Jean M. Hoffman
Senior Editor
Product designers have historically focused on performance
and how much it will cost to mold
parts when spec'ing engineering
resins. With FEA and CAE software, it's easy to narrow the field
of options based on mechanical,
thermal, and physical performance. But these tools won't tell
designers about the environmental footprint the various resins
(including fillers, additives, and
reinforcements) leave at the end
of a widget's useful life.
"Environmental responsibility requires that designers look at
the entire product cycle from basic feedstock to ultimate disposal
from a holistic point of view," says
Ramani Narayan, professor chemical & biochemical engineering at
Michigan State University. Biodegradability is a big part of biobased
polymers' appeal. These renewable resource-derived plastics (as
opposed to petroleum-based plastics) can be disposed of through
composting, soil application, and
biological wastewater treatment.
This makes them prime candidates
for use in short-life and disposable
consumer goods and packaging.
"To use them, however, designers
must engineer products so they
retain the material's biodegradability," says Narayan. "For durable
products, biobased materials are
also an option, but need to be engineered for performance and long
life which may impact how well the
material will biodegrade."
BIODEGRADABLE MATERIALS
"Biodegradation of natural materials (including biodegradable plastics) produce valuable compost as
the major product, along with water and CO2," says Narayan. "But the CO2 produced doesn't contribute to an increase in greenhouse
gases because it is already part of
the biological carbon cycle."
But polymers have historically
been designed to resist degradation as happens in a compost
heap. "The challenge," says Narayan, "is to design polymers that
have the necessary performance
during use, but destruct under
the stimulus of an environmental
trigger when discarded. The trigger could be microbial (anaerobic digestion). They could also
have hydrolytically or oxidatively
susceptible linkages built into
their polymer backbones or additives that catalyze polymer-chain
breakdown in specific environments (marine/ocean and soil)."
"Ideally, polymers should
break down in one or two growing
seasons and not leave any toxic
breakdown products. Most petroleum-based polymers don't pass
this test. Polyethylene (PE) or PEwax-coated paper products, for
example, are problematic in composting. The paper fully biodegrades but the PE or wax coatings
don't. "Paper products coated
with fully biodegradeable films
can provide water resistance and
tear strength comparable to PE
coatings," says Narayan. "And
will be completely biodegradeable and noninterfering in recycling operations.
DEGRADABLE VERSUS BIODEGRADABLE
"Making or calling a product
biodegradable or recyclable
has no meaning whatsoever if it
doesn't end up in a disposal infrastructure that uses biodegradability or recyclability features," says
Narayan. Recycling makes sense
if the recyclable product can be
converted into something useful.
"Likewise, biodegradable products make sense only if they go
into a disposal system that uses
biodegradation," says Narayan.
Disposal systems in this category
include composting, wastewater/sewage-treatment facilities,
and managed, biologically active
landfills (where methane landfill
gas gets harvested for energy).
There is an important distinction between products that degrade and those that biodegrade.
The problem is that products designed to degrade may break up
into small fragments which may
not biodegrade. "These degraded,
hydrophobic, high-surface-area
plastic residues migrate into the
water table and other compartments of the ecosystem to harm
the environment," says Narayan.
It has been reported that plastic debris can degrade into microscopic granular or fiberlike
fragments. These fragments have
been steadily accumulating in the
oceans. Research has shown that
marine animals consume microscopic bits of plastic. "The Algalita Marine Research Foundation
reports that degraded plastic residues can attract and hold hydrophobic elements like PCB and DDT
up to 1 million times background
levels," says Narayan. "The PCBs
and DDTs are at background levels in soil, and diluted out so as
to not pose significant risk. But
degradable plastic residues with
high surface area concentrate
these highly toxic chemicals, resulting in a toxic time bomb, a
poison pill floating in the environment posing serious risks." Fish,
for example, are not only exposed
to background PCBs in the water through skin and breathing,
they consume smaller fish and
insects also contaminated with
PCBs. This food chain "bioaccumulation" reportedly can magnify
PCBs up to a million times that
of background levels. Adverse
health effects from PCBs may include disruption of reproductive
function, neurobehavioral and developmental deficits in children,
and increased cancer risks.
Recently, continues Narayan,
Japanese researchers reported finding high concentrations of PCBs,
DDE (major metabolite of DDT),
and nonylphenols (NP) in degraded
polypropylene (PP) resin pellets collected from Japanese coasts.
"Designing hydrophobic polyolefin plastics like PE to be degradable, without ensuring that
microbial populations completely
assimilate the degraded fragments, poses more harm to the environment than if it was not made
degradable at all," says Narayan.
"Heat, moisture, sunlight, and/or enzymes shorten and weaken
polymer chains," continues Narayan. "This fragments the plastic and causes more cross linking
which, in turn, creates more intractable persistent residues."
ASTM TESTS
A formal life-cycle assessment
(LCA) of a product can give insights into disposal options. And
a new ASTM standard (D7075) has recently been published on
evaluating environmental performance of biobased products
using LCA methodology. ASTM
and other standards gauge biodegradability by measuring the
amount of CO2 given off during
composting. The CO2 is a direct
measure of the amount and rate
of microbial utilization (biodegradation) of the biopolymer.
"The biopolymer serves as the sole carbon source in a test system containing a microbially rich
compost in the presence of air
and under optimal temperature
conditions (preferably at 580°C
the temperature best suited for
thermophile organisms)," says
Narayan. "As carbon converts to
CO2, there is first a lag phase during which the microbial population adapts to the biopolymer.
Next, biodegradation begins as
the adapted microbial population
starts using the carbon for its cellular life processes and converts
carbon in the test material to CO2.
Finally, the output reaches a plateau when all of the substrate is
completely used."
MEASURING BIODEGRADABILITY
The ASTM has developed the
ASTM D6400 standard to cover
products claiming to be biodegradable via composting. It is intended to establish the requirements for labeling of materials
and products, including packaging made from plastics, as "compostable in municipal and industrial composting facilities." It determines if plastics and products
made from plastics compost satisfactorily, including biodegrading at a rate comparable to known
compostable materials (i.e., food
stuffs, lawn wastes, and paper).
The standard identifies three criteria: complete biodegradation,
disintegration, and safety.
Using the ASTM D5338-93 test
method will determine aerobic
biodegradation of plastic materials under controlled composting conditions. The plastic must
completely mineralize — convert
to CO2, water, and biomass via microbial assimilation. The plastic
is mixed with stabilized and mature compost derived from the organic fraction of municipal solid
waste. The net production of CO2 is recorded relative to a control containing only mature compost.
After determining the carbon
content of the test substance, the
percentage biodegradation is calculated as the percentage of solid
carbon of the test substance converted to CO2. In addition to carbon conversion, disintegration
and weight loss can be evaluated.
Sixty percent of single polymer
materials must mineralize in six
months. Polymer blends, copolymers, and plastics with low-molecular weight additives or plasticizers must show 90% biodegradability in the same time frame.
Materials in product form
must show intense microbial
activity. They must disintegrate
into fragments with less than 10%
of the material being caught on
2-mm sieves. Finally, after land
application, remaining materials
must not be toxic nor deter plant
growth. Regulated (heavy) metals
content in the polymer should be
less than 50% of EPA (U.S., Canada) prescribed threshold.
U.S. AND EUROPEAN STANDARDS
ASTM D6400 is in harmony
with standards in Europe, Japan,
Korea, China, and Taiwan. This
includes the European standard
EN13432 "Requirements for Packaging Recoverable through Composting
and Biodegradation – Test Scheme
and Evaluation Criteria for the Final
Acceptance of Packaging." The International Standards Organization
(ISO) is also developing a similar
standard ISO 17088, Specification
for Compostable Plastics.
BIOBASED POLYMERS
There are two basic ways of making polymers out of agricultural
feedstocks. The first is to directly extract natural polymer materials (cellulose, starch, proteins), fibers, and vegetable oils that can
form the platform on which polymer materials and products can
be developed. The second biomass feedstocks can be converted
to biomonomers by fermentation or hydrolysis. The biomonomers
can be further modified by biological or chemical means. The
biomonomers can be fermented to give succinic acid, adipic acid,
1,3-propane diol — precursor chemicals for the manufacture of
polyesters. Sorona polyestyer from DuPont, Wilmington, Del., for
example, is made from a bio 1,3-propane diol.
Biomonomers can be fermented to lactic acid, which is then
converted into poly (lactic acid) — currently commercialized by NatureWorks LLC, Minnetonka, Minn. Biomonomers can also be
microbially transformed to biopolymers including polyhydroxyalkanoates (PHAs).
Instead of microbial fermentative processes, chemical conversion of biomonomers yields intermediate chemicals including
ethylene, and propylene glycols. Vegetable oils offer a platform to
make a portfolio of polyols, lubricants, polyesters, and polyamides.
Likewise, an ozone mediated transformation of vegetable oils can
also produce polyols, urethane foams, polyesters, and polyamides.
Surfactants, detergents, adhesives, and water-soluble polymers can be engineered from biomass feedstocks.
Starch is a polymer of anhydroglucose and is one of the most
abundant renewable polymers found in nature. Cereal grains, primarily corn, are the major sources of starch. Plastic starch can
be synthesized by the use of appropriate plasticizers that break
the hydrogen bonds, and let the starch flow like a thermoplastic.
Through reactive compounding plastic starches with biodegradable polyesters films with excellent performance properties can be
made.
Modification of the starch-OH groups by esterification chemistry
is another method of making starch esters with thermoplasticity
and water resistance. Unmodified starch shows no thermal transitions except the onset of thermal degradation at around 2,600°C.
Starch acetate materials have shown a sharp glass transition (Tg) at
1,550°C and starch propionate has a Tg of 1,280°C.
Starch esters have much more water resistance than unmodified
starch. The starch-ester resin reinforced with biofibers has properties comparable to general-purpose polystyrene. Appropriately
formulated starch esters with plasticizers and other additives provide resin compositions that can be used to make injection-molded
products and for direct lamination onto Kraft paper. Starch acetates can undergo complete and rapid biodegradation. In the case
of starch triacetates, 70% of the carbon is reportedly converted to
CO2 at 580°C in 45 days.
Michigan State University (MSU) has developed a one step,
environmentally friendly extrusion process to manufacture foam
sheets and blocks for packaging. The foam is biobased, nontoxic,
and biodegradable. And is said to have comparable performance
as polyethylene-based foam in targeted applications and complies
with ISO 1401. After use, it can be composted in soil.
The MSU process uses water as the plasticizer and blowing
agent. Water and the shear imparted in the extrusion process helps
break the hydrogen bonds holding the starch molecules in the granule state. This releases the polymer chains without significantly
reducing the molecular weight of the amylose/amylopectin chains.
Nucleating agents and process aids control cell structure and maintain foam flexibility. Screws in the extruder control the foaming process. MSU's focus is to develop process parameters for making a
portfolio of foam products with varying cell structures, resiliences,
and barrier properties.
Green Cell foam sheets made by KTM Industries, Lansing, Mich.,
are used in cushion packaging and insulation. Based on successful
trials, they have been used for over 12 months by Toyota to ship automotive video entertainment systems, windshields, and end caps
without failing.
Ramani Narayan, Dept. of Chemical Engineering and Materials Science, MSU |
MAKE CONTACT
DuPont, (800) 441-0575, plastics.dupont.com
Innovia Films, (785) 379-0571,
innoviafilms.com
KTM Industries, (877) 938-6738,
ktmindustries.com
Nature Works LLC, (877) 423-7659,
www.natureworksllc.com