Bioplastic Cook Book

Bioplastic Cook Book

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Research and Edition by Margaret Dunne

A catalogue of bioplastic recipes.

What is a Bioplastic?

A bioplastic is a biobased polymer derived from a biomass, and it may or may not be biodegradable. The following bioplastic recipes mentioned in this book are all biodegradable. Bioplastics are generally comprised of a biopolymer, a plasticizer and a solvent. Non biodegradable bioplastics include biobased PET and PE.

Apparatus Setup:

pot graduated cylinder electric burner

spoon electric scale

Bioplastic Basics:

-Bioplastics behave like glue and will stick to wood. For casting it is best to pour onto a non porous surface like glass or plastic, especially acrylic. - To make flat sheets of bioplastic, cast the bioplastic mix in a wooden frame, let them dry and then cut them out from the frame. -Bioplastics can be reused. If they are broken into small pieces and heated with water until they dissolve, they can be recasted into a new form. -As bioplastics are thermoplastics with low melting points, they can be deformed by long periods of sun exposure. -Bioplastics are not water resistant. They will deform if they are exposed to rain, or get wet. This also means that they are biodegradable! -To improve water resistance, add wax to the bioplastic solution. -Fibers, minerals, or food waste can be added to bioplastic recipes to create a biocomposite. -Expect bioplastics to shrink as water evaporates during the drying process. Bioplastics with a low percentage of glycerine are likely to shrink more. -If bioplastics are colder than the ambient temperature, when touched, they are still drying. -Casting thick bioplastics may result to mold. Cover them with a textile to keep the bioplastic clean.

_____ grams

This equipment can be used to make any and all of the bioplastic recipes in this book. The recipes were made to be cast into a wooden laser-cut frame, with inner dimensions of 105 mm x 148 mm.

Gelatine Animal Based Bioplastic

Ingredients

Recipe Brittle > Flexible Glycerine (g) 0.0 1.8 3.6 7.2 Water (ml) 60 60 60 60 Gelatine (g) 12 12 12 12

Recipe

1. Add gelatine, water and glycerine into a pot. 2. Cook over medium heat and stir until the gelatine is dissolved and the solution starts to thicken. 3. With a spoon remove the froth, so that the bioplastic will have a glossy, smooth surface. 4. Tape down a wooden frame on a non stick surface and pour in the solution. 5. After 24 hours, remove the frame from the surface and let it hang dry. 6. Once dry, cut out the bioplastic from the frame.

Gelatine is a biopolymer found in pig skin, made from protein polymer chains of amino acid monomers. It dissolves in water, forming a gel substance. Glycerine, a plasticizer creates space between the polymer chains, weakening the intermolecular forces and reducing rigidity. Glycerine has the molecular formula C 3 H 8 O 3 and it occurs naturally in fats/lipids of both animals and plants. Gelatine is combined with glycerine to make more flexible plastics. Bioplastics with more glycerine are more flexible materials, while bioplastics with less glycerine are more brittle.

Agar Agar Plant Based Bioplastic

Ingredients

Recipe Brittle > Flexible Glycerine (g) 0.0 1.4 2.7 5.4 Water (ml) 40 40 40 40 Agar (g) 1.6 1.6 1.6 1.6

Recipe

1. Add agar, water and glycerine into a pot. 2. Cook over medium heat and stir until the solution starts to boil and becomes viscous. 3. With a spoon remove any froth, so that the bioplastic will have a glossy, smooth surface. 4. Tape down a wooden frame on a non stick surface and pour in the solution. 5. After 24 hours, remove the frame from the surface and let it hang dry. 6. Once dry, cut out the bioplastic from the frame.

Agar Agar is a biopolymer made from agarose, (sugar polymer chains). It is found in the cell walls of red algae (Rhodophyta) and has the molecular formula C 14 H 24 O 9 . Agar Agar bioplastics are extremely prone to shrinking. Expect recipes containing 0.0 g to 2.7 g of glycerine to shrink or even crack, depending on drying conditions. However, adding too much glycerine will create a slimy texture. A sample created with 10.8 g of glycerine was oversaturated and never dried completely.

Corn Starch Plant Based Bioplastic

Ingredients

Recipe Brittle > Flexible Glycerine (g) 0 5 10 20 Water (ml) 80 80 80 80 Corn Starch (g) 1.6 1.6 1.6 1.6 Vinegar (ml) 15 15 15 15

Recipe

1. Add corn starch, water, glycerine and vinegar into a pot. 2. Cook over medium heat and stir for 10 minutes. Continue to heat after the solution becomes viscous to evaporate the excess liquid. 3. Tape down a wooden frame onto a non stick surface. Spoon a thin layer of the mixture into the frame (if it is too thick it will crack as it dries). 4. After 24 hours, remove the frame from the surface and let it hang dry. 5. Once dry, cut out the bioplastic from the frame.

Corn Starch, C 27 H 48 O 20 is composed of amylose and amylopectin polymers. Both of these polymers consist of glucose (sugar) monomers. Starch granules will not dissolve on their own in water, but when heated the intermolecular bonds will break, opening up sites for hydrogen bonding. This allows the starch to dissolve in water, creating a viscous fluid. Vinegar, a weak acid, helps to break down the amylopectin, which allows the dried bioplastic to be more flexible.

Gelatine+Spirulina Animal Based Bioplastic with Natural Pigment

Ingredients

Recipe Brittle > Flexible Glycerine (g) 0.0 1.8 3.6 7.2 Water (ml) 50 50 50 50 Gelatine (g) 12 12 12 12 Spirulina (ml) 10 10 10 10 Sugar (g) 4 4 4 4

Recipe

1. Dissolve sugar in 50ml of water on the burner. Once dissolved, remove from heat to cool. 2. Filter water through spirulina powder, until 10 ml of blue spirulina water has been collected. Then combine this with the cooled sugar solution. 4. Add glycerine, gelatine, and 30ml of the sugar/spirulina solution in a pot and cook on a medium heat. After 2 minutes add the remaining 30ml of solution and stir. Quickly pour into a frame on a smooth non stick surface. 5. Let the bioplastic dry according to the previously stated steps.

Spirulina is a type of cyanobacteria (algae). In its dried form it is a green powder. The colour comes from green chlorophyll, which is insoluble in water, and blue phycocyanin, which is soluble in water and therefore can be isolated by filtration. The phycocyanin protein denatures when heated but adding sugar helps to stabilize the colour. Even so, bioplastic mixtures will fade from blue to green to yellow within one minute. The best colour will be achieved if the blue solution is added within 15 seconds of casting the bioplastic.

Gelatine+Clay Animal Based Bioplastic with Red Ochre Clay

Ingredients

Recipe Brittle > Flexible Glycerine (g) 0.0 1.5 3.0 6 Water (ml) 60 60 60 60 Gelatine (g) 12 12 12 12 Clay (g) 5 5 5 5

Recipe

1. Add gelatine, water, glycerine and clay into a pot. 2. Cook over medium heat and stir for 4 minutes until the gelatine is dissolved and the solution thickens. 3. With a spoon remove any froth, so that the bioplastic will have a glossy, smooth surface. 4. Tape down a wooden frame on a non stick surface and pour in the solution. 5. Let the bioplastic dry according to the previously stated steps.

The Red Ochre used in the bioplastic mainly consists of clay and iron oxide, Fe 2 O 3 . Ochre can range from hues of yellow to red to brown, and the red variety comes from the presence of dehydrated iron oxide. On their own, ceramics, such as red ochre, have low toughness and are extremely brittle. Adding red ochre to bioplastic creates a composite material which benefits from the combined properties of both materials. The bioplastic will increase the toughness of the composite and the crystallinity of the ceramic will increase the stiffness of the composite.

Agar Agar+Clay Plant Based Bioplastic with Red Ochre Clay

Corn Starch+Clay Plant Based Bioplastic with Red Ochre Clay

Ingredients

Recipe

Recipe Glycerine (g) 2.7 Water (ml) 40 Agar (g) 1.6 Clay (g) 5

1. Add agar, water, glycerine and clay into a pot. 2. Cook over medium heat and stir until the solution starts to boil and becomes viscous. 3. Tape down a wooden frame on a non stick surface and pour in the solution. 4. Let the bioplastic dry according to the previously stated steps.

Ingredients

Recipe

Recipe Glycerine (g) 5 Water (ml) 130 Corn Starch (g) 15 Vinegar (ml) 15 Clay (g) 5

1. Add corn starch, water, glycerine, vinegar and clay into a pot. 2. Cook over medium heat and stir for 10 minutes. Continue to heat after the solution becomes viscous to evaporate the excess liquid. 3. Tape down a wooden frame onto a non stick surface. Spoon a thin layer of the mixture into the frame (if it is too thick it will crack as it dries). 4. Let the bioplastic dry according to the previously stated steps.

Gelatine Foam Animal Based Bioplastic with Soap

Ingredients

Recipe Brittle > Flexible Glycerine (g) 0 15 30 60 Water (ml) 60 60 60 60 Gelatine (ml) 45 45 45 45 Soap (ml) 6 6 6 6

Recipe

1. Add gelatine, water and glycerine into a pot. 2. Cook over medium heat and stir until the gelatine is dissolved and the solution starts to thicken. 3. Add liquid dish soap and then whisk the solution until it all becomes foam. 4. Tape down a wooden frame on a non stick surface and pour in the foam. 5. Let the bioplastic dry according to the previously stated steps.

Foam is created by trapping air in a solid or liquid, which requires mechanical work and surfactants. Work: By whisking, (doing work) the surface area of the solution increases and air is dispersed within the liquid. Surfactant: Liquid dish soap is a surfactant. It&#;s molecules naturally form bubbles (micelles) with their hydrophobic tails in the center, and their hydrophilic heads on the outside where they are attracted to the water-based bioplastic solution. Surfactants help to stabilize foams because they increase the elasticity of the solution, allowing bubbles to be agitated without rupturing.

Agar Agar Foam Plant Based Bioplastic with Soap

Ingredients

Recipe Glycerine (g) 2.7 Water (ml) 40 Agar (g) 1.6 Soap (ml) 6

Recipe

1. Add agar, water and glycerine into a pot. 2. Cook over medium heat and stir until the solution starts to boil and becomes viscous. 3. Add liquid dish soap and then whisk the solution until it all becomes foam. 4. Tape down a wooden frame on a non stick surface and pour in the foam. 5. Let the bioplastic dry according to the previously stated steps.

*The mixture of corn starch and water is a dilatant, non-Newtonian material that thickens when a force is applied. Foam was not achieved with Corn Starch bioplastic because, even with soap, when the solution was whisked it increased in viscosity and bubbles did not form.

Agar Agar + Burlap Plant Based Bioplastic Textile Composite

Ingredients

Recipe Glycerine (g) 2.7 Water (ml) 40 Agar (g) 1.6 Burlap (mm) 105x148

Recipe

1. Add agar, water and glycerine into a pot. 2. Cook over medium heat and stir until the solution starts to boil and becomes viscous. 3. With a spoon remove the froth. 4. Place the burlap on a non-stick surface, and pour on the bioplastic solution. Place a sheet of non-stick material on top of the burlap and cover with a weight to compress the composite. 5. After 24 hours, remove the weight and the non-stick surfaces. 6. Let the biocomposite hang dry.

The agar + burlap bioplastic composite is more flexible and has better drape than the gelatine + agar bioplastic.

Gelatine + Burlap Animal Based Bioplastic Textile Composite

Ingredients Recipe Glycerine (g) 3.6 Water (ml) 60 Gelatine (g) 12 Burlap (mm) 105x148 Burlap is a plain weave fabric made from yarns spun from coarse jute fibers. Jute is a bast fiber from the plant Corchorus capsularis. Jute is comprised of cellulose and lignin and is known for its high tensile strength and low extensibility. As a plain weave, burlap has poor drape and by combining burlap with bioplastic to create a composite, the drape of this new textile decreases even more. Burlap+bioplastic composite materials have high stability and low extensibility in both the warp and weft direction. These composite materials are characterized by having a high strength to weight ratio. Recipe 1. Add gelatine, water and glycerine into a pot. 2. Cook over medium heat and stir until the gelatine is dissolved and the solution starts to thicken. 3. With a spoon remove the froth. 4. Place the burlap on a non-stick surface, and pour on the bioplastic solution. Place a sheet of non-stick material on top of the burlap and cover with a weight to compress the composite. 5. After 24 hours, remove the weight and the non-stick surfaces. 6. Let the biocomposite hang dry.

Gelatine + Hemp Animal Based Bioplastic Fiber Composite

Agar Agar + Hemp Plant Based Bioplastic Fiber Composite

Ingredients

Recipe Glycerine (g) 3.6 Water (ml) 60 Gelatine (g) 12 Hemp

Hemp fibers are cellulosic bast fibers from the plant Cannabis sativa. They consist mostly of cellulose and lignin. Finer, softer, hemp fibers are taken from the outer layers of thin hemp stalks. Hemp is stronger and more durable than other cellulosic fibers, such as cotton. It is also more absorbent and has anti-microbial properties.

Recipe

1. Add gelatine, water and glycerine into a pot. 2. Cook over medium heat and stir until the gelatine is dissolved and the solution starts to thicken. 3. Pull apart the hemp roving so that the fibers are separated into a non-oriented mass. Submerge the hemp into the bioplastic solution. 4. Remove the hemp and squeeze out as much excess bioplastic solution as possible. Place the saturated hemp on a non-stick surface and then place a sheet of non-stick material on top of the hemp and cover with a weight to compress the composite. 5. After 24 hours, remove the weight and the non-stick surfaces. 6. Let the biocomposite hang dry.

Ingredients

Recipe

Recipe Glycerine (g) 2.7 Water (ml) 40 Agar (g) 1.6 Hemp

1. Add agar, water and glycerine into a pot. 2. Cook over medium heat and stir until the solution starts to boil and becomes viscous. 3. Pull apart the hemp roving so that the fibers are separated into a nonoriented mass. Submerge the hemp into the bioplastic solution. 4. Remove the hemp and squeeze out as much excess bioplastic solution as possible. Place the saturated hemp on a non-stick surface and then place a sheet of non-stick material on top of the hemp and cover with a weight to compress the composite. 5. After 24 hours, remove the weight and the non-stick surfaces. 6. Let the biocomposite hang dry.

Observations

Gelatine Warping

For gelatine bioplastic recipes with 0.0g of glycerine that are left to dry in a frame, they will undergo dry shrinkage warping. Bioplastics dry they shrink, and without a plasticizer such as glycerine they will be under more stress than bioplastics with glycerine, facing similar amounts of strain. To reduce the high levels of stress the bioplastic and its frame assume a warped shape.

The corn starch bioplastic solutions need to be heated for a long period of time for the water to evaporate, which reduces cracks while drying. This creates a highly viscous mixture which cannot be poured into a mold. However, thick uneven surfaces are going to crack when they dry, so the mixture must be spread as thinly as possible, perhaps even spreading the solution on a non-stick surface and then pressing the frame on top.

Observations

Agar Agar Shrinking

The agar bioplastic solution is comprised mostly of water, so when it dries it will shrink as its components are lost to evaporation. In addition to shrinkage, the evaporating water puts a lot of stress on the bioplastic that may lead to cracking. In bioplastics with a low concentration of glycerine, cracking is more likely to occur. It is best to cook the agar solution for longer to boil off more water before leaving the mixture to air dry.

As more heat is required to dissolve agar than gelatine, spirulina was not a successful source of pigment for agar agar bioplastic. The phycocyanin protein denatured within 15 seconds of being added to the hot solution. When all of the phycocyanin sugar water solution was added after the bioplastic solution was removed from heat, the blue colour faded over time while the bioplastic dried. The photos on the left show the colour change over a period of 3 days.

0 hours 24 hours 48 hours

Carbon Footprint

Are bioplastics harmless for the environment?

It is recommended that bioplastics created using these recipes are melted and recast, so that they can be reused endlessly, but if not, make sure that they are disposed of properly. Even though these are plastics, they should not be recycled with petroleum based plastics, or else they will contaminate the recycling stream. If they are disposed of with landfill waste they may take a very long time to biodegrade as they will have limited exposure to oxygen. It is best to compost bioplastics in a hot and aerobic environment.

Agar and corn starch based bioplastics are derived from plants that consume carbon dioxide and release oxygen during their life. But once they are harvested, they are processed and transported around the world. This requires fuel which is most likely sourced from petroleum, a finite resource, and causes carbon dioxide to be emitted into the atmosphere. It is best to make bioplastics from ingredients that are sourced locally to reduce the petroleum used for transport. Furthermore, it is better to have a relationship with the supplier of the materials to understand how they are being processed. Are these plants GMOs? Are they cultivated with fertilizers and pesticides? The idea of plant based plastics seems nice, but the agriculture industry can be extremely damaging to the environment.

The gelatine in gelatine based bioplastics comes from pig collagen. Pig production has a large carbon footprint, as pigs produce greenhouse gases, such as methane and nitrous oxide. They consume processed feed, breathe oxygen, and exhale carbon dioxide. Farming animals takes up land and reduces biodiversity. However, pigs are mainly farmed for pork consumption, so extracting gelatine from pig collagen makes use of waste from the food industry. By using gelatine the negative environmental impact of a pig carcass is decreased, as more of its body will go to use.

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Create your own catalogue of bioplastics by printing out this label with the dimensions 105mm x 88mm:

Bioplastic -

Bioplastic

Biopolymer Plasticizer Additive Solvant Property

Notes :

Material Designer:

I would like to thank Anastasia Pistofidou, my internship mentor, for her guidance and for the commission of this book

&

Clara Davis and Rose Ekwé for their advice on bioplastics.

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Researchers from Michigan State University&#;s top-ranked School of Packaging have developed a way to make a promising, sustainable alternative to petroleum-based plastics more biodegradable.

A team led by Rafael Auras has made a bio-based polymer blend that&#;s compostable in both home and industrial settings. The work is published in the journal ACS Sustainable Chemistry & Engineering.

&#;In the U.S. and globally, there is a large issue with waste and especially plastic waste,&#; said Auras, MSU professor and the Amcor Endowed Chair in Packaging Sustainability.

Less than 10% of plastic waste is recycled in the U.S. That means the bulk of plastic waste ends up as trash or litter, creating economic, environmental and even health concerns.

&#;By developing biodegradable and compostable products, we can divert some of that waste,&#; Auras said. &#;We can reduce the amount that goes into a landfill.&#;

Another bonus is that plastics destined for the compost bin wouldn&#;t need to be cleaned of food contaminants, which is a major obstacle for efficient plastic recycling. Recycling facilities routinely must choose between spending time, water and energy to clean dirty plastic waste or simply throwing it out.

&#;Imagine you had a coffee cup or a microwave tray with tomato sauce,&#; Auras said. &#;You wouldn&#;t need to rinse or wash those, you could just compost.&#;

PLA and a &#;sweet spot&#; for starch

The team worked with what&#;s known as polylactic acid, or PLA, which seems like an obvious choice in many ways. It&#;s been used in packaging for over a decade, and it&#;s derived from plant sugars rather than petroleum.

Pooja Mayekar stands in front of a bioreactor, a clear glass jar filled with composting material. She&#;s in a small, conditioned chamber where several of these reactors line metal shelves, all connected to rubber tubing.

When managed properly, PLA&#;s waste byproducts are all natural: water, carbon dioxide and lactic acid.

Plus, researchers know that PLA can biodegrade in industrial composters. These composters create conditions, such as higher temperatures, that are more conducive to breaking down bioplastics than home composters.

Yet, the idea of making PLA compostable at home seemed impossible to some people.

&#;I remember people laughing at the idea of developing PLA home composting as an option,&#; said Pooja Mayekar, a doctoral student in Auras&#; lab group and the first author of the new report. &#;That&#;s because microbes can&#;t attack and consume PLA normally. It has to be broken down to a point where they can utilize it as food.&#;

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Although industrial compost settings can get PLA to that point, that doesn&#;t mean they do it quickly or entirely.

&#;In fact, many industrial composters still shy away from accepting bioplastics like PLA,&#; Auras said.

In its experiments, supported by the U.S. Department of Agriculture and MSU AgBioResearch, the team showed that PLA can sit around for 20 days before microbes start digesting it in industrial composting conditions.

Two clear glass jars called bioreactors are filled with compost and plastic materials. White plastic tubes are sealed near the base of both jars and both have another tubing connection on their lid. Each jar also bears a sample ID: one reads &#;BLANK BIO 92&#; and the other &#;BLANK BIO 26.&#;

To get rid of that lag time and enable the possibility of home composting, Auras and his team integrated a carbohydrate-derived material called thermoplastic starch into PLA. Among other benefits, the starch gives composting&#;s microbes something they can more easily chow down on while the PLA degrades.

&#;When we talk about the addition of starch, that doesn&#;t mean we just keep dumping starch in the PLA matrix,&#; Mayekar said. &#;This was about trying to find a sweet spot with starch, so the PLA degrades better without compromising its other properties.&#;

Fortunately, postdoctoral researcher Anibal Bher had already been formulating different PLA-thermoplastic starch blends to observe how they preserved the strength, clarity and other desirable features of regular PLA films.

Working with doctoral student Wanwarang Limsukon, Bher and Mayekar could observe how those different films broke down throughout the composting process when carried out at different conditions.

&#;Different materials have different ways of undergoing hydrolysis at the beginning of the process and biodegrading at the end,&#; Limsukon said. &#;We&#;re working on tracking the entire pathway.&#;

The team ran these experiments using systems that Auras and lab members, past and present, largely built from scratch during his 19 years with MSU. The equipment the researchers have access to outside their own lab in the School of Packaging also makes a difference.

&#;Working with Dr. Auras, the School of Packaging, MSU &#; it&#;s great,&#; Bher said. &#;Because, at some point, we want to be making actual products. We are using facilities around campus to make materials and test their properties. MSU offers a lot of resources.&#;

&#;There&#;s a reason why this is one of the best schools for packaging,&#; Mayekar said.

Changing the conversation

Using their expertise and the resources at hand, the researchers have demonstrated that completely compostable bio-based plastic packaging is possible. Yet Auras stressed that this alone won&#;t be enough to guarantee its commercial adoption.

Eight metal shelves &#; four on either side of a long narrow chamber &#; support rows of bioreactors, clear jars filled with composting material. The bioreactors are all connected to rubber tubing.

The challenges there aren&#;t solely technical. They&#;re social and behavioral as well.

&#;There&#;s not going to be one solution to the entire problem of plastic waste management,&#; Mayekar said. &#;What we&#;ve developed is one approach from the packaging side.&#;

Beyond industrial composters&#; skepticism about plastics that Auras mentioned earlier, there&#;s a public misconception that biodegradable and compostable materials can break down relatively quickly anywhere in the environment.

These materials require certain conditions, like those found in an active compost, to decompose in a timely fashion. Outside of those, biodegradable plastics that are disposed of in the environment are still just litter.

&#;If people think we develop something biodegradable so it can be littered, that will make the problem worse,&#; Auras said. &#;The technology we develop is meant to be introduced into active waste-management scenarios.&#;

&#;We need to be conscious of how we manage waste, especially plastics,&#; Bher said. &#;Even at home, you&#;ll need to think about how you&#;re managing that small composting process.&#;

&#;It&#;s really easy to just blame plastic for its problems, but I think we need to change the conversation about how we manage it,&#; Mayekar said.

With its work, the team wants to help educate folks and raise awareness around this issue. And they have reason to believe they can change attitudes. After all, nobody&#;s laughing at the idea of potentially composting PLA at home anymore.

Reference:

Mayekar PC, Limsukon W, Bher A, Auras R. Breaking It Down: How Thermoplastic Starch Enhances Poly(lactic acid) Biodegradation in Compost&#;A Comparative Analysis of Reactive Blends.

ACS Sustainable Chem Eng

. ;11(26):-. doi:

10./acssuschemeng.3c

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