An introductory research on the capabilities of PANI in NR latex article

1. PRELIMINARY FINDINGS IN PREPARATION OF DOPED
POLYANILINE AS FILLER FOR VULCANIZED LATEX
ARTICLE
F. AMMAR, S. MANROSHAN, A.K. NOR, A.Y. AHMAD NAIM, A.H. HAMIDAH, F. SYIMIR, M.Y. HARIS, A. DULAIMI, Z.
MUZAFAR*

2. PROBLEM STATEMENT
What actually is the
real issue?
• Most studies in the last 50 years= Application of PANI
+ dry rubber, PANI + plastics (applications) (Constantino,2003;
Constantino,2005; Mahmod,2015)
• PANI being disperse in synthetic latex medium (PANI-
PS Latex) (Taghipora,2013; Kim,2009; Jingyuan 2008)
• Gloves- bacterial and contaminant migration into work
areas (Vesna,2014; Pandiselvi,2015)
Difficulties to
investigate
• Compatibility of dispersion
• - PANI and Pre-vulcanized latex (PVL) is not
homogeneous and different surface charges
• - Different types of templates produce PANI better
mechanical or conductivity (Langkammer,2015; Mahmod 2015)

3. OBJECTIVES (SMART CONCEPT)
■ To prepare different types of PANI (undoped and doped) through polymerization
technique.
■ To disperse PANI in latex cast film successfully.
■ To evaluate the mechanical, morphological properties and conductivity of the
produced modified cast film
■ To investigate the conductivity of the produced PANI.
■ To evaluate the antimicrobial properties of PVL-PANI films (yet to be done)

4. LITERATURE REVIEW

5. • PANI is known a conductive polymer
with ease of synthesis and good
electrical conductivity.
• Oxidative chemical synthesis/
Emulsion Polymerization
• Benzenoid and quinoid ring
(Majhi & Maji, 2015)
• Polyaniline (PANI) is a conducting
polymer of the semi-flexible rod
polymer family.
• PANI is an excellent dispersing agent,
is expected to drastically modify the
electrical, optical and microscopic
properties.
• Aniline is a monomer, needs to be
polymerize.
(Vikash, 2018)
Figure 1: Polyaniline structure
Metal Oxides
(Copper Oxide &
Zinc Oxide)
Microcrystalline
Cellulose
(Samad, 2018)

6. The synthesis of doped PANI
PANI synthesis Highlights Decision
• -PANI-ZnO improved capacitance
due to surface effects (Mostafei &
Ashkan,2012)
• -PANI easy synthesis combined
with strong antimicrobial
properties of Cu0 nanoparticles
(Una et al, 2018)
• -Cellulose aids the interaction of
PANI and improves the mechanical
properties (Mahmood & Azarian, 2015; Silva
et al,2014; Avelar et al, 2015)
• Study of PANI with dry rubber
(Constantino et al,2003; MH Azarian & Kamil
Mahmood,2015)
• Uses ZnO as a dopant for
electric conductivity
• Uses CuO for antimicrobial
properties and conductivity
• Microcrystalline cellulose used
in study
• Priority on establishing
homogeneity between latex
and PANI

7. Novelty of Study
• Study of the surface charges effect
• Modify the surface charges to be disperse properly
• Usage surfactant, pH value to get the best dispersion
capability
• Outcome
• Expanding conductive Doped PANI into wide
applications
• New possibilities in glove applications, paint
application, finger cord for electronic application

8. METHODOLOGY

9. MATERIALS INVOLVED
TYPE OF
MATERIALS
INVOLVED
• Main Ingredients for udoped and doped PANI
• - Aniline (Bendosen)
• - Pre-Vulcanized latex (PVL) (LGM)
• -Sodium dodecyl sulfate (SDS) (R&M Chemicals)
• -Ammonium Persulphate (APS) (R&M Chemicals)
• -Hydrochloric acid (HCl)
• - Microcrystalline cellulose (MMC) (R&M Chemicals)
• - MetalOxides (Zinc Oxide and Copper Oxide) (R&M
Chemicals)
• Dispersion of PANI- PVL
• - PV Latex
• - Potassium Hydroxide (KOH)

10. METHDOLOG
Y
Distillation of Aniline
Preparation of PANI Templates
 PANI
 PANI-MCC
 PANI-ZnO
 PANI-CuO
 PANI-MCC-ZnO
 PANI-MCC-CuO
Casting of Templates into Latex
 PVL-PANI
 PVL-PANI-MCC
 PVL-PANI-ZnO
 PVL-PANI-CuO
 PVL-PANI-MCC-ZnO
 PVL-PANI-MCC-CuO
Result analysis
Polymerization of PANI
(Molar ratio of Aniline:APS)
Analytical Test
 Fourier Transform Infrared
(FTIR)
Analytical Test
 Fourier Transform Infrared
(FTIR)
Morphological Analysis
 Scanning Electron
Microscopy (SEM)
Thermal Test
 Thermogravimetric
Analysis (TGA)
Mechanical Test
 Tensile Testing
Electrical Conductivity Test
 Atomic Force Microscopy
(AFM)
Objective 1&3
Objective 2&4
+ antimicrobial tests

11. Polymerization of PANI (Molar concentration)
Aniline ratio 0.1M + APS 0.3M
Brown PANI precipitate
Polymerization of PANI (adding HCl)
PANI molar ratio (0.1M:0.3M)
Aniline ratio 0.2M + APS 0.2M
Dark green PANI precipitate
Polymerization of PANI (adding HCl)
PANI molar ratio
(0.2M:0.2M)

12. Doped PANIs Preparation Method
Table 1.: Preparation of undoped and doped PANIs
Polymerization of
undoped PANI
• 5mL 0.2M aniline mixed with 4g
SDS, 6mL 0.2M APS in 200mL
1M HCl
• Mixture stirred at 800 rpm and
kept at 0°C for 5 hours
Polymerization of
doped PANI
(ZnO/CuO/Cellulose)
• 5mL 0.2M aniline mixed with 4g
SDS, 6mL 0.2M APS & 4g of metal
oxides or 4g cellulose in 200mL 1M
HCl
• Mixture stirred at 800 rpm and kept
at 0°C for 5 hours
Drying of
undoped and
doped PANI
• PANI samples are filtered and
washed with distilled water
and ethanol 3 times
• Samples are dried at 70°C for
24 hours

13. Casting of PANI fillers with PVL
PANI and PVL is prepared
Dispersion of PANI in PVL
before drying
Mixing using homogenizer
Table 2. PV latex-PANI mixing formulation

14. RESULTS & DISCUSSION

15. RESULTS & DISCUSSION
■ Findings are divided into 5 stages
– Determination of suitable molar concentration for PANI polymerization
– Morphological analysis on Doped PANI
– Tensile properties of PANI-PVL films
– Visual inspection of PANI-PVL films
– Electrical Conductivity of PANI-PVL films

16. Determination of suitable molar
concentration for PANI
PANI ratio (Aniline : APS) Sample
0.1M : 0.3M
0.2M : 0.2M
Formation of
PANI

17. Polymerization of Doped PANIs

18. Energy Dispersive X-Ray Analyzer(EDX)
Figure 4.1: PANI-template
Figure 4.3: PANI-MCC-CuO-template
Figure 4.2: PANI-MCC template
Element Wt% Wt%
Sigma
Atomic %
C 57.11 0.69 67.68
N 8.02 0.64 8.15
O 19.33 0.45 17.20
Na 0.40 0.08 0.25
S 15.14 0.33 6.72
Total: 100.00 100.00
Element Wt% Wt%
Sigma
Atomic %
C 52.34 0.67 62.85
N 2.29 0.55 2.35
O 33.47 0.56 30.17
S 7.75 0.26 3.49
Cl 1.13 0.15 0.46
Cu 3.02 0.28 0.69
Total: 100.00 100.00
Element Wt% Wt%
Sigma
Atomic %
C 57.41 0.60 66.43
N 3.12 0.55 3.10
O 30.57 0.48 26.55
Na 0.40 0.08 0.24
S 8.49 0.24 3.68
Total: 100.00 100.00

19. SEM OUTLOOK ON PANI
Conclusion
• Presence of MCC
encapsulated in PANI
• Presence of MCC and
CuO in PANI template
Pure PANI
MCC in PANI surface
Presence of CuO in
PANI-MCC

20. CHEMICAL BONDING FORMATION VIA FTIR FOR
DOPED PANIs
Conclusion
• The first region between 1650-1500 cm-1, shows the C=N bond form
for quinoid and benzenoid. PANI shows similar trend in reading, the
presence is there.
C=N C-NOH C-N C-CN-H

21. TENSILE PROPERTIES FOR PVL-PANI
films(MCC,ZnO,CuO, MCC-ZnO,MCC-CuO)
15
25
35
45
Tensile Strength of PANI-PVL based latex articles
0
1
2
3
M100 of PANI-PVL based latex articles
4000
5000
6000
7000
Elongation at break(%) of PANI-PVL based latex
articles
Conclusion
• Addition of PANI increases the tensile
properties of latex
• PANI-ZnO gives the best overall tensile
properties

22. IMPROVEMENT OF LATEX ARTICLE WITH ADDITION
OF PANI FILLERS
PANI fillers addition in PVL
latex increase
PANI fillers addition in PVL
latex increase
PANI fillers addition in PVL
latex increase

23. THERMAL ANALYSIS FINDINGS
Conclusion:
• Effect of addition of CuO, ZnO and MCC in doped PANI increases the thermal resistance compared to PVL film
alone.
PANI based templates Inflection point (oC) Residue content (%)
PV-Latex 388.16 3.51
PANI-PVL 391.72 6.19
PANI-ZnO-PVL 391.94 2.15
PANI-CuO-PVL 390.27 18.79
PANI-MCC-PVL 393.98 19.03
PANI-ZnO-MCC-PVL 391.86 3.82
PANI-CuO-MCC-PVL 389.22 3.41

24. Visual Inspection of PVL-PANI films from manual
mixing to using KOH with homogenizer
• Agglomeration
• Large particle size
• pH 3
• Less agglomeration(-
grinding with no KOH)
• Good dispersion particle
size is large
• pH 3
• No agglomeration (-Effect
of grinding with KOH)
• Good dispersion is
achieved
• pH 9

25. Predicted Electrical Conductivity of PVL-
PANI films (Base from current analysis and
trend)
Conclusion
• PVL-PANI and PVL-doped PANI will
show improvement on current flow
based from previous studies (Mostafei &
Ashkan,2012)
Samples Electrical
Conductivity (pA)
Electrical
Conductivity
(pA) with PVL
film
PANI (0.3:0.1) 1.98 -5.33
PANI (Equal Molar) 8.73 2.78
PVL -7.23 -
PANI-ZnO 9.77 4.90
PANI-CuO 9.17 3.23
PANI-MCC 8.67 0.80
PANI-MCC-ZnO 9.72 3.82
PANI-MMC-CuO 9.13 4.42
Table 3.0: Predicted electrical conductivity of PVL-PANI films

26. Overall Properties
Conclusion:
• PANI-PVL, shows good mech prop, thermal prop and better electrical properties
• PANI-ZnO-PVL gives better props for PVL-doped PANI with outstanding properties
Table 2.0: Comparison of overall mechanical properties
PANI based
template
Mechanical Properties Thermal Properties Electrical Properties
TS(MPa) M100 EB(%) Inflection Point (oC) ResidueContent (%) Conductivity (pA)
PVL 17.389 1.34 4731.68 388.16 3.51 -7.23
PANI-PVL 44.55 2.03 4551.68 391.72 6.19 2.78
PANI-ZNO -PVL 42.16 1.94 6720.71 391.94 2.15 4.90
PANI-CUO-PVL 43.16 2.28 6201.80 390.27 18.79 3.23
PANI-MCC-PVL 26.31 1.19 4851.68 393.98 19.03 0.80
PANI-CuO-MCC-PVL 28.93 1.32 5901.15 389.22 3.41 4.42
PANI-ZnO-MCC-
PVL
37.71 1.49 5961.82 391.86 3.82 3.82

27. PANI, PANI-MCC, PANI-ZnO, PANI-
CuO, PANI-MCC-ZnO hybrid and PANI-
MCC-CuO hybrid templates shows an
increase in mechanical properties and
conductivty
CONCLUSION
Reducing the pH of PANI and balance
the surface charges to improve
dispersion
PVL-PANI,PVL-PANI-CuO & PVL-
PANI-MCC-CuO content too low to
show any conductivity
PANI, PANI-MCC, PANI-ZnO, PANI-
CuO, PANI-MCC-ZnO hybrid and
PANI-MCC-CuO hybrid templates
have been successfully prepared
CONCLUSION
Objective 2: To disperse
PANI into PVL successfully.
(DONE)
Objective 1: To prepare
different types of PANI
based templates through
polymerization technique.
(DONE)
Objective 4: To investigate
the conductivity of the
produced PANI based
templates(ON-GOING)
Objective 3: To evaluate the
mechanical, morphological,
and antimicrobial
properties of the produced
modified cast film (DONE)

28. RECOMMENDATIONS
■ RECOMMENDATIONS
– To use different percentage of surfactants, MCC and metal oxides to
produce an optimum doped PANI for conductivity and antimicrobial studies.

29. Cost comparison
No. Materials / Chemicals Quantity Price (RM)
1. Polyaniline 1L 770.00
2. Ammonium persulphate 1kg 46.00
3. Pre-vulcanized latex 1 kg 28.80
4. Microcrystalline cellulose 1 kg 268.00
5. Zinc Oxide 500g 53.00
6. Copper Oxide 500g 84.00
Total (RM) 1249.80
Using 0.0005% per 100 glove = RM 0.63 per 100
glove

30. Acknowledgement
This project is performed via financial assistance by Govt grant.
Author would like to convey appreciation to Universiti Kuala
Lumpur and Malaysian Rubber Board staffs for the help in both
laboratory assistance and materials.

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