Nathanael Balete, Rachelle Lao, Christian Wong, Raine Go, Jenica Juanitas, Chynna Ramos Science IP Proposal #19

Casein and Eggshells as Components in Agar-Based Bioplastics

CHAPTER I: THE PROBLEM AND ITS SETTING INTRODUCTION: The global annual production of plastic products is about 100 million tons. About 8% of total oil production is consumed for the plastic industry both as raw material and energy source. Most plastic products have a short life cycle of less than one year; therefore, plastic waste constitutes a relatively large part in the total waste weight - about 10% - and 26% by volume. Only 1 percent of plastic is recycled globally each year. (http://www.substech.com and http://edition.cnn.com) Improperly disposed plastic materials are a significant source of environmental pollution, harming life. The plastic sheets or bags do not allow water and air to seep into the earth, thereby reducing the fertility of the soil, depleting underground water and harming animal life. Plastics were reported to have exacerbated the floods by choking drains and gutters. One of the biggest challenges with plastic waste is that it is extremely hard to dispose of and persists in the environment for almost 400 years for they are petroleum-based. Disposal by burning, which according to the claims of plastic manufacturers only releases carbon dioxide and water, actually throws up some of the most poisonous chemicals known to us, like polyvinyl chlorides, polyurethene, polystyrene and acrilonitriles. Also, carbon dioxide and methane produced during plastic burning are greenhouse gases. In addition, even minute amounts of the compounds used as additives in plastic have been linked to reproductive damages like falling sperm counts, increase in testicular cancer cases, and other abnormalities. (http://www.substech.com and http://indiatogether.org/2006/jun/env-plastics.htm) Most of today's plastics and synthetic polymers are produced as by-products from petrochemicals - nonrenewable energy resources such as oil, coal and natural gas. The central problem with plastics from hydrocarbons is that they are not biodegradable because of their long polymer molecules. "Biodegradable" means that a substance can naturally decompose with the aid of microbial organisms and will not persist in the environment beyond a certain time period. The usual range for biodegradability lies between 60-90% decomposition within two to three months in standard composting environments. The polymer molecules of conventional plastics are too large and their underlying chemical bonds too tight to be broken apart by microbes. Bioplastics or organic plastics are a form of plastics derived from renewable biomass sources, such as vegetable oil, corn starch, pea starch, or microbiota, rather than fossil-fuel plastics which are derived from petroleum (http://www.wikipedia.org). Bioplastics could be really good for the environment the manufacturing process produces fewer greenhouse-gas emissions than that for petroleum-based plastics, and these biomaterials don't contain an allegedly hormonedisrupting chemical, bisphenol A (BPA) that some regular plastics do. (http://www.time.com/time/magazine) Biodegradable plastics that are easily decomposed by microorganisms persist for much shorter time in nature, and they may provide viable alternatives. The chemical bonds of biodegradable compounds are easily destroyed by a variety of bacteria over a small period of time that facilitates their decomposition. For example, organic products or produce could be deliberately 1

Nathanael Balete, Rachelle Lao, Christian Wong, Raine Go, Jenica Juanitas, Chynna Ramos Science IP Proposal #19 packaged in biodegradable plastics to ensure decomposition of the product and the package together, when disposed. Agar either by itself or with other biopolymers appears to impart favorable properties to plastic sheets. In plastics containing agar and glycerol, glycerol as a plasticizer is environmentally safe to give flexibility to the plastics and agar will make the effectiveness of the glycerol lasts longer, because the agar seems to slow down the increase in brittleness. Agar films have a much higher tensile strength than starch films, so the more agar in the film, the larger the tensile strength (http://green-plastics.net) The idea of incorporating food wastes such as calcium carbonate from eggshells and casein from spoiled milk will not only help our environment reduce wastes; saves our food crops but could possibly improve the quality of an agar-based plastic in terms of tensile strength. Eggshell contains calcium carbonate (also called whiting) which is the most widely used mineral due to its wide availability, ease of processing to specific particle sizes and it is compatible with a wide range of polymer types thus can improve the mechanical properties of plastic such as tensile strength and elongation. (http://www.imerys-perfmins.com/calciumcarbonate/eu/calcium-carbonate-plastic.htm) Casein is the name for a family of related phosphoprotein proteins (S1, S2, , ). These proteins are commonly found in mammalian milk, making up 80% of the proteins in cow s milk and between 20% and 45% of the proteins in human milk. Casein consists of a fairly high number of proline peptides, which do not interact. There are also no disulfide bridges. As a result, it has relatively little tertiary structure. It is relatively hydrophobic, making it poorly soluble in water. (http://en.wikipedia.org/wiki/Casein) STATEMENT OF THE PROBLEMS: Are agar-based bioplastics with casein or eggshells better than those without casein or eggshells in terms of strength, flexibility, waterproofness, heat resistance, cold resistance, biodegradability in soil, biodegradability in water, and resistance to burning? Are the bioplastics better than petroleum based plastics in the said qualities? HYPOTHESIS: The researchers hypothesized that adding casein or eggshells to the agar-based bioplastic would improve the plastics quality and that their qualities would be better than that of petroleum-based plastics. SIGNIFICANCE OF THE STUDY: The Earth has been facing immense pollution from our garbage and consumption. One of the deadly pollution we are facing is from petroleum-based plastics. With plastic becoming a growing concern, utilizing food wastes in making bioplastics will not only help our local government in their waste disposal problem but will also help saves our mother nature from the harmful effects of the petroleum-based plastics and of the global food crisis.

Nathanael Balete, Rachelle Lao, Christian Wong, Raine Go, Jenica Juanitas, Chynna Ramos Science IP Proposal #19 DEFINITION OF TERMS: > Agar is a transparent gelatinous substance obtained from certain species of red seaweed. > Bioplastics are biodegradable plastics whose components are derived from renewable raw materials. > Biopolymers are polymers that are biodegradable, these may be either renewable (based on agricultural plant or animal products) or synthetic. > Calcium carbonate is a chemical compound with the formula CaCO3. It is a common substance found in rocks in all parts of the world and is the main component of shells of marine organisms, snails, pearls, and eggshells. > Casein is a protein that is found in milk and used independently in many foods as a binding agent. Technically, it is part of a group called phosphoproteins, a collection of proteins bound to something containing phosphoric acid. > Glycerol or glycerin is a simple polyol compound. It is a colorless, odorless, viscous liquid that is widely used in pharmaceutical formulations. CHAPTER II: REVIEW OF RELATED LITERATURE Bioplastics or organic plastics are a form of plastics derived from renewable biomass sources, such as vegetable oil, corn starch, pea starch, or microbiota, rather than fossil-fuel plastics which are derived from petroleum. (http://en.wikipedia.org/wiki/Bioplastic) Bioplastics are environmentally friendly because, compared with traditional plastics, their production results in the emission of less carbon dioxide, which is thought to cause global warming. They are also biodegradable, meaning that the material returns to its natural state when buried in the ground. When ordinary plastics made from petroleum are burned, they release the carbon dioxide contained in the petroleum into the atmosphere, leading to global warming. Bioplastics, however, are made from plants that grow by absorbing carbon dioxide from the atmosphere, so when they are burned, the level of carbon dioxide in the atmosphere does not change. Because petroleum is not used, emissions of carbon dioxide are cut, and a contribution is made to the fight against global warming. In addition, bioplastics are biodegradable. If something made of bioplastics is buried in the ground, microorganisms will break it down into carbon dioxide and water. (http://en.wikipedia.org/wiki/Bioplastic) However, many of the bioplastics are contributing to the global food crisis by taking over large areas of land previously used to grow crops for human consumption. The market for bioplastics, which are made from maize, sugarcane, wheat and other crops, is growing by 20-30% a year. (http://www.guardian.co.uk/environment/waste.pollution) Thus, using alternative sources in making bioplastics are being encouraged nowadays. Agar is a galactose polymer (or agarose) obtained from the cell walls of some species of red algae (Rhodophyta) or seaweed (Sphaerococcus euchema) and species of Gelidium and Gracilaria, chiefly from eastern Asia, Chile and California. Chemically, agar is a polymer made up of subunits of the sugar galactose, with a sugar skeleton consisting of alternating 1,3-linked galactopyranose and 1,4-linked 3,6 anhydro--galactopyranose units; it is a component of the algae's cell walls. Dissolved in hot water and cooled, agar becomes gelatinous; its chief use is as a culture medium for microbiological work. Other uses are as a laxative, a vegetarian gelatin substitute a thickener for soups, in jellies, ice cream and Japanese desserts such as anmitsu, as 3

Nathanael Balete, Rachelle Lao, Christian Wong, Raine Go, Jenica Juanitas, Chynna Ramos Science IP Proposal #19 a clarifying agent in brewing, and for paper sizing fabrics. (http://en.wikipedia.org/wiki/Agar) Algae is not an alternative food crop (like corn) which is edible, so agar-based plastics is a promising source for bioplastics. (http://www.icis.com/Articles/2010/06/21/9368969/algaebased-bioplastics-a-fast-growing-market.html) Calcium carbonate, CaCO3, is found in nature giving hardness and strength to things such as eggshells. Approximately 94% of a dry eggshell is calcium carbonate. If the calcium from the shell is removed, the organic matrix material is left behind. This organic material has calcium binding properties, and its organization during shell formation influences the strength of the shell. The organic material must be deposited so that the size and organization of the crystalline components (mostly calcium carbonate) are ideal, thus leading to a strong shell. The majority of the true shell is composed of long columns of calcium carbonate. There are other zones that are involved in the self-organization giving the eggshell its strength properties. (http://www.sas.upenn.edu/~kushnert/webport/teacheregginquiry.pdf) Calcium carbonate is costeffective functional filler for plastics. Besides reducing formulation costs, calcium carbonate provides opacity and surface gloss. It also improved the tensile strength of the plastics (http://www.specialtyminerals.com/specialty-applications/specialty-markets-forminerals/plastics/gcc-in-plastics/) and its elongation properties. (http://www.imerysperfmins.com) Casein is the principal protein found in cows milk and is responsible for the white, opaque appearance of milk in which it is combined with calcium and phosphorus as clusters of casein molecules called micelles. (http://www.nzic.org.nz/ChemProcesses/dairy/3E.pdf) It consists of a fairly high numbers of proline peptides, which do not interact. There are also no disulfide bridges. As a result, it has relatively little tertiary structure and is relatively hydrophobic. (http://en.wikipedia.org/wiki/Casein) It is a phosphoprotein complex precipitated from milk by acidification. The precipitate produced in this way is insoluble in water, alcohol and other organic solvents, but a colloidal suspension can be created in alkaline conditions. Casein proteins were one of the first plastics. Thin plastic films of casein can be made by adding glycerol or sorbitol as a plasticizer, a substance that lowers the temperature at which a plastic softens, and makes it more pliable. It is hygroscopic, a characteristic which prevented exterior use, though wartime research was reported to have produced a casein adhesive which was waterproof, uniform and reliable. (http://sci-toys.com/ingredients/casein.html) Casein, the protein in milk was used by the Ancient Egyptians as a fixative for pigments in wall paintings. It has also been used as a constituent in various glues but it appears not to have been used as the basis of a solid plastics material until the end of the 19th century. (http://www.plastiquarian.com) CHAPTER III: METHODOLOGY The researchers compared 4 different kinds of plastics: plain agar-based bioplastic, agar-based bioplastic with casein, agar-based bioplastic with eggshells, and petroleum-based plastics. MATERIALS AND COSTS: Agar (powder) Php200.00/500g Glycerol (pure) Php40.00/250mL Milk (spoiled) Php0.00 (waste) 4

Nathanael Balete, Rachelle Lao, Christian Wong, Raine Go, Jenica Juanitas, Chynna Ramos Science IP Proposal #19 Eggshells (powder) Php0.00 (waste) Water Php0.00 (insignificant) PROCESS: The spoiled milk was filtered using cheesecloth and the residue (casein) was washed thoroughly to ensure that no whey was left. The collected eggshells were cleaned and dried, then pulverize into fine powder using a mortar and pestle. In producing plain agar-based bioplastic, the researchers used 20ml of agar, 25 ml of glycerol, and 500 ml of water. The researchers mixed and stirred all of the ingredients together. Then, they heated the mixture to 95 C or until it started to froth. The mixture was then poured into a drying pan and left to cool. After cooling, a gelatinous sheet was formed and it was left to dry until little moisture is left. The same procedure was followed in making the casein bioplastic and the eggshell bioplastic except that 1 tablespoon of casein was added to the casein bioplastic and 1 tablespoon of eggshell powder was added to the eggshell bioplastic. The plain bioplastic, the casein bioplastic, the eggshell bioplastic, and the petroleum-based plastic underwent the following tests: Flexibility Test: The plastics should be flexible enough to be bent without breaking. Strength Test: Marbles were placed on a basket until the strip plastic breaks and the weight was recorded. The plastic was hooked using a piece of metal wire. Waterproof Test: The plastic should not dissolve or weaken immediately when wetted. It also should not let water pass through. Heat Test: The strips of plastic should not melt when submerged into the boiling water for 10 minutes. Freezing Test: The plastic was frozen and the researchers saw if the plastic has become brittle or not. Biodegradability Test (in soil): A plastic sheet was buried in soil and physical changes were observed after one month. Biodegradability Test (in water): This was similar to the Biodegradability Test in land but the plastic would be immersed in 500mL of water. Flammability Test: The plastic should not burn easily when exposed to open flame. CHAPTER IV: REFERENCES http://edition.cnn.com http://green-plastics.net http://www.fao.org/docrep/X5822E/x5822e03.htm http://www.guardian.co.uk/environment/waste.pollution http://www.icis.com/Articles/2010/06/21/9368969/algae-based-bioplastics-a-fast-growingmarket.html) http://www.imerys-perfmins.com/calcium-carbonate/eu/calcium-carbonate-plastic.htm 5

Nathanael Balete, Rachelle Lao, Christian Wong, Raine Go, Jenica Juanitas, Chynna Ramos Science IP Proposal #19 http://www.pharmainfo.net/pharma-student-magazine http://www.sas.upenn.edu/~kushnert/webport/teacheregginquiry.pdf http://www.substech.com http://www.vam.ac.uk/content/journals/conservation-journal/issue-21/milk-and-modernismconservation-of-a-smokers-cabinet-designed-by-charles-rennie-mackintosh/ http://www.wikipedia.com