Bioplastic

Bioplastics are plastic materials produced from renewable biomass sources, such as vegetable fats and oils, corn starch, straw, woodchips, sawdust, recycled food waste, etc. Bioplastic can be made from agricultural by-products and also from used plastics (i.e. plastic bottles and other containers) by using microorganisms. Bioplastics are usually derived from sugar derivatives, including starch, cellulose, and lactic acid. Common plastics, such as fossil-fuel plastics (also called petrobased polymers) are derived from petroleum or natural gas.

As of 2014, bioplastics represented approximately 0.2% of the global polymer market (300 million tons).Although bioplastics are not commercially significant, research continues on this topic.

Biodegradable plastic utensils
Packaging peanuts made from bioplastics (thermoplastic starch)
Plastics packaging made from bioplastics and other biodegradable plastics


In addition to being decoupled from the petrochemical industry, bioplastics are attractive because they are biodegradable. Not all bioplastics are biodegradable nor biodegrade more readily than commodity fossil-fuel derived plastics.

Proposed applications

Flower wrapping made of PLA-blend bio-flex

Bioplastics are used for disposable items, such as packaging, crockery, cutlery, pots, bowls, and straws. Few commercial applications exist for bioplastics. Cost and performance remain problematic. Typical is the example of Italy, where biodegradable plastic bags and shoppers are compulsory since 2011 with the introduction of a specific law. Beyond structural materials, electroactive bioplastics are being developed that promise to carry electric current.

Biopolymers are available as coatings for paper rather than the more common petrochemical coatings.

Bioplastics called drop-in bioplastics are chemically identical to their fossil-fuel counterpart but made from renewable resources. Examples include bio-PE, bio-PET, bio-propylene, bio-PP, and biobased nylons. Drop-in bioplastics are easy to implement technically, as existing infrastructure can be used. A dedicated bio-based pathway allows to produce products that can not be obtained through traditional chemical reactions and can create products which have unique and superior properties, compared to fossil-based alternatives.

Types

Starch-based plastics

Thermoplastic starch represents the most widely used bioplastic, constituting about 50 percent of the bioplastics market. Simple starch bioplastic film can be made at home by gelatinizing starch and solution casting. Pure starch is able to absorb humidity, and is thus a suitable material for the production of drug capsules by the pharmaceutical sector. However, pure starch-based bioplastic is brittle. Plasticizer such as glycerol, glycol, and sorbitol and can also be added so that the starch can also be processed thermo-plastically. The characteristics of the resulting bioplastic (also called "thermoplastic starch") can be tailored to specific needs by adjusting the amounts of these additives. Conventional polymer processing techniques can be used to process starch into bioplastic, such as extrusion, injection molding, compression molding and solution casting. The properties of starch bioplastic is largely influenced by amylose/amylopectin ratio. Generally, high-amylose starch results in superior mechanical properties. However, high-amylose starch has less processiblity because of its higher gelatinization temperature and higher melt viscosity.

Starch-based bioplastics are often blended with biodegradable polyesters to produce starch/polylactic acid, starch/polycaprolactone or starch/Ecoflex (polybutylene adipate-co-terephthalate produced by BASF) blends. These blends are used for industrial applications and are also compostable. Other producers, such as Roquette, have developed other starch/polyolefin blends. These blends are not biodegradable, but have a lower carbon footprint than petroleum-based plastics used for the same applications.

Starch is cheap, abundant, and renewable.

Starch-based films (mostly used for packaging purposes) are made mainly from starch blended with thermoplastic polyesters to form biodegradable and compostable products. These films are seen specifically in consumer goods packaging of magazine wrappings and bubble films. In food packaging, these films are seen as bakery or fruit and vegetable bags. Composting bags with this films are used in selective collecting of organic waste. Further, starch-based films can be used as a paper.

Starch-based nanocomposites have been widely studied, showing improved mechanical properties, thermal stability, moisture resistance, and gas barrier properties.

Cellulose-based plastics

A packaging blister made from cellulose acetate, a bioplastic

Cellulose bioplastics are mainly the cellulose esters, (including cellulose acetate and nitrocellulose) and their derivatives, including celluloid.

Cellulose can become thermoplastic when extensively modified. An example of this is cellulose acetate, which is expensive and therefore rarely used for packaging. However, cellulosic fibers added to starches can improve mechanical properties, permeability to gas, and water resistance due to being less hydrophilic than starch.

A group at Shanghai University was able to construct a novel green plastic based on cellulose through a method called hot pressing.

Protein-based plastics

Bioplastics can be made from proteins from different sources. For example, wheat gluten and casein show promising properties as a raw material for different biodegradable polymers.

Additionally, soy protein is being considered as another source of bioplastic. Soy proteins have been used in plastic production for over one hundred years. For example, body panels of an original Ford automobile were made of soy-based plastic.

There are difficulties with using soy protein-based plastics due to their water sensitivity and relatively high cost. Therefore, producing blends of soy protein with some already-available biodegradable polyesters improves the water sensitivity and cost.

Some aliphatic polyesters

The aliphatic biopolyesters are mainly polyhydroxyalkanoates (PHAs) like the poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV) and polyhydroxyhexanoate (PHH).

Polylactic acid (PLA)

Mulch film made of polylactic acid (PLA)-blend bio-flex

Polylactic acid (PLA) is a transparent plastic produced from maize or dextrose. Superficially, it is similar to conventional petrochemical-based mass plastics like PS. It has the distinct advantage of degrading to nontoxic products. Unfortunately it exhibits inferior impact strength, thermal robustness, and barrier properties (blocking air transport across the membrane). PLA and PLA blends generally come in the form of granulates with various properties, and are used in the plastic processing industry for the production of films, fibers, plastic containers, cups and bottles. PLA is also the most common type of plastic filament used for home fused deposition modeling.

Poly-3-hydroxybutyrate

The biopolymer poly-3-hydroxybutyrate (PHB) is a polyester produced by certain bacteria processing glucose, corn starch or wastewater. Its characteristics are similar to those of the petroplastic polypropylene. PHB production is increasing. The South American sugar industry, for example, has decided to expand PHB production to an industrial scale. PHB is distinguished primarily by its physical characteristics. It can be processed into a transparent film with a melting point higher than 130 degrees Celsius, and is biodegradable without residue.

Polyhydroxyalkanoates

Polyhydroxyalkanoates are linear polyesters produced in nature by bacterial fermentation of sugar or lipids. They are produced by the bacteria to store carbon and energy. In industrial production, the polyester is extracted and purified from the bacteria by optimizing the conditions for the fermentation of sugar. More than 150 different monomers can be combined within this family to give materials with extremely different properties. PHA is more ductile and less elastic than other plastics, and it is also biodegradable. These plastics are being widely used in the medical industry.

Polyamide 11

PA 11 is a biopolymer derived from natural oil. It is also known under the tradename Rilsan B, commercialized by Arkema. PA 11 belongs to the technical polymers family and is not biodegradable. Its properties are similar to those of PA 12, although emissions of greenhouse gases and consumption of nonrenewable resources are reduced during its production. Its thermal resistance is also superior to that of PA 12. It is used in high-performance applications like automotive fuel lines, pneumatic airbrake tubing, electrical cable antitermite sheathing, flexible oil and gas pipes, control fluid umbilicals, sports shoes, electronic device components, and catheters.

A similar plastic is Polyamide 410 (PA 410), derived 70% from castor oil, under the trade name EcoPaXX, commercialized by DSM. PA 410 is a high-performance polyamide that combines the benefits of a high melting point (approx. 250 °C), low moisture absorption and excellent resistance to various chemical substances.

Bio-derived polyethylene

The basic building block (monomer) of polyethylene is ethylene. Ethylene is chemically similar to, and can be derived from ethanol, which can be produced by fermentation of agricultural feedstocks such as sugar cane or corn. Bio-derived polyethylene is chemically and physically identical to traditional polyethylene – it does not biodegrade but can be recycled. The Brazilian chemicals group Braskem claims that using its method of producing polyethylene from sugar cane ethanol captures (removes from the environment) 2.15 tonnes of CO
2
per tonne of Green Polyethylene produced.

Genetically modified feedstocks

With GM corn being a common feedstock, it is unsurprising that some bioplastics are made from this.

Under the bioplastics manufacturing technologies there is the "plant factory" model, which uses genetically modified crops or genetically modified bacteria to optimise efficiency.

Polyhydroxyurethanes

The condensation of polyamines and cyclic carbonates produces polyhydroxurethanes. Unlike traditional cross-linked polyurethanes, cross-linked polyhydroxyurethanes are in principle amenable to recycling and reprocessing through dynamic transcarbamoylation reactions.

Lipid derived polymers

A number bioplastic classes have been synthesized from plant and animal derived fats and oils. Polyurethanes, polyesters, epoxy resins and a number of other types of polymers have been developed with comparable properties to crude oil based materials. The recent development of olefin metathesis has opened a wide variety of feedstocks to economical conversion into biomonomers and polymers. With the growing production of traditional vegetable oils as well as low cost microalgae derived oils, there is huge potential for growth in this area.

Environmental impact

Confectionery packaging made of PLA-blend bio-flex
Bottles made from cellulose acetate biograde
Drinking straws made of PLA-blend bio-flex
Jar made of PLA-blend bio-flex, a bioplastic

Materials such as starch, cellulose, wood, sugar and biomass are used as a substitute for fossil fuel resources to produce bioplastics; this makes the production of bioplastics a more sustainable activity compared to conventional plastic production. The environmental impact of bioplastics is often debated, as there are many different metrics for "greenness" (e.g., water use, energy use, deforestation, biodegradation, etc.). Hence bioplastic environmental impacts are categorized into nonrenewable energy use, climate change, eutrophication and acidification. Bioplastic production significantly reduces greenhouse gas emissions and decreases non-renewable energy consumption. Firms worldwide would also be able to increase the environmental sustainability of their products by using bioplastics

Although bioplastics save more nonrenewable energy than conventional plastics and emit less GHG compared to conventional plastics, bioplastics also have negative environmental impacts such as eutrophication and acidification. Bioplastics induce higher eutrophication potentials than conventional plastics. Biomass production during industrial farming practices causes nitrate and phosphate to filtrate into water bodies; this causes eutrophication, the process in which a body of water richness gains excessive richness of nutrients. Eutrophication is a threat to water resources around the world since it causes harmful algal blooms that create oxygen dead zones, killing aquatic animals. Bioplastics also increase acidification. The high increase in eutrophication and acidification caused by bioplastics is also caused by using chemical fertilizer in the cultivation of renewable raw materials to produce bioplastics.

Other environmental impacts of bioplastics include exerting lower human and terrestrial ecotoxicity and carcinogenic potentials compared to conventional plastics. However, bioplastics exert higher aquatic ecotoxicity than conventional materials. Bioplastics and other bio-based materials increase stratospheric ozone depletion compared to conventional plastics; this is a result of nitrous oxide emissions during fertilizer application during industrial farming for biomass production. Artificial fertilizer increase nitrous oxide emissions especially when the crop does not need all the nitrogen. Minor environmental impacts of bioplastics include toxicity through using pesticides on the crops used to make bioplastics. Bioplastics also cause carbon dioxide emissions from harvesting vehicles. Other minor environmental impacts include high water consumption for biomass cultivation, soil erosion, soil carbon losses and loss of biodiversity, and they are mainly are a result of land use associated with bioplastics. Land use for bioplastics production leads to lost carbon sequestration and increases the carbon costs while diverting land from its existing uses

Although bioplastics are extremely advantageous because they reduce non-renewable consumption and GHG emissions, they also negatively affect the environment through land and water consumption, using pesticide and fertilizer, eutrophication and acidification; hence one's preference for either bioplastics or conventional plastics depends on what one considers the most important environmental impact.

Another issue with bioplastics, is that some bioplastics are made from the edible parts of crops. This makes the bioplastics compete with food production because the crops that produce bioplastics can also be used to feed people. These bioplastics are called "1st generation feedstock bioplastics". 2nd generation feedstock bioplastics use non-food crops (cellulosic feedstock) or waste materials from 1st generation feedstock (e.g. waste vegetable oil). 3rd generation feedstock bioplastics use algae as the feedstock.

Biodegradation of Bioplastics

Packaging air pillow made of PLA-blend bio-flex

Biodegradation of any plastic is a process that happens at solid/liquid interface whereby the enzymes in the liquid phase depolymerize the solid phase Certain types of bioplastics as well as conventional plastics containing additives are able to biodegrade. Bioplastics are able to biodegrade in different environments hence they are more acceptable than conventional plastics. Biodegradability of bioplastics occurs under various environmental conditions including soil, aquatic environments and compost. Both the structure and composition of biopolymer or bio-composite have an effect on the biodegradation process, hence changing the composition and structure might increase biodegradability. Soil and compost as environment conditions are more efficient in biodegradation due to their high microbial diversity. Composting not only biodegrades bioplastics efficiently but it also significantly reduces the emission of greenhouse gases. Biodegradability of bioplastics in compost environments can be upgraded by adding more soluble sugar and increasing temperature. Soil environments on the other hand have high diversity of microorganisms making it easier for biodegradation of bioplastics to occur. However, bioplastics in soil environments need higher temperatures and a longer time to biodegrade. Some bioplastics biodegrade more efficiently in water bodies and marine systems; however, this causes danger to marine ecosystems and freshwater. Hence it is accurate to conclude that biodegradation of bioplastics in water bodies which leads to the death of aquatic organisms and unhealthy water can be noted as one of the negative environmental impacts of bioplastics.

Industry and markets

Tea bags made of polylactide (PLA), (peppermint tea)

While plastics based on organic materials were manufactured by chemical companies throughout the 20th century, the first company solely focused on bioplastics- Marlborough Biopolymers- was founded in 1983. However, Marlborough and other ventures that followed failed to find commercial success, with the first such company to secure long-term financial success being the Italian company Novamont, founded in 1989.

Bioplastics remain less than one percent of all plastics manufactured worldwide, Most bioplastics do not yet save more carbon emissions than are required to manufacture them. It is estimated that replacing 250 million tons of the plastic manufactured each year with bio-based plastics would require 100 million hectares of land, or 7 percent of the arable land on Earth. And when bioplastics reach the end of their life cycle, those designed to be compostable and marketed as biodegradable are often sent to landfills due to the lack of proper composting facilities or waste sorting, where they then release methane as they break down anaerobically.


COPA (Committee of Agricultural Organisation in the European Union) and COGEGA (General Committee for the Agricultural Cooperation in the European Union) have made an assessment of the potential of bioplastics in different sectors of the European economy:

History and development of bioplastics

  • 1862: At the Great London Exhibition, Alexander Parkes displays Parkesine, the first plastic. Parkesine is made from nitrocellulose. (White 1998)
  • 1897: Still produced today, Galalith is a milk-based bioplastic that was created by German chemists in 1897. Galalith is primarily found in buttons. (Thielen 2014)
  • 1907: Leo Baekeland invented Bakelite, which received the National Historic Chemical Landmark for its non-conductivity and heat-resistant properties. It is used in radio and telephone casings, kitchenware, firearms and many more products. (Pathak, Sneha, Mathew 2014)
  • 1912: Brandenberger invents Cellophane out of wood, cotton, or hemp cellulose. (Thielen 2014)
  • 1920s: Wallace Carothers finds Polylactic Acid (PLA) plastic. PLA is incredibly expensive to produce and is not mass-produced until 1989. (Whiteclouds 2018)  
  • 1926: Maurice Lemoigne invents polyhydroxybutyrate (PHB) which is the first bioplastic made from bacteria. (Thielen 2014)
  • 1930s: The first bioplastic car was made from soy beans by Henry Ford. (Thielen 2014)
  • 1940-1945: During World War II, an increase in plastic production is seen as it is used in many wartime materials. Due to government funding and oversight the United States production of plastics (in general, not just bioplastics) tripled during 1940-1945(Rogers 2005). The 1942 U.S. government short film The Tree in a Test Tube illustrates the major role bioplastics played in the World War II victory effort and the American economy of the time.
  • 1950s: Amylomaize (>50% amylose content corn) was successfully bred and commercial bioplastics applications started to be explored. (Liu, Moult, Long, 2009) A decline in bioplastic development is seen due to the cheap oil prices, however the development of synthetic plastics continues.
  • 1970s: The environmental movement spurred more development in bioplastics. (Rogers 2005)
  • 1983: The first bioplastics company, Marlborough Biopolymers, is started which uses a bacteria-based bioplastic called biopal. (Feder 1985)
  • 1989: The further development of PLA is made by Dr. Patrick R. Gruber when he figures out how to create PLA from corn. (Whiteclouds 2018). The leading bioplastic company is created called Novamount. Novamount uses matter-bi, a bioplastic, in multiple different applications. (Novamount 2018)
  • 1992: It is reported in Science that PHB can be produced by the plant Arabidopsis thaliana. (Poirier, Dennis, Klomparens, Nawrath, Somerville 1992)
  • Late 1990s: The development of TP starch and BIOPLAST from research and production of the company BIOTEC lead to the BIOFLEX film. BIOFLEX film can be classified as blown film extrusion, flat film extrusion, and injection moulding lines. These three classifications have applications as follows: Blown films - sacks, bags, trash bags, mulch foils, hygiene products, diaper films, air bubble films, protective clothing, gloves, double rib bags, labels, barrier ribbons; Flat films - trays, flower pots, freezer products and packaging, cups, pharmaceutical packaging; Injection moulding - disposable cutlery, cans, containers, performed pieces, CD trays, cemetery articles, golf tees, toys, writing materials. (Lorcks 1998)
  • 2001: Metabolix inc. purchases Monsanto's biopol business (originally Zeneca) which uses plants to produce bioplastics. (Barber and Fisher 2001)
  • 2001: Nick Tucker uses elephant grass as a bioplastic base to make plastic car parts. (Tucker 2001)
  • 2005: Cargill and Dow Chemicals is rebranded as NatureWorks and becomes the leading PLA producer. (Pennisi 2016)  
  • 2007: Metabolix inc. market tests its first 100% biodegradable plastic called Mirel, made from corn sugar fermentation and genetically engineered bacteria. (Digregorio 2009) 
  • 2012: A bioplastic is developed from seaweed proving to be one of the most environmentally friendly bioplastics based on research published in the journal of pharmacy research. (Rajendran, Puppala, Sneha, Angeeleena, Rajam 2012) 
  • 2013: a patent is put on bioplastic derived from blood and a crosslinking agent like sugars, proteins, etc. (iridoid derivatives, diimidates, diones, carbodiimides, acrylamides, dimethylsuberimidates, aldehydes, Factor XIII, dihomo bifunctional NHS esters, carbonyldiimide, glyoxyls, proanthocyanidin, reuterin). This invention can be applied by using the bioplastic as tissue, cartilage, tendons, ligaments, bones, and being used in stem cell delivery. (Campbell, Burgess, Weiss, Smith 2013) 
  • 2014: It is found in a study published in 2014 that bioplastics can be made from blending vegetable waste (parsley and spinach stems, the husks from cocoa, the hulls of rice, etc.) with TFA solutions of pure cellulose creates a bioplastic. (Bayer, Guzman-Puyol, Heredia-Guerrero, Ceseracciu, Pignatelli, Ruffilli, Cingolani, and Athanassiou 2014)
  • 2016: An experiment finds that a car bumper that passes regulation can be made from nano-cellulose based bioplastic biomaterials using banana peels. (Hossain, Ibrahim, Aleissa 2016)
  • 2017: A new proposal for bioplastics made from Lignocellulosics resources (dry plant matter). (Brodin, Malin, Vallejos, Opedal, Area, Chinga-Carrasco 2017)
  • 2018: Many developments occur including Ikea starting industrial production of bioplastics furniture (Barret 2018), Project Effective focusing on replacing nylon with bio-nylon (Barret 2018), and the first packaging made from fruit (Barret 2018).
  • 2019: Five different types of Chitin nanomaterials were extracted and synthesized by the 'Korea Research Institute of Chemical Technology' to verify strong personality and antibacterial effects. When buried underground, 100% biodegradation was possible within 6 months.

*This is not a comprehensive list. These inventions were by the author to show versatility of bioplastics and important breakthroughs. New applications and inventions of bioplastics happen every year.

Bioplastics Development Center - University of Massachusetts Lowell
A pen made with bioplastics (Polylactide, PLA)

Testing procedures

A bioplastic shampoo bottle made of PLA-blend bio-flex

Industrial compostability – EN 13432, ASTM D6400

The EN 13432 industrial standard must be met in order to claim that a plastic product is compostable in the European marketplace. In summary, it requires multiple tests and sets pass/fail criteria, including disintegration (physical and visual break down) of the finished item within 12 weeks, biodegradation (conversion of organic carbon into CO2) of polymeric ingredients within 180 days, plant toxicity and heavy metals. The ASTM 6400 standard is the regulatory framework for the United States and as similar requirements.

Many starch-based plastics, PLA-based plastics and certain aliphatic-aromatic co-polyester compounds, such as succinates and adipates, have obtained these certificates. Additive-based bioplastics sold as photodegradable or Oxo Biodegradable do not comply with these standards in their current form.

Compostability – ASTM D6002

The ASTM D 6002 method for determining the compostability of a plastic defined the word compostable as follows:

This definition drew much criticism because, contrary to the way the word is traditionally defined, it completely divorces the process of "composting" from the necessity of it leading to humus/compost as the end product. The only criterion this standard does describe is that a compostable plastic must look to be going away as fast as something else one has already established to be compostable under the traditional definition.

Withdrawal of ASTM D 6002

In January 2011, the ASTM withdrew standard ASTM D 6002, which had provided plastic manufacturers with the legal credibility to label a plastic as compostable. Its description is as follows:

The ASTM has yet to replace this standard.

Biobased – ASTM D6866

The ASTM D6866 method has been developed to certify the biologically derived content of bioplastics. Cosmic rays colliding with the atmosphere mean that some of the carbon is the radioactive isotope carbon-14. CO2 from the atmosphere is used by plants in photosynthesis, so new plant material will contain both carbon-14 and carbon-12. Under the right conditions, and over geological timescales, the remains of living organisms can be transformed into fossil fuels. After ~100,000 years all the carbon-14 present in the original organic material will have undergone radioactive decay leaving only carbon-12. A product made from biomass will have a relatively high level of carbon-14, while a product made from petrochemicals will have no carbon-14. The percentage of renewable carbon in a material (solid or liquid) can be measured with an accelerator mass spectrometer.

There is an important difference between biodegradability and biobased content. A bioplastic such as high-density polyethylene (HDPE) can be 100% biobased (i.e. contain 100% renewable carbon), yet be non-biodegradable. These bioplastics such as HDPE nonetheless play an important role in greenhouse gas abatement, particularly when they are combusted for energy production. The biobased component of these bioplastics is considered carbon-neutral since their origin is from biomass.

Anaerobic biodegradability – ASTM D5511-02 and ASTM D5526

The ASTM D5511-12 and ASTM D5526-12 are testing methods that comply with international standards such as the ISO DIS 15985 for the biodegradability of plastic.

See also

Further reading

External links

Uses material from the Wikipedia article Bioplastic, released under the CC BY-SA 3.0 license.