Sugarcane bagasse- filled poly (vinyl chloride) composites: An alternative use of sugarcane bagasse Riza Wirawan1 Mohd. Sapuan Salit2 Robiah Yunus2 Khalina Abdan2 1Faculty of Engineering, Universitas Negeri Jakarta, Indonesia 2Faculty of Engineering, Universiti Putra Malaysia. SugarAsia 2012 Bangkok, 16-17 ay 2012

What is poly (vinyl chloride) PVC? Source: Chlorine (56.8%): NaCl Hydrocarbon: ethylene less affected by the cost of petroleum and natural gas than other polymer Atomic mass: Cl=35.5; H=1; C=12

Why (PVC)? Advantages low cost easy to fabricate high durability outstanding chemical resistance to wide range of corrosive fluids offer more strength and rigidity than most of the other thermoplastics Widely used!

Why (PVC)? Price of Thermoplastics (March 2009)* *http://www.plastemart.com

Disadvantages: Safety and environmental issues Vinyl chloride (VC) is reported can make serious health problem When PVC is processed, it produces hydrogen chloride and dioxins => damage the atmosphere The issues have provoked environmental groups to criticize concerning its mass utilization!

PVC Ban PVC? many factories will be closed many labours will loose their job Generates many social problems* *especially in developing countries

An alternative: Mixing PVC with natural fibre, as natural fibre/PVC composites: reduce the utilization of PVC reduce its inconveniences while conserving its advantages

What is sugarcane bagasse (SB)? Chemical contents of bagasse: cellulose (35-40%) natural rubber (20-30%) lignin (15-20%) sucrose (10-15%) Fibre can be found in two parts of bagasse: inner (pith) outer (rind) Vilay V., Mariatti M., Taib R., and Todo M. (2008). Effect of fiber surface treatment and fiber loading on the properties of bagasse fiber–reinforced unsaturated polyester composites. Composites Science and Technology , 68(3-4), 633–638.

Why SB? One of the natural fibres: environmental friendly It is a residue (low cost) the availability of it, as a waste, is high Worldwide production of sugarcane: Over 1.4 billion (109) tonnes per year** Utilization of sugarcane bagasse may contributes to environmental and economic development. *Lee, S.C and Mariatti, M. (2008). The effect of bagasse fibers obtained (from rind and pith component) on the properties of unsaturated polyester composites. Materials Letters. 62, 2253–2256 * * FAO. Food and Agricultural Commodities Production. http://ww.fao.org, retrieved on 23 January 2010.

Potential application Trend of natural fibre composites: thermoset thermoplastics Demand: window/door profiles, fencing/siding/railings, furniture, flooring, automotive interior parts, pallets/crates/boxes, marine components, electrical plugs, wiring ducts. Kline & Company, inc. (2000). Opportunities for Natural Fibers in Plastic Composites, 2000, http://www.marketresearch.com., retrieved on October 14th 2008.

The challenges Pith or Rind? Compatibility? Effect of thermal history & recyclability?

Effect of fibre content to mechanical properties of natural fibre PVC composites Treatment Fibre Content Reinforcement Effect* Source s E Wood Nontreated - + Djidjelli et al. 2002; Ge et al (2004) PMPPIC Kokta et al. 1990; Bamboo Silane Ge et al. 2004 Sisal Maleic Anhydride Djidjelli et al. 2007 Oil Palm Abu Bakar et al. 2005 Acrylic Rice Straw NaOH N/A Kamel 2004 Sugarcane Bagasse Benzoic Acid Zheng et al. 2007 * + represents increasing of the property with the increasing of fibre content - represents decreasing of the property with the increasing of fibre content Abu Bakar, A., A., H., and A.F.M., Y. (2005). Mechanical and thermal properties of oil palm empty fruit bunch-filled unplasticized poly (vinyl chloride) composites. Polymers and Polymer Composites , 13 (6), 607-617. Djidjelli H., Vega J.J.M., Farenc J., Benachour D. (2002). Effect of wood flour content on the thermal, mechanical and dielectric properties of poly(vinyl chloride). Macromolecular Materials and Engineering, 287(9), 611–618. Kamel S. (2004). Preparation and properties of composites made from rice straw and poly (vinyl chloride) (PVC). Polymers for Advanced Technologies , 15(10), 612-616 Kokta B.V., Maldas D., Daneault C., and Beland, P. (1990). Composites of polyvinyl chloride-wood fibers. I. effect of isocyanate as a bonding agent. Polymer-plastics Technology and Engineering, 29 (1-2), 87-118. Zheng Y.-T., Cao D.R., Wang D.S., and Chen, J.-J. (2007). Study on the interface modification of bagasse fibre and the mechanical properties of its composite with PVC. Composites: Part A , 38 (1), 20-25.

Thermal History Recyclability Thermal history affects the morphology of polymer (i.e. degree of crystallinity). In SB/PVC composites? Recyclability One of the thermoplastic’s advantages against thermoset is the recyclability. In SB/PVC composites?

Objectives to investigate the effect of fibre loading and fibre source (pith and rind) on the mechanical properties of SB/PVC composite. to investigate the effect of fibre loading and fibre source (pith and rind) on the thermal properties of SB/PVC composite. to determine the influence of various chemical treatments on the tensile properties of SB/PVC. to examine the influence of thermal history on the tensile properties of SB/PVC composite.

Materials PVC: unplasticised poly (vinyl chloride) compound (PVC) IR045A supplied by Polymer Resources Sdn. Bhd., Kelang, Selangor, Malaysia. SB: residue of the sugarcane milling process gathered from sugarcane juice makers in Malaysia 15

material characterizations Start literature study General Flow Chart specimen preparation fibre preparation composite processing PVC preparation Heat Treatment recycling material characterizations data analysis Conclusion

Pith PVC Rind Pith/PVC Rind/PVC Tensile Density Tensile DMTA 10 20 30 40 10 20 30 40 Tensile Density Tensile DMTA Thickness swelling Impact Water absorption Flexural Density Tensile Density

Single fibre tensile test

Single fibre tensile test: Weibull distribution The cumulative failure probability, s0 is Weibull scale parameter or the characteristic stress value m is Weibull parameter that measures the variability of the fibre strength. Larger value of m means smaller scatter in strength value.

Single fibre tensile test: Weibull distribution The cumulative failure probability, Pi, under a particular strength was approximated by Where n is the number of fibres that failed at or below a certain value of stress. N is the total number of fibres measured Li, Y., Hu, C., and Y. Yu. 2008. Interfacial studies of sisal fiber reinforced high density polyethylene (HDPE) composites. Composites: Part A , 39, 570-578.

Single fibre tensile test: Weibull distribution Failure probability distribution of SBF at certain tensile stress m = 2.6028 and s0 = 187.32 MPa

  Weibull Parameter Value Variability Tensile Strength (Mpa) Pith 52.35 2.56 Rind 187.32 2.60 Young's Modulus (Mpa) 2147.42 4.16 10174.49 2.68 Maximum Strain (%) 3.80 2.79 3.28 4.12

Tensile test of PVC and composites

Impact test of PVC and composites

Flexural test of PVC and composites

Fibre loading & fibre source vs thermal properties Pith PVC Rind Pith/PVC Rind/PVC 10 20 30 40 10 20 30 40 DMTA

DMTA of PVC and composites pith rind

C coefficient the effectiveness of fillers on the modulus of the composites* measured E’ values at 60 and 100 oC were employed as E’G and E’R, respectively Lower value=more effective *L. A. Pothan, Z. Oommen and S. Thomas, Dynamic mechanical analysis of banana fiber reinforced polyester composites, Composites Science and Technology (2) 63 (2003), 283-293 28

DMTA of PVC and composites pith rind

Peak width of loss modulus Volume of interface layer. matrix Interface layer Fibre

Benzoic acid treatment Bagasse Washing (sugar removal) Benzoic acid treatment Alkali treatment PMPPIC treatment Composite processing Benzoic Acid Alkali PMPPIC Washed Untreated

Tensile test of composites after various treatments

SEM a: washed b: unwashed

SEM SEM micrograph of (a) unwashed, (b) untreated sugar-free, (c) benzoic acid treated, (d) alkali treated, and (d) PMPPIC treated SB/PVC composites

Material preparation Melt mixing Hot pressing Quenching Annealing HP-Q HP-A Tempering at 60 oC (30 min) Quenching Annealing T-Q T-A

Tensile strength of heat-treated PVC and composites No effect to the tensile strength of PVC Significant effect to the tensile strength of composite (especially for HP-A)

Tensile modulus of heat-treated PVC and composites No effect to the tensile modulus of PVC Significant effect to tensile modulusof composite (especially for HP-A)

Strain at break of heat-treated PVC and composites Significant effect to the strain at break of PVC No significant effect to strain at break of composite.

Recycling T-Q-R T-A-R HP-A-R HP-Q-R T-Q T-A HP-A HP-Q Melt mixing Hot pressing Quenching

Conclusions Best tensile strength and modulus: 40% rind/PVC. However, its impact strength is lower than that of unfilled PVC. Pith/PVC offers higher thermal stability. Thermal stability of pith/PVC composites increased with the increase of fibre content. Best treatment: no treatment Among all of the studied thermal histories, quenching process offers the highest tensile properties of SB/PVC composites. Cooling of PVC at a lower rate resulted in lower strain at break, while low-rate cooling on SB/PVC composite resulted in lower tensile strength and modulus.

Thank you… rwirawan@unj.ac.id riza.wirawan@gmail.com