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PHB and PLA Coated Bagasse Paper for Biodegradable Food Packaging
Thara Manangan 1,2* and Sarinya Shawaphun 1,2*

-3- (PHB) ( PLA) (Dip-coating) ATR-IR Spectroscopy Goniometry 8 20 PHB PLA PHB PLA 122.9 99.3
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2 PHB PLA : -3
Abstract In this paper, the possibility of poly-3hydroxybutyrate (PHB) and poly-L-lactide (PLA) in paper coating for food packaging was investigated on baggasse paper, a cheap renewable by-product from sugar industries, using an easy and economical dip coating process. The effects of coating operating parameters such as solvents used, polymer concentrations, dipping period and withdrawal speed were investigated. The dip-coated papers were examined by gravimetric analysis, ATR-IR spectroscopy and goniometry. The results showed that the polymer film weight also increased, as the polymer concentration and dipping period increased,

Lecturer, Department of Industrial Chemistry, Faculty of Applied Science, King Mongkuts University of Technology North Bangkok. Research Center of Nano-Industries and Bio-plastics, King Mongkuts University of Technology North Bangkok.

* Corresponding Author, Tel. 0-2913 2500 Ext. 4821, E-mail: jxudel@yahoo.com

Received 22 December2009; Accepted 23 March 2010

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and then slowly increased at the concentration at 8%w/v and the dipping period at 20 minutes. Solubility test of PHB and PLA with over the shelf solvents suggested that PHB is only be completely soluble in chloroform, dichloromethane and mixture thereof, while PLA is only be completely soluble in chloroform, dichloromethane, ethyl acetate and mixture thereof at RT. Among these solvents and mixtures, chloroform and dichloromethane gave almost the same satisfactory result for PHB coating and ethyl acetate provided optimal result for PLA coating. Also, the bleached baggasse paper showed satisfactory results with this method and provided smooth coated layers with maximum amount of PHB and PLA at 122.9 and 99.3 mg/g of paper, respectively. Furthermore, the coated papers showed better surface properties than the non-coated paper in terms of smoothness, air resistance, water resistance and oil resistance. In addition, the PHB coated paper showed almost the same air resistance as PLA coated paper but slightly lower in water and oil resistance. Keywords: Biodegradable Plastics, poly-3-hydroxy butyrate (PHB), poly-L-lactide (PLA), Paper Coating, Food Packaging 1. Introduction Variety of renewable biomaterials has been studied in order to replace the conventional plastic packaging. Starch-based or cellulose-based materials have been widely used in various packaging industries. Papers have been widely used as packages and containers for food because papers are cheap, biodegradable, renewable, recyclable, light weight, strong and dimensionless [1], [2]. In addition, sugar

industries in Thailand produces 12,000 tons a day and generates bagasse fiber by product about 3,000 tons daily. Besides incineration to obtain energy, bagasse pulps can be made into packaging in Thailand recently. This bagasse paper food packaging has been launched for commercialization over 2,000,000 pieces annually under BiO brand name. However, cost of imported binder used in casting is still expensive making baggasse packages 1.5 times more expensive than the Styrofoam package. We envisioned using polymer coating after product casting process. Since, paper food packaging essentially requires improvement of chemical and mechanical properties of paper food packaging such as durability when contacts with water, oil and heat. Currently, the commodity plastics (e.g. PE and PP) and wax have been widely used as coating materials and still caused environmental problems from undesired properties, non-recyclability and nondegradability [3]. Biodegradable plastics especially poly-3-hydroxybutyrate (PHB) and poly-L-lactide (PLA) can be synthesized from renewable resource and biodegradable, so they are definitely more sustainable and environmental friendly than current coating materials [4]-[6]. These polyester resins can be coated on paper via solution to provide antiwicking and water or oil resistance, while making the container degradable [7], [8]. PLA and PHB coating can enhance the resistance to water and oil, including increase strength of the paper container at the same time [9], [10]. 2. Materials and Methods 2.1 Materials A commercial grade of poly-3-hydroxybutyrate (PHB, [] = 1.4967, Mv = 286 kDa, Tm = 164.15oC)

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was obtained from Tianan Biological Material Co. Ltd. (Ningbo, China) and poly-L-lactide (PLA, [] = 2.1828, M v = 86 kDa, T m = 140.08 o C) was purchased from NatureWorks LLC (MN, USA). Chloroform (analytical grade), dichloromethane (analytical grade), ethyl acetate (analytical grade) were purchased from Sigma Aldrich. Three different bagasse papers: commercial bleached Beermat bagasse paper (160m thick, 490 g/m 2 ), nonbleached Beermat bagasse paper (160m thick, 700 g/m ) and the homemade bagasse paper (165m
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Figure 1 Schematic of dip coating assisted PHB and PLA deposition on paper. 2.4 ATR-FTIR Spectroscopy To monitor the adsorption of PHB and PLA on the bagasse paper surface, a Perkin Elmer spectrum 2000 ATR-FTIR (Attenuated Total ReflectanceFourier Transform Infrared) spectrometer was used. Expected C=O stretching of the polyester was observed and the peak area was integrated to quantify amount of polyester on polymer surface. 2.5 Contact Angle Measurement In order to characterize the surface property, the paper (1cm x 6cm) was first coated with polymer as described above. Contact angle measurement was performed at 30oC by the sessile drop method using a Contact Angle System OCA 15 plus. Five measurements were conducted on different areas of one piece of the coated paper. 2.6 Analysis of Paper Properties The physical properties of biopolymers coated and non-coated bagasse papers were tested such as air resistance and smoothness. The chemical properties of paper were also tested such as water and oil absorption (Cobb test, ISO 535).

thick, 490 g/m , given by Department of Science

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Service, Thailand) were used as substrate materials. 2.2 Dip Coating Process The schematic of the dip coating process is shown in Figure 1. A self developed controller was used in the experiment for the dip coating process. The instrument can move a clamp vertically at constant speed 1.95 mm/s. The paper (1cm x 6 cm) were then immersed into various concentrations of polymer solutions and kept an uncoated area on the top of paper. After soaking paper at various desired dipping period, the paper was then withdrawn from the bath at a withdrawal velocity of 1.95 mm/s. The drying process of the coated paper was done by putting the coated paper in the oven at 80oC for 5 h. 2.3 Film Weight Measurement The paper was weighed and then immersed in polymer solution. After submerged in the polymer solution to specified dipping period, the paper was taken out of the solution, dried in convection oven at 80 C for 5 h, and weighed again. The coated
o

polymer film weight was calculated by the weight difference before and after coating.

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3. Results and Discussion 3.1 Film Weight In order to find the optimal condition for maximum PHB and PLA adsorption on the bagasse paper substrate, some parameters e.g. concentrations of polymers and dipping period that can affect the self-assembly adsorption of polymer on the bagasse paper substrate during dipping step of dip coating process have been studied. The experimental results of film weight versus dipping period of dip coating process for PHB and PLA solutions in chloroform with PHB and PLA concentrations of 4 %w/v as shown in Figure 2 suggested that the film weights of PHB and PLA on the paper primarily increased quickly as the dipping period increased, after that the film weights of both polymers slowly increased after 5 minutes of dipping period. This trend was almost the same for both PHB and PLA solutions. Similarly, in Figure 3, the observation was done at dipping period of 20 minutes using various concentrations of PHB and PLA solutions led to the increase of PHB and PLA film weights on the bagasse paper surface and tended to slowly increase at higher polymer concentration. This concentration effect might be due to the increase in driving force for diffusion, self-assembly adsorption and aggregation with polymer concentration. In addition, PHB tended to adsorb on the paper substrate slightly better than PLA under this condition. 3.2 Carbonyl Peak Area In order to be certain that the weight increment on the paper after adsorption came from polymer adsorption only not from other impurities, carbonyl index or carbonyl peak area on the surface comparing with blank paper were measured using ATR-IR technique. Carbonyl peaks were found in polyester e.g. PHB or PLA but not found in paper substrate or solvent used. Thus, this method is much more reliable than gravimetric analysis to quantify amount of PHB and PLA on the paper surfaces. In Figure 4, the carbonyl peak area of paper substrate without coated PHB or PLA layers was close to zero. The results also indicated the increase of carbonyl peak area corresponded to the increase of Figure 3 Solid PHB and PLA film weight as a function of concentration solution with 20 minutes of dipping time performed on the commercial bleached bagasse paper. Figure 2 Solid PHB and PLA film weight as a function of dipping period with 4%w/v concentration solution performed on the commercial bleached bagasse paper.

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Figure 4 Solid PHB and PLA film carbonyl peak area as a function of dipping time with 4%w/v concentration solution performed on the commercial bleached bagasse paper. Figure 6 Solid PHB and PLA film contact angles as a function of dipping time with 4%w/v concentration solution performed on the commercial bleached bagasse paper. 3.3 Water Contact Angle In order to characterize the hydrophobic property of the surface after coated by PHB or PLA layer, contact angle measurement (goniometry) was used. This technique is involved with measuring the contact angle of liquid drop on the surface. The contact angle of the liquid drop is corresponding to Figure 5 Solid PHB and PLA film carbonyl peak areas as a function of concentration solution with 20 min of dipping time performed on the commercial bleached bagasse paper. dipping period for both PHB and PLA solution similar to the results shown in Figure 2 when measuring film weight. Figure 5 depicted the effect of PHB and PLA concentrations on the polymer adsorption. The increase of the carbonyl peak areas again corresponded to the amount of PHB or PLA on paper substrate. The trends of the plots in both Figure 3 and Figure 5 were almost identical suggesting that weight increment on paper came from polymer adsorption. the polarity of the liquid and the surface. For example, when we use distilled water as a liquid, we might expect the high contact angle if the surface is hydrophobic and the lower contact angle if the surface is more hydrophilic. The contact angle value is the average values that measured many different positions on the surface. Thus, the standard deviations (error bars) of contact angle values are corresponding with the homogeneity on the surface. In Figure 6, the contact angles of papers coated with PHB and PLA were decreased corresponding to the increase of dipping period. The increased amount of hydrophilic polymer on the paper surface caused the contact angles of coated paper became

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Figure 8 Solid PHB and PLA film contact angles as a function of contact time of water Figure 7 Solid PHB and PLA film contact angles as a function of concentration solutions with 20 min of dipping time performed on the commercial bleached bagasse paper. lower and got close to the contact angle of PHB (169.0 0.8 ) and PLA film (1720.5), respectively. The standard deviation of contact angle of coated paper was corresponding with the homogeneity of surface. By increase dipping period, the coated layer became much smoother (the decrease of error bars). This might be due to more polymer molecules cover on the substrate surface, so the surface become smoother and defects become lower. As shown in Figure 7, using higher concentrations of PHB and PLA solutions led to the decrease of the contact angles of paper surfaces. The increase of hydrophilic polymers (PHB and PLA) on the substrates caused the surface became more hydrophilic. In addition, the surface homogeneity became much more improved as shown with the decrease of error bars with the increase of polymer concentrations. 3.4 Water Barrier (Contact Angle) The contact angles of water drop on paper surface were decreased with contact time because of the absorption of water by the paper. As shown in 3.5 Paper Treatment Effect To investigate the effect of substrate treatment on the adsorption of polymer, the 3 different bagasse paper substrates including bleached and nonbleached commercial bagasse papers (Beermat ), as well as our homemade bagasse paper have been used in this study compared with regular drawing paper and non-bleached Kraft paper. However, nonbleached commercial bagasse paper and Kraft paper can not be used to perform the adsorption study because the lignin in the paper was coming out during dipping period and turned the color of polymer solution to be yellow. The results in Figure 9 liquid prepared by using 4%w/v concentration solution and 20 min of dipping time performed on the commercial bleached bagasse papers. Figure 8, the contact angles of paper surface without polymers on it decreased much faster than the surfaces of paper coated with PHB or PLA. Thus, the polymer coated layers would perform the water barrier for paper. In addition, PHB coated paper showed the decrease of water contact angle slower than PLA coated paper, so PHB coated paper provided a better water barrier than PLA coated paper.

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Figure 9 Solid PHB and PLA film weight on different types of paper prepared by using 6%w/v concentration solution and 20 min of dipping time. showed that the commercial bleached bagasse paper (Beermat) gave the optimum result for both PHB and PLA coating and provided smooth coated layers with maximum amount of PHB and PLA at 122.9 and 99.3 mg/g of paper, respectively. 3.6 Solvent Effects From solubility test of PHB and PLA with over the shelf solvents, PHB can only be completely dissolved in chloroform, dichloromethane while PLA can only be completely dissolved in chloroform, dichloromethane, ethyl acetate at room temperature. To investigate the effect of solvents on the adsorption of polymer, the three different solvents including chloroform, dichloromethane and ethyl acetate have been used in this study. As shown in Figure 10, the changing of solvent from chloroform to dichloromethane did not cause the significant effect on the film weight of PHB on the commercial bleached bagasse paper. However, the changing of solvent from chloroform to ethyl acetate caused significant effect on the amount of PLA adsorption onto the paper.

Figure 10 Solid PHB and PLA film weight on different types of solvent prepared by using 8%w/v concentration solution and 20 min of dipping time performed on the commercial bleached bagasse paper.

3.7 Physical Properties of Non-coated and Coated Bagasse Paper Based on the purpose to use PHB and PLA coated bagasse paper for food containers, so we also investigated the physical properties of coated paper by measuring smoothness, air resistance, water and oil absorption (Cobb) comparing with the bare paper. The results were shown in Figure 11. Generally, most coated bagasse papers showed better physical properties than the non-coated paper (Blank). In terms of physical properties e.g. smoothness and air resistance, the coated paper showed much more improvement when compared with blank paper. While water and oil absorption (Cobb) of coated bagasse papers with PHB and PLA showed the decrease of values when compared with blank paper. This suggested that the polymer coated layers increased the water and oil resistance to paper. In addition, the PHB coated paper showed smoothness very close to the PLA coated paper. Also, the PLA coated paper showed slightly higher air, water and oil resistance than PHB coated paper.

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bagasse paper were used. The bleached bagasse paper (Beermat) showed the most satisfactory results with this method and provided smooth coated layers with maximum amount of PHB and PLA at 122.9 and 99.3 mg/g of paper, respectively. Generally, most coated papers showed better surface properties than the non-coated paper in terms of smoothness, air resistance, water resistance and oil Figure 11 Percentage of change in physical properties of PHB and PLA coated on commercial bagasse paper comparing with blank paper (A= smoothness, B= air resistance, C = water absorption (Cobb test), D = oil absorption (Cobb test). 4. Conclusions The dip-coated PHB and PLA papers were analyzed by gravimetry, ATR-IR and goniometry. The results showed that the polymer film weights increased as the polymer concentration and dipping period increased, and then gradually increased after the polymer concentration at 8%w/v and the dipping period at 20 minutes. From solubility test of PHB and PLA with over the shelf solvents, PHB can only be completely dissolved in dichloromethane or chloroform and mixture thereof, while PLA can only be completely dissolved in dichloromethane, chloroform, ethyl acetate and mixture thereof at room temperature. Among these solvents, only chloroform and dichloromethane gave almost the same satisfactory result for PHB coating and ethyl acetate provided optimal result for PLA coating. In this study, various types of paper including the commercial bleached and non-bleached bagasse papers (Beermat), regular drawing paper, nonbleached Kraft paper as well as our homemade References [1] M.J. Kirwan, Paper and paperboard packaging technology. Oxford: Blackwell, 2005. [2] H. Kjellgren, M. Gallstedt, G. Engstrom, and L. Jarnstrom, Barrier and surface properties of chitosan-coated greaseproof paper, Carbohydrate Polymers, vol. 65, pp. 453-460, 2006. [3] Y. Zou, S.J. Hsieh, E. Mehnert, and J. Kokoszka, The study of PET recyclable polymers as paper coatings, Progress in Organic Coatings, vol.60, pp. 127-131, 2007. [4] K. Sudesh, H. Abe & Y. Doi, Synthesis, structure and properties of polyhydroxyalkanoates: biological polyesters, Progress in Polymer Science, vol. 25, pp.15031555, 2000. [5] J. T. P. Derksen, F. P. Cuperus, and P. Kolster, Renewable resources in coatings technology: a review, Progress in Organic Coatings, vol. 5. Acknowledgements The authors would like to thank Department of Science Service (Thailand) for homemade bagasse paper and also National Research Council of Thailand (NRCT) for financial support in this project. resistance.

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27, pp. 45-53, 1996. [6] D.L. Kaplan, Biopolymers from renewable resources, Heidelberg: Springer-Verlag, 1998. [7] D.Z. Bucci, L.B.B. Tavares, and I. Sell, PHB packaging for the storage of food products, Polymer Testing, vol. 24, pp. 564-571, 2005. [8] E. Chiellini, Environmentally compatible food packaging, Cambridge: Woodhead, 2008. [9] S. Butkinaree, T. Jinkarn, and R. Yoksan,

Effects of biodegradable coating on barrier properties of paperboard food packaging, Journal of Metals, Materials and Minerals, vol. 18, pp. 219-222, 2008. [10] D. Erkske, I. Viskere, A. Dzene, V. Tupureina, and L. Savenkova, Biobased polymer composites for films and coatings, Proc. Estonian Acad. Sci. Chem., vol. 55, no. 2, pp. 70-77, 2006.

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