Polyaniline with natural latex
- 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)
- 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
- 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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Editor's Notes
- #3: In the last 50 years, There are research and commercialize of dry rubber with PANI giving excellent conductive, some even mentioned improvement in mech prop. But rarely shown the dispersion of PANI with latex. Insulating rubber matrix (EPDM). Conducting elastomer blends based on pani & unsaturated rubber give several potentila applications such as pressure sensor. Blend PANI and NBR coating electrode with a thin film of nbr. Pani/adbs/pani/atbs different surfactant in elastomer both showing conductivity. Double doped pani composite film with abs Electrically conductive fiber. The demand for it is growing rapid industrial needs for sensing, electrostatic discharge, germ free clothing eg pani and poly p phenylene terephthamide (Kevlar) In the last 5 years PANI is dispersed in a synthetic medium (ps-lx)= the study is more on the morphological I never came across a journal or book on dispersion of PANI with lx Inhibition of e.coli,s.aures and C. albicans fungi smaller fungal reductuion The compatibility of dispersion between pani and lx as you know pani is acidic and lx is basic and have different surface charges making them immiscible Even thought I didnnt study the effect of surface charges, ph study for now is adequate to be used as a benchmark for pani based template dispersion in latex The dispersion study of pani-lx is my research gap. Taking note this is still a preliminary study Latex gloves has been around for quite some time. Alarming rate of AIDS and other bodily fluid transfusion diseases gave opportunity for Malaysia to be the main exporter of this product. For surgical procedures, gloves are sometimes subjected to very complicated practices; which sometimes numbers of surgical site infections (SSIs) were reported due to the failure of these gloves to perform as physical barrier (tearing) against the transmission of skin flora from the surgeon’s hand to the surgical site. The same can be said for examination or household gloves but not to the extent of life threatening. The solution that these problems are not by increasing of the gloves thickness; but a smart material with enhanced conductivity which acts as antimicrobial agent, low percolation thresholds and high mechanical properties material to supplement the drawbacks.
- #4: Specific,measurable, attainable,realistic,time bound
- #6: Benzenoid and quinonoid; oxidative chemical synthesis of PANI PANI carries different charges, hence will break the cell walls Advantages of Polyaniline Able to replace metals and semiconductors – conductivity, low density and easy processability Easy to synthesis and high environmental stability Doping is the procvess by which polymer that insulator/semi conductor as synthesized as expected to chain transfer agent (dopant) through electrochemical oxidation. This process will increase the polymer ability to conduct electricity because of the increased conc of charge carriers. Pani undoped state, it’s a poor semiconductor. However once doped it, its conductivity increase. Pani holds a special position amongst conducitn polymers in that its most highly conducitve doped. Protonic acid doping with hcl result in increase in condcutivity
- #8: This the problem when to try to disperse pani into latex This where the novelty come into the pic For surgical, the glove tougher to break, if they break, skin floral goes thtrough perforation and enter the work area With the right conductivity value dispersing pani into latex opens new possibilities in glove applications,paint application, finger cord for electronic applicationIncorporate conductive additives into elastomeric matrix excellent approach of development of special mtrls.
- #10: PV latex and KOH
- #11: In order the poly from ftir to be succesfult ,the peak aniline not see but pani see We just use one percentage content, because we would like to see if this work or not
- #17: PANI FTIR peak is at 1560, 1306 and 1148 cm−1 Selecting the molar conc of pani is crucial to obtain comparable properties. In this table, there two ratio of pani polymerization. The first is 01m,0.3 m the precipitate shown brown precipitate, according to study ratio above than 1 shows favorable quality and yield. Past research shows an equal molar ratio of pani polymeratizon gives best in terms of quality.
- #19: Content element in PANI is controlled, PANI-MCC the amount of C is more because presence of cellulose in template, 0H in cellulose. For PANI-MCC-CuO presence of CuO and increase amount of c and o
- #20: This figure the sem imag es of pani, pani-mcc and pani-mcc-cuo. From the edx earlier we can see that the the content of the pani based templates. The sem images to confirm the presences of mcc and cuo CONTRAST
- #21: As you can see in the ftir,
- #24: From the figure, with addition of cuo by right higher temp resistance compared to plain latex, as for now resistance to thermal degradation of CuO is the best.
- #28: Pani based temaplate (pani,mcc,pani-metal oxide AND HYBRID WS SUCCESFULLY PREPARARED) THE FIRST CONC. THE CONC, FOR MY PROJECT FOR NOW ,ALL THE BASED TEMPLATES HAS BEEN SUCESSFULLY POLY, WHICH SETTLE MY OBJECTIVE NO1
- #30: This a budget allocation for this project