food edibility

✓Starch/polyaniline (PANI) biopolymer
3
• Biodegradable • Antistatic
• Renewable • Food edibility
indicator

Starch PANI
NH3

4
1. To synthesize PANI powder and starch/PANI films.

2. To characterize the resulted PANI and starch/PANI.

3. To apply starch/PANI film as colorimetric sensor to detect ammonia.

4. To study the sensor performance of starch/PANI film

- effect of PANI ratio & Tsurrounding on the sensitivity
- selectivity for starch/PANI sensor towards ammonia detection.
5
Part 1a:PANI Synthesis

Oxidative Polymerization

Yield : 90.80%
6
Part 1b: Starch/PANI Synthesis

Temp : 70℃

Starch Film Starch/PANI Film

7
Starch/PANI synthesis (Different PANI wt%)
Mass of Mass of Mass of Volume of
Film
Starch (g) PANI (g) Glycerol (g) Distilled Water (mL)
Starch 10.00 0.00 5.00 85

Starch/PANI 0.1% 10.00 0.01 5.00 85

Starch/PANI 0.2% 10.00 0.02 5.00 85

Starch/PANI 0.3% 10.00 0.03 5.00 85

Starch/PANI 0.4% 10.00 0.04 5.00 85

Starch/PANI 0.5% 10.00 0.05 5.00 85

8
 Part 2: Characterization

UV-Vis
FT-IR (oxidation state)
(chemical structure)

STA
XRD (TGA&DSC)
(crystallinity)
9
(thermal properties)
Part 3: Application
NH3

𝐵Τ𝐺
𝐶ℎ𝑎nge of colour signal =
𝐵0 Τ𝐺0
10
❖ [NH3]: 200, 400, 600 800, 1000 ppm

1.Starch/PANI with different wt%

• 0.1, 0.2, 0.3, 0.4, 0.5%

2. Temperature
• -18, 4, 30℃

3.Selectivity of the sensor

(Ethanol, Methanol, Toluene, Acetone)

11
Part 2: Characterization
Polaron-bipolaron
polaron → π* (benzenoid)
Quinoid
π → π*
Benzenoid
Absorbance

➢ Confirmed oxidation
250 350 450 550 650 750 850 state of PANI :
Wavelength (nm) emeraldine salt

Figure 1 UV-Vis spectrum of PANI 12

 Glycosidic
%Transmittance

H-O-H C-H
O-H C-H & C-OH

C-O

➢ Confirmed chemical
4000 3500 3000 2500 2000 1500 1000 structure of PANI &
Wavenumber (cm-1)
Starch/PANI 0.4% Starch PANI starch

Figure 2 FT-IR spectra of PANI, starch & starch/PANI 0.4%

13
 Deconvolution : Gaussian-Lorentzian Model
➢ Confirmed incorporation of PANI in starch/PANI
Starch Film Starch/PANI Film
0.08
(a) (b)

0.06

2933 cm-1 0.06 2933 cm-1

2883 cm-1 2883 cm-1
Absorbance

0.04

Absorbance
0.04
2850 cm-1

0.02
0.02

0 -0.01
3000 2950 2900 2850 2800 2750 2700 2975 2925 2875 2825 2775

Wavenumber (cm-1) Wavenumber (cm-1)

Original Spectrum Composite Spectrum Deconvoluted Peaks Original Spectrum Composite Spectrum Deconvoluted Peaks

Figure 3 Deconvolution of the FT-IR spectra of (a) starch & (b) starch/PANI 0.4%
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 300

18.3°
200 16.7° 19.5° 22.1°
14.1°
12.7°
Intensity (arbitrary unit)

100

20.9°
25.7° ➢ Confirmed
0
19.5° 22.4° incorporation of PANI
17.2° 27.2° in starch/PANI
200

14.9°
12.7°
100

0
5 10 15 20 25 30

2θ (Degree)
Starch/PANI 0.4% Starch
Smoothing of Diffractogram
Figure 4 XRD diffractograms of starch & starch/PANI
15 0.4% (Savitsky-Golay filter)
(a) 100 (b)
0.00

-5.00

-10.00

-15.00

80 0.00

-5.00

-10.00

-15.00
Mass Change (%)

0.00

60 -5.00 Starch
-10.00
Starch/PANI 0.1%

DTG (%/min)
-15.00

0.00 Starch/PANI 0.2%

-5.00
40 -10.00 Starch/PANI 0.3%
-15.00

0.00
Starch/PANI 0.4%
-5.00 Starch/PANI 0.5%
-10.00
20 -15.00

0.00

-5.00

-10.00
-15.00
0
30 130 230 330 430 530 630 730
0 200 400 600 800
Temperature (℃) Temperature (℃)

Figure 5 (a) TGA and (b) DTG thermograms of starch & starch/PANI
16
Decomposition Stages of Starch and Starch/PANI Films

Temperature (℃)
Polymer Films
Stage I Stage II Stage III Stage IV

Starch 120.0 NIL 274.2 316.5

Starch /PANI 0.1% 140.1 NIL 292.4 318.7

Starch /PANI 0.2% 122.3 236.7 292.4 319.5 Thermal stability ↑

Starch /PANI 0.3% 128.0 228.8 287.5 319.3

Starch /PANI 0.4% 124.4 211.3 280.4 319.8

Starch /PANI 0.5% 116.5 189.6 277.5 317.8

Moisture loss Glycerol evaporation Decomposition of
starch chains
Decomposition of dopant HCl
17
 Exothermic
Heat Flow (mW/mg)

Heat Flow (mW/mg)

Endothermic

Starch
Starch/PANI 0.1%
Starch/PANI 0.2%
Starch/PANI 0.3%
Starch/PANI 0.4%
Starch/PANI 0.5%

45 65 85 105 125 150 180 210 240 270 300 330 360 390 420 450
Temperature (℃) Temperature (℃)

Figure 6 DSC thermograms of starch & starch/PANI

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Tq, Tm, ∆Hf of Starch and Starch/PANI Films
Polymer Film Tg (℃) Tm (℃) ∆Hf (J/g)
Starch 77.0 277.6 23.8
Starch/PANI 0.1% 77.0 281.3 19.5

decreases
decreases
Starch/PANI 0.2% 77.0 287.5 9.1
Starch/PANI 0.3% 76.3 282.5 6.3
Amorphous
characteristics ↑
Starch/PANI 0.4% 71.3 270.0 4.1
Starch/PANI 0.5% 68.4 262.6 3.2

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Part 3: Application of Polymer Film as Ammonia Sensor
1.Starch/PANI with different wt%:
200 ppm 400 ppm 600 ppm 800 ppm 1000 ppm
2.0 2.0 2.0 2.0 2.0

1.67
1.54 1.58 1.58 1.59
1.50 1.42
1.40 1.43 1.48
1.5 1.5 1.5 1.5 1.45 1.5
1.34 1.37 1.29
1.26 1.33 1.34
1.28 1.24
Normalized Signal

1.22 1.21 1.23

1.18 1.14
1.12
1.00 1.00 1.00 1.00 1.00
1.0 1.0 1.0 1.0 1.0

0.5 0.5 0.5 0.5 0.5

0.0 0.0 0.0 0.0 0.0

PANI wt% PANI wt% PANI wy% PANI wt% PANI wt%

Figure 7 Sensitivity of starch/PANI films at different

20
ammonia concentration
 1.7
y = 0.00037x + 1.30151
R²= 0.93790
y = 0.00040x + 1.16695
R²= 0.93595
y = 0.00040x + 1.15618
R²= 0.92000
Normalized signal

1.5 y = 0.00033x + 1.12266

R²= 0.92076
y = 0.00017x + 1.08909 Starch/PANI 0.1%
R²= 0.92381
Starch/PANI 0.2%
Starch/PANI 0.3%
1.3 Starch/PANI 0.4%
Starch/PANI 0.5%

1.1
0 200 400 600 800 1000
Concentration of ammonia solution (ppm)

Figure 8 Regression lines of the sensitivity of starch/PANI films at different ammonia concentration
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Colour Changes of Starch/PANI Films
after Ammonia Vapour Exposure

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2. Different Tsurrounding:
2.5

30℃ : Troom
2 4℃ : Trefrigerator
1.67 -18℃ : Tfreezer
Normalized Signal

Polymer Film
1.5
1.17 1.15
1.00
1

0.5

Moisture
0
Control 30℃ 4℃ -18℃
Temperature

Figure 9 Sensitivity of starch/PANI at different Tsurrounding Ammonia

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2. Different Tsurrounding:
2.5

30℃ : Troom
2 4℃ : Trefrigerator
1.67 -18℃ : Tfreezer
Normalized Signal

Polymer Film
1.5
1.17 1.15
1.00
1

0.5
Moisture

0
Control 30℃ 4℃ -18℃
Temperature

Figure 9 Sensitivity of starch/PANI at different Tsurrounding Ammonia

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 3. Selectivity of the sensor:

2.5
Hanson Solubility Parameter (HSP) of the substrate
2.0
1.67
Substrat HSP (δ) / MPa1/2 ∆δ with Starch (Dexstran) / MPa1/2
Normalized Signal

Dextran 38.6 0.0

1.5
Glycerol 36.1 2.5
1.00 1.04 1.05 0.95 0.95 Ammonia 33.3 5.0
1.0
Ethanol 26.5 12.1
Methanol 29.6 9.0
0.5
Toluene 18.2 20.4
0.0 Acetone 20.0 18.6
Control Ammonia Ethanol Methanol Toluene Acetone
Volatile Solvent

Figure 10 Sensitivity of starch/PANI towards different volatile solvent

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1. The PANI & starch/PANI films were successfully synthesized.

2. The samples were characterized

- Oxidation state of PANI: emeraldine salt
- Confirm the incorporation of PANI in starch/PANI
- PANI improves the thermal stability of the film

3. Starch/PANI films can be applied as colorimetric ammonia sensor for intelligent food packaging
- Optimum composition : starch/PANI 0.4%
- Best working T: Troom
- Selective towards ammonia

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 Grant:GP-2020-K007256

Prof. Dr. Ishak Ahmad Assoc. Prof. Dr. Phang Sook Wai
Universiti Kebangsaan Malaysia (UKM) 27
Tunku Abdul Rahman University College (TARUC)
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