SATUAN ACARA PENGAJARAN (SAP)

Pertemuan Tanggal Pokok Bahasan

BIOMATERIAL 1
2
Sept 2015
Sept 2015
3 Sept 2015
TPE 4163- 3 (2-1) SKS 4 Sept 2015
5 Sept 2015
6 Okt 2015
7 Okt 2015
pengetahuan dasar mengenai biomaterial
Klasifikasi, struktur, sifat material dan biomaterial
Struktur Kristal
Keramik
Polimer
Biopolimer dan Bioplastik
Biomaterial di bidang teknik, biologi

JURUSAN KETEKNIKAN PERTANIAN 8 Okt 2015 Kapita Selekta 1 (Antifouling Biomaterial)

9 Okt 2015 UJIAN TENGAH SEMESTER
September – Desember 2015 10 Nov 2015 Kapita Selekta 2 (Drug Delivery)
11 Nov 2015 Kapita Selekta 3 (Microalgae Sebagai Bio-based material)
Kapita Selekta 4 : Lignin dan Selulosa sebagai Bio0Based
12 Nov 2015
material
13 Nov 2015 Karakterisasi Biomaterial 1
Dina Wahyu Indriani, S.TP, M.Sc 14 Des 2015 Karakterisasi Biomaterial 2
Email: dinawahyu@ub.ac.id
15 Des 2015 Tugas Besar
16 Des 2015 Presentasi Kelompok
17 Jan 2016 UJIAN AKHIR SEMESTER

Life cycle of products

Bioplastik dan PLA

Factors to using Bioplastics Why Use Bioplastics?

 Bioplastics
 Diffusion properties
 Tensile strength
 Thermal properties
 Permeability
 Environmental Factors
 Life span
 Manufacturing
 Applications
 Bottling, resins, packaging, etc
 Main constituents
 Polylactic acids from starch (Corn, Potatoes, etc)
 Oils, sugars, fibers, etc
 Pros
 Reduces or eliminates GHG in production
 Requires less or no petrochemicals
 Plants decreases CO2 in the atmosphere
 Biodegradable - byproducts water, CO2, and organic materials
 Can be utilized as fuel
 Slow Release of CO2 allows for plants to absorb CO2 than release
it in the atmosphere
 Potential Cons
 Uses Genetically Modified processes
 Cost up to three times more than regular Plastic
 Use of fertilizers and pesticides for crops

1
 Problems with Conventional
Composition
Plastic  Polylactic acids (PLA)
 Similar to regular plastic
 Polyhydroxyalkanoic acids
(PHAs)
 Aliphatic polyester that does not
require synthetic processing
 Uses bacteria/enzymes
 Better heat resistance than PLA
 Pros  Broader range of materials can
be used to make PHAs
 Cheap and Easy to Manufacture  Polyhydroxybutyrate-co-
 Good Commercial Properties valerate (PHBVs)
 Polyols
 Cons  Plant oil
 Complex entanglements of polymer chains (usually PET or PBT)  Variety of other Bioplastics
make it hard to decompose
 Extracted or Used
 Relies heavily on petrochemicals  oil, starch, sugars, lactic acid,
 Needs processing fatty acids, proteins, bacteria,
 Recycling requires energy and money fibers
 Releases toxic chemicals
 Fragmentation or Cyclization occurs
 200 million tons produced each year and most of it is not recycled

Lactic Acid Polymerization Broad Range of Bioplastics

 Bioplastics made from starch use sorbitol and glycerine which
plasticizes the starch into a plastic.
 Different amounts of these additives are used to fit the use of the
plastic
 Bottling, packages, cloth,etc
 Similar properties of regular plastic but environmental friendly
 Starch can also be fermented into lactic acid to make PLA
 Bioplastics derived from fatty acids (oils) can be utilized as a fuel
resource
 Center for Biocatalysis and Bioprocessing of Macromolecules
(CBBM) created a new plastic that degrades in a form similar to
diesel.
 Thermal Properties
 Can exceed stainless steel, which can be utilized in household
appliances and mobile devices.
 High conductivity increases heat dissipation can be used in
electronics
 Easy to mold due to lower melting temperature

Currently:
 We showed DARPA that we could make a new plastic Potentials:
from plant oils that has remarkable properties, which  Utilizes waste materials
includes being tougher and more durable than typical  Reduces Municipal waste
 Use manure or compost  Improving biodegradability
polyethylenes. Additionally, the bioplastic can be placed  Reduces methane for certain environments
in a simple container where it is safely broken down to  High moisture content  Metallization could provide
liquid fuel.  Replace regular cloths better barrier properties
 Addition of SiO2, carbon
 —Prof. Gross  Can be converted back to
monomer, purified, and further fiber, or other metals
utilized as a plastic  Increases thermal
conductivity
• Military units generate substantial quantities of  Biodegradable
 Specialized enzymes can
packaging waste when engaging in stationary field  Requires less energy to enhance production
manufacture
operations. If we can turn this waste into fuel, we will  Less petrochemicals or none
 Could be cost effective as
see a double benefit—we will reduce the amount of required petrochemicals increase in
price
waste that we have to remove, and we will reduce the  Requires no processing
amount of new fuel that we must deliver to the units.  Can use conventional plastic
factories for manufacturing
• —Khine Latt, program manager for DARPA’s Mobile  Can replace fertilizers
Integrated Sustainable Energy Recovery program

2

Overview
Overall even though bioplastics are generally more
expensive than regular plastic, the variety of uses and
benefits could outweigh the cost. It cuts down on
municipal waste, reduces GHGs, it’s environmentally
friendly, and it can be used as a fuel. Lastly with
developing technologies, these benefits will improve
and the cost will be competitive in the market.
Polylactic acid (PLA)
Bacterial fermentation is used to produce lactic acid from corn starch or cane
• One of the few polymers in which the stereochemical structure can
easily be modified by polymerizing a controlled mixture of L and D
isomers to yield high molecular weight and amorphous or semi-
crystalline polymers.
• Properties can be both modified through the variation of isomers
(L/D ratio) and the homo and (D, L) copolymers relative contents.
• PLA can be tailored by formulation involving adding plasticizers,
other biopolymers, fillers, etc
Catalytic and thermolytic ring-opening polymerization of lactide (left) to polylactide (right)
BIOPOLYMER USES
• Biopolymers (also called renewable polymers) are
produced from biomass for use in the packaging industry.
• Biomass comes from crops such as sugar beet, potatoes or
wheat: when used to produce biopolymers, these are classified
as non food crops. These can be converted in the
following pathways:
• Sugar beet > Glyconic acid > Polyglonic acid
• Starch > (fermentation) > Lactic acid > Polylactic acid (PLA)
• Biomass > (fermentation) > Bioethanol > Ethene > Polyethylene
• Many types of packaging can be made from biopolymers: food
trays, blown starch pellets for shipping fragile goods, thin
films for wrapping.
Polylactic acid (PLA)
Poly(lactic acid) or polylactide (PLA) is a thermoplastic aliphatic
polyester commonly made from a-hydroxy acids, derived from renewable
resources, such as
• corn starch (in the United States),
• tapioca products (roots, chips or starch mostly in Asia) or
• sugarcanes (in the rest of world).
It can biodegrade under certain conditions, such as the presence of
oxygen, and is difficult to recycle.
PLA is not a polyacid (polyelectrolyte),
but rather a polyester
Polylactic acid (PLA)
sugar.
Two lactic acid molecules undergo a single esterfication and then
catalytically cyclized to make a cyclic lactide ester.
PLA of high molecular weight is produced from the dilactate ester by ring-
opening polymerization.
Polymerization of a racemic mixture of L- and D-lactides usually leads to the
synthesis of poly-DL-lactide (PDLLA) which is amorphous.
Stannous octonate
Or tin(II) chloride
3
 Due to the chiral nature of lactic acid, several
distinct forms of polylactide exist: poly-L-
poly-DL-lactide (PDLLA) lactide (PLLA) is the product resulting from
polymerization of L,L-lactide (also known as L-
lactide). heat resistant PLA can withstand
temperatures of 110C (230F)
PDLA (poly-D-lactide): optically transparent.
PLA has similar mechanical properties to PETE polymer, but has a significantly
lower maximum continuous use temperature.
PETE: Polyethylene terephthalate, commonly abbreviated PET, PETE, or the obsolete PETP
or PET-P, is a thermoplastic polymer resin of the polyester family and is used in synthetic
fibers; beverage, food and other liquid containers
APPLICATIONS
• Woven shirts (ironability), microwavable trays, hot-fill
applications and even engineering plastics (in this case, the
stereocomplex is blended with a rubber-like polymer such as
ABS).
• PLA is currently used in a number of biomedical applications,
such as sutures, stents, dialysis media and drug
delivery devices. The total degradation time of PLA is a few
years. It is also being evaluated as a material for tissue
engineering.
• Because it is biodegradable, it can also be employed in the
preparation of bioplastic, useful for producing loose-fill
packaging, compost bags, food packaging, and disposable
tableware. In the form of fibers and non-woven textiles, PLA
also has many potential uses, for example as upholstery,
disposable garments, awnings, feminine hygiene products, and
diapers.
Plastics are resistant to biodegradation accumulating at the rate of 25million
tonnes per year. Much disposed in landfill sites. Possibility of recycling plastics is
limited and incineration yields toxic compounds
As of Jun 2010, NatureWorks was the primary producer of PLA (bioplastic) in
the United States.
The Korean research center KAIST has announced that they have found a way
to produce PLA using bio-engineered Escherichia coli.
Polylactic acid (PLA): Biodegradability
• PLA is considered both as biodegradable (e.g. adapted for short-term
packaging) and as biocompatible in contact with living tissues (e.g. for
biomedical applications such as implants, sutures, drug encapsulation,
etc.).
• PLA can be degraded by abiotic degradation (i.e. simple hydrolysis of
the ester bond without requiring the presence of enzymes to catalyze
it). During the biodegradation process, and only in a second step, the
enzymes degrade the residual oligomers till final mineralization (biotic
degradation).
• As long as the basic monomers (lactic acid) are produced from
renewable resources (carbohydrates) by fermentation, PLA complies
with the rising worldwide concept of sustainable development and is
classified as an environmentally friendly material.
• PLA is a sustainable alternative to petrochemical-derived
products, since the lactides from which it is ultimately
produced can be derived from the fermentation of agricultural
by-products such as corn starch or other carbohydrate-rich
substances like maize, sugar or wheat.
• PLA can be an alternative to high-impact polystyrene by using
as much as 1 wt% non-PLA due to creating co-polymers which
can strengthen PLA plastic.
PLA is more expensive than many petroleum-derived commodity
plastics, but its price has been falling as production increases.
The demand for corn is growing, both due to the use of corn for
bioethanol and for corn-dependent commodities, including PLA.
Due to PLA's relatively low glass Mulch film made of polylactic
transition temperature, PLA cups acid (PLA)-blend bio-flex
cannot hold hot liquids. However,
much research is devoted to
developing a heat resistant PLA
Biodegradable cups at a restaurant
4
 Bioplastics from Microorganisms
Degradable plastics can be biodegradable or photodegradable
Photodegradable plastics can break down to small fragments and lose Degradable polymers that are naturally degraded by the action of
structure but small fragments are not degradable. microorganisms such as bacteria, fungi and algae
Biodegradable plastics can be metabolized by MO
Benefits
• 100 % biodegradable
Semidegradable plastics contain starch, cellulose and polyethene
For complete degradation 50% mix is required which compromises • Produced from natural,
structural properties renewable resources
• Able to be recycled, composted
or burned without producing
Biodegradable plastics toxic byproducts
Polyhydroxy alkanoates (PHAs): PHB
Polyactides
Aliphatic polyesters
Several legislations enacted but demand for bioplastics
Polysaccharides
have not increased
Blends of above

IMPORTANCE
Carbon Cycle of Bioplastics
CO2
• 2003- North America H2O
Photosynthesis
– 107 billion pounds of Biodegradation
synthetic plastics
produced from petroleum
– Take >50 years to degrade
– Improper disposal and
Plants Recycle
failure to recycle 
overflowing landfills
Plastic Products
Carbohydrates

Fermentation PHA Polymer

Polyhydroxyalkanoates (PHAs) Polyhydroxyalkanoates (PHAs)

• Polyesters accumulated inside microbial cells • Produced under conditions of:

as carbon & energy source storage – Low limiting nutrients (P, S, N, O)
– Excess carbon

 2 different types:
 Short-chain-length 3-5 Carbons
 Medium-chain-length 6-14 Carbons

 ~250 different bacteria have been found to

produce some form of PHAs
Ojumu et al., 2004

5
 PHA Biosynthesis
Polyhydroxybutyrate (PHB)

• Example of short-chain-length
PHA
• Produced in activated sludge
• Found in Alcaligenes eutrophus
• Accumulated intracellularly as
granules (>80% cell dry weight)

Ojumu et al., 2004

Lee et al., 1996

PHB: polyhydroxybutyrate
phbC-A-B Operon in A. eutrophus
Intracellular microbial plastic first found in Bacillus megaterium
80 different types of PHAs formed from 3-hydroxyalkanoate acid monomers
3-14 carbons in length
Energy store when nutrient is limited
• Structural genes encoded in single operon
Alcaligenes eutrophus (Ralstnia etropha) to produce PHB
– PHA synthase
Polymer had low thermal stability and brittle
Addition of propionate to culture produced P (3HB-co-3HV)
– b-ketothiolase
and polymer was flexible and tough – NADPH-dependent acetoacetyl-CoA reductase
Marketed as BIOPOLTM used to make films, coated paper, compost bags,
disposable foodwares , bottles, razors

COST is still HIGHER than chemically synthesized polymers

Propylene: 1$/kg
PHVB: 3-5$/kg
Lee et al., 1996

HB: hydroxybutyrate HV: hydroxyvalerate

Recovery of PHAs from Cells Bioplastic Properties

• Some are stiff and brittle

• PHA producing microorganisms stained with – Crystalline structure  rigidity
• Some are rubbery and moldable
Sudan black or Nile blue
• Properties may be manipulated by blending
• Cells separated out by centrifugation or polymers or genetic modifications
filtration • Degrades at 185°C
• PHA is recovered using solvents (chloroform) • Moisture resistant, water insoluble, optically
pure, impermeable to oxygen
to break cell wall & extract polymer
• Must maintain stability during manufacture
• Purification of polymer and use but degrade rapidly when disposed of
or recycled

6
 Biodegradation Biodegradation by
PHA depolymerases
• Fastest in anaerobic sewage and slowest in
seawater
• Depends on temperature, light, moisture,
exposed surface area, pH and microbial activity
• Degrading microbes colonize polymer surface &
secrete PHA depolymerases
• PHA  CO2 + H2O (aerobically)
• PHA  CO2 + H2O + CH4 (anaerobically)

Conclusions
POLY(LACTIC ACID)
• Need for bioplastic optimization:
– Economically feasible to produce
– Cost appealing to consumers
– Give our landfills a break

 How many of you would be willing to pay 2-3 times

more for plastic products because they were
“environmentally friendly”?

References
 http://www.nec.co.jp/eco/en/annual2006/02/2-1.html
 http://biopact.com/2007_09_25_archive.html
 http://www.greencarcongress.com/2007/03/researchers_dev_1.html
 http://www.european-bioplastics.org Thank You
 http://www.environmentalleader.com/2007/10/23/bioplastics-carve-
out-niche/
 http://www.epo.org/topics/innovation-and-economy/emerging-
technologies/article-6.html
 http://www.thenakedscientists.com/HTML/articles/article/bioplastics/
 http://www.waste-management-
world.com/display_article/273126/123/ARTCL/none/BIOTR/1/Beaut
y-of-bioplastics/
 http://www.biobasics.gc.ca/english/View.asp?x=790
 http://www.immnet.com/articles?article=3135