Lecture Biopolymers

Renewable resources
Biopolymers
Bild: Siemens
© 2013 Renewable Resources Engeneering / Biopolymers
FH Schmalkalden, Fakultät Maschinenbau 1
Renewable Resources Engineering / Biopolymers
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Index
» Introduction
» Motivation
» Concepts involved
» Biopolymers
 Structure and Production

 Technical properties
» Applications
» Future

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Definition

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Definition
Biopolymers
“[…] polymer material that fulfills at least one of the following

properties:
• Consists of bio-based raw material
• Is in some way biodegradable “
[1]

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Overview
 World Commission on Environment and Development, 1987
Sustainable development
“[…] is development that meets the needs of the present without

compromising the ability of future generations to meet their own
needs“
[2]
» use of new materials in construction

» recycling of reusable materials

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Overview – Spheres of Sustainability
[14]
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Overview – Historical background
[1]
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[9]
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[9]
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[9]
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[9]
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Index
» Introduction
» Motivation
» Biopolymers

» Applications
» Future

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Petroleum sector
“[...] Nothing remains forever in the oil sector, and prices are already rising for
quite some time. [...] The oil sector is unstable due to geopolitical and economic
crises. [..] The difference between production capacity and consumption is
increasing. Therefore, sooner or later, there may be a collapse.”
Leonardo Maugeri/ Researcher at Harvard Kennedy School

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Production- Comparison
[9]
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Market size - Comparison
[9]
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Market size - Analyse
[9]
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Index
» Introduction
» Motivation
» Involved concepts
» Biopolymers

» Applications
» Future

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Petrochemical raw materials
5,3 trillion
liters/ year *
Million of years
* Opep - 2013 [27]

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CO2 Closed Cycle
Bio-ethanol  Bio-ethylene
(Bio-PE)  HDPE, LDPE,
PV, PUR’s, PVC, PA’s [1]
[28]
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Life Cycle of Bioplastics
[29]
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“Bio-based X Biodegradable” - polymers
 Are there some differences? – YES!!!
[1]
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Degradability
Degradability
“[…] is ultimately influenced only by the chemical and physical

microstructure of the polymers, and neither by the origin of the raw
materials used nor by the process used for manufacturing these
polymers.”
“[…] they decompose under exposure to microorganisms and/or

enzymes”
[1]

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Degradability
» Primary and final degradation
» Increases fundamentally as the

ratio of heteroatoms (Ex.: O and
N) increases, in the Main chain
Intracellular
Starch /
Degradability
Cellulose
PLA
PCL
PVAL
Ratio: Heteroatom / carbon (in the main chain) [1]

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Degradability
» There are two types of degradable polymers:
 Degradable Petroleum-based
• based on hydrocarbon monomers and oligomer (crude oil, natural gas,…)

• expended for degradability by incorporating various heteroatom into their molecular
structure ( oxygen and nitrogen)
 Degradable Bio-based
• Ex.: starch-based polymers and their blends, polymers based on sugar, vegetables oils

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Degradability - Standards
» Aerobic biodegradation ( aquatic or terrestrial )
» Anaerobic biodegradation
Aerobic biodegradation Aerobic biodegradation Anaerobic

-aquatic- -terrestrial- biodegradation
• Composting
- DIN EN ISO 14851/ JISK 6950 - DIN EN ISO 14855/ JISK 6953 -DIN EN ISO 14853
- DIN EN ISO 14852/ JISK 6951 -ASTM D 5338
- DIN EN ISO 9408 - DIN EN ISO 15985
- DIN EN ISO 10634 • Disintegration
- DIN EN ISO 16929/ JISK 6952 - DIN EN ISO 11734
- DIN EN ISO 20200/ JISK 6954
- DIN EN 14045, DIN EN 14046,
DIN EN 14806
• Soil
- DIN EN ISO 17556/ JISK 6955
•OECD 208 [1]
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Degradability – Tests / Composting
The tests are based:
» measurement of oxygen demand

»amount of carbon dioxide evolved in the process
 Definition of “ Bio-degradable polymers” : DIN EN 13432
Composting
“A material or materials mix and parts produced from it is considered

compostable, when under defined conditions in a composting system,
it is entirely transformed into CO2, H2O, CH4 and biomass within a
specifies length of time, mostly during a composting cycle ranging.”
[1]

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Certification of Compostability
Biodegradable Japan Compostable

Jätelaitosy DIN Avfall
Certification Products AIB Vincotte, BioPlastics Italian
hdistys, CERTCO / Norge,
organizatio Institute (BPI), Belgium Association, Association,
Finland European Norway
n USA Japan Italy
Bioplastics,
Germany
Green Pla
DIN EN EN 13432 DIN EN
Reference ASTM D6400 DIN EN 13432 identification DIN EN 13432
13432 ASTM 13432
standard system
D6400
Logo
[1]
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Principles of polymers production - Polyaddition
» Definition: method where monomers are added one by one to an active site
on the growing chain without by-products. Based on protons transference and
opening the double bond.
» Components:
 molecules with carbon-carbon double bonds or with triple bonds
 molecules containing with bifunctional groups
» Examples: PU, POM, …
[13]
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Principles of polymers production - Polycondensation
» Definition: method where two molecules combine to form a larger molecule,

together with the loss of small molecule. Possible small molecules lost are
water, hydrogen chloride, methanol or acetic acid.
» Components: Monomers containing at least two functional groups (i.e.

hydroxyl, carboxyl and amino groups; -OH; -COOH; -NH2)
» Examples: Nylon, PCs, PEs and PET
[30]
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Principles of polymers production - Polymerisation
» Definition: method monomers react to polymers by breaking the double

bonds. Occur in three steps: initiation, propagation and termination, involving
free radicals (initiators).
» Components:
 unsaturated monomers
 initiators
» Examples: PP, PE, PS, ….
[31] modified
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Index
» Introduction
» Motivation
» Biopolymers

» Applications
» Future

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Biopolymer-The most important (next 5 years)
[9]
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Biopolymer- Production and Capacity
[9]
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Biopolymer- Production and Capacity
[9]
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Biopolymers- Potential substitutes
Polymer PVC PEAD PEBD PP PS PMMA PA PET PC
Starch - + + + + - - - -
PLA - + - + + - + + -
PHB - + - ++ + - - - -
PHBHx + ++ ++ ++ + - - + -
++ Total replacement , + Partial replacement, - Not replace
[5]
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Biopolymers- Process production
[1]
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Bio- based polyesters
» PLA
Starch, Bigenic
wast material
Corn
» Characteristics
H2O Hydrolytic Corn-based
Cracking Starch
 Thermoplastic
 Molecular weight: 100000-300000
 High resistant to attack by
microorganisms
 High elastic modulus, rigidity,
transparency
 Good biocompatibility and moldability
» Renewable sources: starch, sugar from

corn, wheat, sugar cane, sugar beet and
potato
[9]
[5]
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» Applications
 Drug carriers [15]

Automotive
 High potential for packaging
 Module for hemodialysis
 Fibers for textile Interference screws for
fixation of grafts
 Films for agriculture
 Surgical implants
 Fibers for sutures
 Automotive industries
» Commercial producers of PLA Module for hemodialysis Vascular prothesis
[5]
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» PHA
» Characteristics
 Polymer that is intracellularly deposited by

bacterias
 Biodegradable and Biocompatible
 Best representative of this biopolymers
family: PHB, PHBV
 Disadvantages: relatively high price (3,7- [1]
15 €/kg [1])
» Biotechnological production
 Bacterial fermentation
 Synthesis in genetically modified plants
 Enzymatic catalysis in cell-free systems
[5]

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[17] [9]
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» Renewable sources:
recombinant and wild
microorganisms, transgenic plants, sources of glucose
and sucrose (Obs.: can also be produced by in vitro
process)
» Applications
 Packaging industry
 Printing & photographic industry
 Other bulk chemicals
 Medical implant biomaterials
 Medical
 Healthy food additives
 Biofuels or fuel additives
[16]
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» Commercial producers of PHA
[5]

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Starch-based polymers
» TPA
» Characteristics
 Starch: major source of energy

 Versatile for potential use in polymers
 Low cost
 Biocompatibility
 Biodegradable and by-products non-toxic
(dehydration and depolymerization)
 capable of being modified or blended
(substitution of hydroxyl groups)  improve
the processing conditions and properties
 Polymers blended: chitin, chitosan, pectin,
cellulose, poly (lactic acid) - PLA
» Renewable sources: seeds of cereals

(corn, wheat, and rice), tubers (potato), and
roots (manioc) [9]

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Starch-based polymers
» Applications
 Food industry ( food packaging, edible

films)
 Agriculture (covering of greenhouse,
mulch film and fertilizers con trolled
release materials)
 Medical field ( hydrogel, bone tissue
engineering scaffold)
» Commercial producers of Starch
[5]
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Cellulose based polymers
» Characteristics
Cellulose
 Carbohydrates
 Strong natural polymer
Fibers/cellulose
 Biocompatibility
 Easy to recycle by combustion
 Very hygroscopic (expand as much as 90% in
water) Regenerated Cellulose
 Good mechanical properties: high tensile cellulose derivates
strength and Young’s modulus, low coefficient
of thermal expansion
Cellulose
Fibers
ester
» Classification
Cellulose
• Regenerated cellulose Filmes
ether
• Cellulose derivates
[1] modified
[1]
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Cellulose based polymers – Global production
Regenerated cellulose and cellulose derivates; global

production 4.940.000 t/a - 2011
10%
Cellulose ester
25%
Cellulose ether
Regenerated cellulose
65%
[1] modified
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» Regenerated cellulose
» Characteristics
 Essentially cellulose that has been

chemically dissolved and reconstituted in
the form or fibers or films
 Different properties are resulted by different
solvents
 Biologically degradable
 High modulus of elasticity and good thermal
stability
 Most important: viscose silk
Scanning electron microscopic image of bamboo viscose (left) compared with

native bamboo fibers (right) [1] [9]
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» Applications
 Treatment of Chronic Wounds and Burns

 Haemodialysis membranes [20]
 Syringe filters
 Packaging (Ex: Casings)
 Textile industry
 Cellophane films
[19]
[21] [20]

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» Cellulose derivates
» Classification
 Cellulose ether  Cellulose ester

 generated by etherification with  Complex structure
alcohols
[9]
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» Applications
 Cellulose ether
Additives to stabilize viscosity or as water binders in

building materials (Ex: wall coatings), glues,
cosmetics, detergents, pigments, drilling fluids, and in
the paper industry [1].
 Cellulose ester
Organic membranes, pharmaceutical applications (Ex: Membrane

drug delivery [22]), film base in photography,
component in some adhesives, and frame material
for eyeglasses; it is also used as a synthetic fiber and
in the manufacture of cigarette filters, as well as a
coating material (in particular the automotive coating)

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Bio-based polyolefins
» Bio-PE
Drop-in-solutions
“[…] represent an attempt to maintain traditional synthesis processes

developed for petrochemical feedstock while completely substituting
petrochemical raw material components with biogenic feedstock. “
[1]
» Characteristics
 “Green PE”- Braskem (2002)

 Non-degradable
 Each ton of green polyethylene  2,5 tons of carbon dioxide (CO2) is removed from the
atmosphere [11]
 Manufactured from bio-ethanol (Raw materials: sugar cane, sugar beet, corn)
 Bio-ethylene have potencial to produce also PS, PVC and also PURs, PAs and polyesters

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Bio-based polyolefins - Production and Land use
requirements
[9]
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Bio-based polyolefins
» Applications
 food packaging
 cosmetics
 personal care
 automotive parts and toys
 Cables and pipes
 Textiles
(Obs.: Just as petrochemical PE [23])

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Bio-based polyurethanes
» Bio-PUR
» Characteristics
 Known since the early 1950s

 Produced by polyaddition (multivalent
alcohols and di-or polyfunctional aromatic
or aliphatic isocyanates)
 Comparing with conventional, are not
microbiologically stable
 Isocyanates  petro-based (Ex: TDI, MDI)
» Renewable sources: biogenic polyols

based on vegetable oils [9]
General formation reaction for polyurethanes [1]

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Bio-based polyurethanes
» Applications
 Insulation for roofs and walls,

appliances and coolers
 Coatings
 Adhesives and sealants
 Shoe soles
» Commercial producers of Bio-

PUR
Metzeler Schaum (Germany), Bayer
MaterialScience (Germany), Dow
Polyurethanes (USA), Mitsui Chemical
(Japan), DuPont (USA), Urethane Soy
System (USA), Vertellus Performance
Materials (USA), Cargill (USA).

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Bio-based polyamides
» Bio-PAs
» Characteristics
 Partial or entire substitution

by biogenic feedstock
 Non-biodegradable
 Properties (some Bio-PAs)
» Renewable sources
 natural dicarbonic acids and

their decomposition products
(castor oil)
[9]
 sources of carbohydrates
(corn, sugar beet and sugar
cane)

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» Bio-PAs based on caster oil
[3]
Ricinus communis - Castor oil plant

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» Manufacturing routes:
 Three most importants manufacturing routes:
- Condensation reaction of bio-based

dicarboxylic acids with diamines
- Condensation reaction of amino acids
as bi-functional monomers
- Ring-opening polymerization of
lactams (cyclic amide). Obs.: Penicillin
is a kind of lactam.
 New routes
− Fermentative (Drop-in-solution) - PA 6,
PA 66
− Based on natural material lysine
(animals, vegetable proteins) - PA 5.10
− Butadiene as feedstock based on
bioethanol [9]

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» Applications
 Automotive
 Offshore pipes
 Consumer goods
 Electronic materials [35]
[36]
[37] [34] [32]

» Commercial producers of Bio-PAs
Arkema (France), BASF (Germany), DuPont

(USA), Toray (Germany), Evonik (Germany) and
Rhodia (France).
[33]
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Others
» Bio-PET
» Characteristics
 Consists of 70% terephthalic acid and 30%

monoethylene glycol (based on renewable
resource)
 100% recyclable
 Advantages: good heat-resistence, durability
performance, shink resistence
» Appications
 Automotive sector (seats and carpeting and

other interior components –Toyota 2015)
 Bottles (Coca-Cola – 30%; PepisiCo- 100%
biobased)

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Index
» Introduction
» Motivation
» Biopolymers

» Applications
» Future

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Biopolymers vs. Conventional: Price
[1]
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Biopolymers vs. Conventional: Density
[1]
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Biopolymers vs. Conventional: Modulus of
elasticity
[1]
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Biopolymers vs. Conventional: Tensile strength
[1]
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Biopolymers vs. Conventional: Charpy impact
strength
[1]
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Biopolymers vs. Conventional: Hardness
[1]
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Biopolymers vs. Conventional: Glass transition
temperature
[1]
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Biopolymers vs. Conventional: Melting range
temperature
[1]
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Biopolymers vs. Conventional: Tm vsTg
[1]
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Biopolymers vs. Conventional: Shrinkage
[1]
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Index
» Introduction
» Motivation
» Biopolymers

» Applications
» Future

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Applications - Overview
[9]
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Applications - Overview
[9]
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Index
» Introduction
» Motivation
» Biopolymers

» Applications
» Future

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Acreage: Food vs. Polymeric materials
[9] modified
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Theoretical minimum and maximum yields per
acreage of Biopolymers
[9] modified
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Land use of Biopolymers
Necessary land use for

Annual polymers Annual biopolymer biopolymer production in
Arable land
production production in 2015 2015
[km2]
[106t] [106t] ( assumption 0,34 kt BP/km2)
[km2]
World 250 1.7 5000 15 million

EU 65 0.5 900 1.8 million
Germany 20 0.25 450 0.17 million
Lake
540
Constance
Full replacement of Full replacement of Full replacement of

Land used for the annual petrochemical based petrochemical based total petrochemical
biopolymer production in plastics in the plastics in the based plastics with
automotive industry with packaging industry with
2015: 0,03% of the world- biopolymers requires
biopolymers requires biopolymers requires
wide available land 4-5% of world-wide
0,3% of world-wide 2% of world-wide available arable land
available arable land available arable land
[9]
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Future
[9]
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Future – 3rd Generation
Biopolymers
I. Modifications (Blends, Additives)

II. Drop-in-solutions
(similar chem. Structure)
[9] modified
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References
[1]Endres, H. J.; Rath, A. S. Engineering Biopolymers – [9]Endres, H. J. IfBB- Institut für Biokunstoffe und
Markets, Manufacturing, Properties and Applications. Bioverbundwerkstoffe Hochschulu Hannover.
Hanser, 2011. Fakultät Maschinenbau und
[2]European Bioplastics. Driving the evolution of plastics. Bioverfahrenstechnik.Site: http://ifbb.wp.hs-
http://en.europeanbioplastics.org/wpcontent/uploads/201 hannover.de/downloads/index.php?site=Statistics&n
2/publications/Imagebroschuere_De 2012.pdf av=6-1-1-0-0
[3]Shen K, Haufe J, Patel MK. Product overview and market [10]Neváreza, L. M.; Casarrubiasb, L. B.; Cantoa, O. S.;
projection of emerging bio-based plastics. Final report of Celzardc, A.; Fierroc, V.; Gómeza, R. I.; Sáncheza,
Utrecht University to European Bioplastics 2009. G. G. Biopolymers-based nanocomposites:
[4]Chiou, B. S.; Glenn, G. M.; Imam, S. H.; Inglesby, M. K.; Membranes from propionated lignin and cellulose for
Wood, D. F.; Orts W. J. Starch Polymers: Chemistry, water puriﬁcation. Carbohydrate Polymers, Elservier,
Engineering, and Novel Products. In: Mohanty, A. K.; 2011.
Misra, M.; Drzal, L. T. Natural Fibers, Biopolymers, and [11]Biopolietileno baseado no etanol. Polímeros [online].
Biocomposites. Boca Raton: Taylor & Francis, 2005. V. 19, n. 2, 2009.
[5]Brito, G. F. Agrawal, P. Araújo, E. M. Mélo, T. J. A.
[12]Amates, A. A.; Barros, G. V.; Yamanishi, V. F.;
Biopolímeros, Polímeros Biodegradáveis e Polímeros
Furigo, A. Jr. Biopolímeros. UFSC, Florianópolis,
Verdes. Revista Eletrônica de Materiais e Processos,
2009.
v.6.2 (2011) 127-139. REMAP, 2011.
[6]Bastioli, C. Handbook of Biodegradable Polymers. [13]Site: Wikipedia/Polyurethane
Shawbury: Rapra Technology Limited, 2005. [14]Sandra I.; Rodriguez, S. I.; Roman, M. S.; Sturhahn,
[7]Belgacem, M. N. Gandini, A. The State of the Art. In: S. C.; Terry, E. H. Sustainability Assessment and
Belgacem, M. N.; Gandini, A. Monomers, Polymers and Reporting for the University of Michigan's Ann Arbor
Composites from Renewable Resources. Oxford: Campus. 2002.
Elsevier, 2008. [15]Ma,W.; Yuan, X.; Kang, C.; Su, T.; Yuan, X.; Pu, P.;
[8]Kaushika, A. Singhb, M. Vermaa, G. Green nanocomposites Sheng, J. Evaluation of blood circulation of
based on thermoplastic starch and steam exploded polysaccharide surface-decorated PLA
cellulose nanoﬁbrils from wheat straw. Carbohydrate nanoparticles. Carbohydrate Polymers, 2008.
Polymers, Elsevier, 2009.
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References
[16] Williams, S. F.; Martin, D. P.; Horowitz, D. M.; [25] Site:
Peoples, O. P. PHA applications: addressing the price http://www.bioplasticsmagazine.com/bioplasticsmagazi
performance issue I. Tissue engineering. International newAssets/docs/complete_issues/bioplastics1003.pdf
Journal of Biological Macromolecules, 1999. [26] Site: http://www.erp.se/pdf/GreenLine.pdf
[17] Chen, G. A microbial polyhydroxyalkanoates (PHA) [27] Site:
based bio- and materials industry. Chemical Society http://www.globalization101.org/uploads/Image/Energy
Reviews, 2009. /Graph-6-petroleum-natural-gas-formation
[18] Lu, D. R.; Xiao, C. M.; Xu, S. J. Starch-based [28] Site:
completely biodegradable polymer materials. http://www.besteurope.org/upload/BEST_images/envir
eXPRESS Polymer Letters Vol.3, No.6, 2009. onment/co2_cycle_ethanol
[19] Czaja, W. K.; Young, D. J.; Kawecki, M.; Brown, R. M. [29] Site: http://library.thinkquest.org/10aug-oracle-
Jr. The Future Prospects of Microbial Cellulose in 62/659780467/files/the_life_cycle_of_bioplastics_l_1.j
Biomedical Applications. American Chemical Society, pg
2007. [30] Site:
[20] Hoenich, N. Cellulose for medical applications: past, http://www.scottsmithonline.com/interests/medicalscho
present, and future. ncsu.edu/bioresources ol/biology/110a/Midterm1Materials/Notes/graphics/figu
[21] Sie: http://generon.co.uk re%25252003-02b.jpg
[22] Edgar, K. J. Cellulose esters in drug delivery. Springer, [31] Site:
2006. http://www.bbc.co.uk/schools/gcsebitesize/science/ima
ges/gcsechem_29.gif
[23] Shen, L.; Worrell, E.; Patel, M. Present and future
development in plastics from biomass. Biofuels, [32] Site:
Bioprod. Bioref. 4:25–40, 2010. http://www.designnews.com/document.asp?doc_id=24
3546&dfpPParams=ind_183,industry_auto,aid_24354
[24] Site: 6&dfpLayout=article
http://www3.braskem.com.br/upload/rao/2010/en/pdf/
[33] Site:
Braskem-ASR Complete.pdf
http://www.adream2012.eu/sites/default/files/styles/larg
e/public/material/45_d2.jpg
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References
[34] Site:
http://www2.dupont.com/Plastics/en_US/assets/edma
g/img092/ed09201d2.jpg
[35] Site: http://3.bp.blogspot.com/-
3vNSoz_U0wI/UDL4XkWfUqI/AAAAAAAAAAA/jC80y
VJB3MM/s1600/nylon.jpg
[36] Site: http://www.plasticsinfomart.com/wp-
content/uploads/2013/03/Mercedes-Benz-A-Class-
engine-cover-in-bio-based-polyamide-from-DSM.jpg
[37] Site:
http://www.vestamid.com/product/vestamid/en/market
s/electronics/cables/pages/default.aspx

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Renewable resources

 Structure and Production

© 2013 Renewable Resources Engeneering / Biopolymers

© 2013 Renewable Resources Engeneering / Biopolymers

“[…] polymer material that fulfills at least one of the following

© 2013 Renewable Resources Engeneering / Biopolymers

 World Commission on Environment and Development, 1987

“[…] is development that meets the needs of the present without

» use of new materials in construction

© 2013 Renewable Resources Engeneering / Biopolymers

 Structure and Production

© 2013 Renewable Resources Engeneering / Biopolymers

© 2013 Renewable Resources Engeneering / Biopolymers

 Structure and Production

© 2013 Renewable Resources Engeneering / Biopolymers

* Opep - 2013 [27]

 Are there some differences? – YES!!!

“[…] is ultimately influenced only by the chemical and physical

“[…] they decompose under exposure to microorganisms and/or

© 2013 Renewable Resources Engeneering / Biopolymers

» Primary and final degradation

» Increases fundamentally as the

Ratio: Heteroatom / carbon (in the main chain) [1]

» There are two types of degradable polymers:

• based on hydrocarbon monomers and oligomer (crude oil, natural gas,…)

© 2013 Renewable Resources Engeneering / Biopolymers

» Aerobic biodegradation ( aquatic or terrestrial )

Aerobic biodegradation Aerobic biodegradation Anaerobic

The tests are based:

» measurement of oxygen demand

 Definition of “ Bio-degradable polymers” : DIN EN 13432

“A material or materials mix and parts produced from it is considered

© 2013 Renewable Resources Engeneering / Biopolymers

Biodegradable Japan Compostable

» Examples: PU, POM, …

» Definition: method where two molecules combine to form a larger molecule,

» Components: Monomers containing at least two functional groups (i.e.

» Examples: Nylon, PCs, PEs and PET

» Definition: method monomers react to polymers by breaking the double

» Examples: PP, PE, PS, ….

 Structure and Production

© 2013 Renewable Resources Engeneering / Biopolymers

Polymer PVC PEAD PEBD PP PS PMMA PA PET PC

++ Total replacement , + Partial replacement, - Not replace

» Renewable sources: starch, sugar from

 Drug carriers [15]

» Commercial producers of PLA Module for hemodialysis Vascular prothesis

 Polymer that is intracellularly deposited by

© 2013 Renewable Resources Engeneering / Biopolymers

» Commercial producers of PHA

© 2013 Renewable Resources Engeneering / Biopolymers

 Starch: major source of energy

» Renewable sources: seeds of cereals

© 2013 Renewable Resources Engeneering / Biopolymers

 Food industry ( food packaging, edible

» Commercial producers of Starch

Regenerated cellulose and cellulose derivates; global

 Essentially cellulose that has been

Scanning electron microscopic image of bamboo viscose (left) compared with

 Treatment of Chronic Wounds and Burns

© 2013 Renewable Resources Engeneering / Biopolymers

 Cellulose ether  Cellulose ester

Additives to stabilize viscosity or as water binders in