Sunday, March 9, 2008

Biodegradability Test

“Compatibility of the ISO standard 10708 (biodegradability test method) with the ultimate biodegradability requirements imposed through Annex III of Regulation 648/2004 of Parliament and of the Council”

EUROPEAN COMMISSION
HEALTH & CONSUMER PROTECTION DIRECTORATE-GENERAL
Directorate C - Public Health and Risk Assessment
C7 - Risk assessment

Adopted by the SCHER
during the 3rd plenary of 28 January 2005

ISO standard 10708

1. BACKGROUND

Annex III of Regulation 648/2004 lists a set of OECD / ISO test methods aiming at providing International standardised methodologies to quantify the ultimate biodegradability of surfactants in aerobic conditions.

The international ISO 10708 standard, not included in Annex III of Regulation 648/2004, aims to determine the ultimate aerobic biodegradability of organic compounds in an aqueous medium. This test method is apparently similar to the “closed bottle test” (OECD 301 D).

The Scientific Committee on Toxicology, Ecotoxicology and the Environment (CSTEE) already examined a request addressing a similar issue (ultimate test methods on biodegradability currently listed in Annex III, Regulation 648/2004) and adopted an opinion on “a proposed ready biodegradability approach to update detergent legislation” at its 12th plenary meeting of 25 November 1999.

According to Industry, ISO standard 10708 method provides an equivalent level on reliability compared to the other OECD test methods addressing the ultimately biodegradability features of surfactants (Annex III of Regulation 648/2004).

2. TERMS OF REFERENCE
The Scientific Committee on Health and Environmental Risks (SCHER) is requested to address this issue and give an opinion whether
1) the methodology and
2) the pass criterion
of ISO 10708 provide an equivalent level of reliability and stringency to the international test methods set out in Annex III of the Regulation 648/2004.

3. OPINION
3.1. Methodology
The biodegradability test method ISO 10708 was developed to have a relatively inexpensive and simple method for the ultimate aerobic degradability of poorly soluble chemicals. It was called BODIS (BOD of insoluble chemicals) or two-phase Closed bottle test, the latter because BOD bottles and an oxygen electrode are used like in the “Closed-Bottle-Test (OECD 301 D)”. One third of the bottle (headspace) acts as an oxygen reservoir. Consequently, higher test substance concentrations than in the “Closed-Bottle-Test (OECD 301 D)” can be used, as the oxygen concentration in the (saturated) medium is no longer the limiting factor for degradation. Concentrations of up to 100 mg COD/l can be weighed directly into the test flasks. The method was included in an OECD ring-test (OECD, 1989) which will be discussed under section 3.2.

The procedure and technical requirements of the ISO 10708 test are relatively simple. Considering the test conditions, the method is congruent with most of the biodegradability methods included in Annex III of Regulation 648/2004 in terms of the test medium, inoculum type and concentration, test duration, etc.(Table 1).


Table 1 - Comparison of the ISO 10708 test conditions and those included in Annex III of the Regulation 648/2004


Considering the test design, it is equivalent to the ISO 14593, test which is the reference method in the Annex III of the Regulation 648/2004 except for the detection parameter. Eisentraeger et al. (202) presents a combined biodegradation test system where both parameters are measured, the test results for 15 samples (poorly soluble lubricants, ester oil or mineral oil) after 28 days of incubation demonstrated that results obtained for both parameters are in a comparable range.

Overall, the ISO 10708 test is comparable in terms of the methodology to the tests described in Annex III of the Regulation 648/2004; combining in its methodological design elements of the reference method ISO 14593 and of other methods described in OECD 301. The reasons for not including this test in the OECD guideline 301 does not seem to be related to scientific issues but are rather of a managerial nature. In this context OECD (1989) states “The Set I Two Phase Closed-Bottle test does not appear to offer any significant advantages over the existing respirometric tests, being labour and space intensive”.

3.2. Pass criterion
There are three main sources of information allowing a comparison of the biodegradation results obtained with the ISO 10708 to those acquired by other ready biodegradation methods.

Ritcherich et al. (1998) compared biodegradation data from the “Two- phase closed bottle test” (BODIS test) and the OECD 301D (Closed Bottle test). 54 poorly soluble compounds were compared. For 46 % of the substances the ISO 10708 biodegradation was significantly higher (i.e., data differed ≥10% relatively to each other) than that observed in the Closed Bottle test; 7% of the substances degraded better in the Closed Bottle test and 44 % gave comparable results (difference less than 10%). Taking the 60 % BOD/COD pass criterion, for 83% of the substances the same conclusion on ready biodegradability was obtained, whereas for the remaining 17 % only the ISO 10708 test indicated readily biodegradability.

The CESIO (European Committee of Organic Surfactants and their Intermediates) has provided biodegradation test (OECD 301 D/F tests and ISO-10708) results for a set of anionic, cationic and non-ionic surfactants, allowing a comparative evaluation. The information was supplied by CESIO (Appendix 2) in tabular form without additional information and, therefore, the SCHER cannot confirm the quality and validity of the data.

Figure 1 presents a comparison of both methods. In general a relatively good linear correlation between both methods is observed. On average, the degradation value obtained in the BODIS test tend to be higher than in the OECD methods (as suggested by the slope of the line); for three out of 24 surfactants the differences in biodegradability were larger than 20%.

Figure 1 - Comparison of ISO 10708 and OECD 301D/F using degradation data on surfactants provided by CESIO (2004).

Using the biodegradability pass criterion of the 60% BOD/COD, comparison of the biodegradability test data of 24 surfactants shows that 21 compounds (88%) reached the same evaluation (14 above and 7 below the pass level) whereas 3 compounds (12%) only passed the ISO-10708 test.

A calibration exercise of methods for determining ready biodegradability was performed by the OECD in 1988 and a final report on the evaluation of these results was issued in 1989. This report compared the biodegradability data obtained for 4 organic compounds applying different OECD ready biodegradability tests (301B, 301C, 301 D and 301F) and the ISO 10708 test.

The variability inter- and intra-assays observed in the inter-calibration exercise was high, as expected for these biological assays. The results obtained in the OECD intercalibration exercise must be considered for putting into context the comparison presented in Figure 1. Similar levels of discrepancy were observed among other tests included in Annex III of the Regulation 648/2004 and even among laboratories conducting the same tests (OECD, 1989).

From the evaluation of the above mentioned studies and considering the observed variability, the biodegradation results obtained with the ISO 10708 are consistent (i.e., results in a similar final evaluation) with those obtained with the OECD ready biodegradability methods.

4. CONCLUSION
Referring to the terms of reference, the SCHER concludes that:
the ISO 10708 test is comparable in terms of the methodology to the tests described in Annex III of the Regulation 648/2004, and the ISO 10708 provides an equivalent level of reliability and stringency to the international test methods set out in Annex III of the Regulation 648/2004.

5. LIST OF ABBREVIATIONS
BOD Biological Oxygen Demand
CBT Closed Bottle Test (OECD 301 D)
COD Chemical Oxygen Demand
DOC Dissolved Organic Carbon

6. REFERENCES
CESIO (2004) Appendix 2: Comparison of Biodegradability Test Data. CESIO Oct 2004.
EisentrĂ€ger A., Schmidt M., Murrenhoff H., Dott W. and Hahn S. (2002) Biodegradability testing of synthetic ester lubricants – Effects of additives and usage, Chemosphere 48, 89-96.

OECD (1989) Ring test of methods for determining ready biodegradability, Final report, Paris, 1989.

Richterich K., Berger H. and Steber J. (1998) The ‘two-phase closed bottle test’ a suitable method for the determination of ‘ready biodegradability’ of poorly soluble compounds. Chemosphere 37 (2) 319-326.

7. ACKNOWLEDGEMENTS
Members of the working group are acknowledged for their valuable contribution to this opinion. The members of the working group are:

Prof. M. T. Garcia Ramon (external expert) Dr. S. Hahn (external expert), Prof. C. Janssen, Prof. J. Tarazona (rapporteur).

Sunday, March 2, 2008

Graft polymerization of acrylonitrile onto starch-coated polyethylene film surfaces (**)

Journal of Applied Polymer Science
Volume 89, Issue 12, Pages 3323-3328
Received: 8 October 2002; Accepted: 17 December 2002
Published Online: 1 Jul 2003
George F. Fanta (a) (*) , Frederick C. Felker (b), John H. Salch (a)
(a) Plant Polymer Research, National Center for Agricultural Utilization Research, United States Department of Agriculture, 1815 North University Street, Peoria, Illinois 61604-3999
(b) Cereal Products and Food Science Research, National Center for Agricultural Utilization Research, United States Department of Agriculture, 1815 North University Street, Peoria, Illinois 61604-3999

(*)Correspondence to George F. Fanta, Plant Polymer Research, National Center for Agricultural Utilization Research, United States Department of Agriculture, 1815 North University Street, Peoria, Illinois 61604-3999. email: George F. Fanta (fantagf@ncaur.usda.gov)
(**)Mention of a trademark, proprietary product, or vendor does not constitute a guarantee or warranty of the product by the U.S. Department of Agriculture and does not imply its approval to the exclusion of other products or vendors that may also be suitable.

Keywords: starch • polyethylene • acrylonitrile • polyacrylonitrile • graft copolymer

Starch-coated polyethylene (PE) films were prepared by immersing PE in a hot, jet cooked solution of starch. They were allowed to react with acrylonitrile (AN) in the presence of ceric ammonium nitrate initiator, and the graft polymerization that occurred produced starch-g-polyacrylonitrile (PAN) coatings that contained about 25 wt % grafted PAN. The starch-g-PAN coatings tightly adhered to the PE film surfaces. When grafted starch coatings were wetted with water and the surfaces vigorously rubbed, less than 20% of the coating was removed. The fact that PAN-grafted coatings were not removed with boiling water provided further evidence for their strong adherence. When starch was removed from the coating by acid hydrolysis, the residual grafted PAN still remained adsorbed on the PE surface. Because the grafted coating was completely removed by treatment with refluxing 0.7N sodium hydroxide, there is apparently no chemical bonding between starch-g-PAN and PE. The dimensional changes associated with the evaporation of water from these PAN-grafted coatings caused the films to curl during drying. Because the final shape of these coated films depends upon the presence or absence of water in the surrounding environment, these films may be considered to be a type of stimulus-responsive polymer. Attempts to graft polymerize methyl methacrylate and methyl acrylate onto starch-coated PE surfaces, under conditions similar to those used with AN, were unsuccessful. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3323-3328, 2003

Radiation-induced grafting polymerization of MMA onto polybutadiene rubber latex

Jing Peng (a), Maolin Wang (a), Jinliang Qiao (b) and Genshuan Wei (a)
(a) Department of Applied Chemistry, College of Chemistry, Peking University, Beijing 100871, PR China
(b) SINOPEC Beijing Research Institute of Chemical Industry, Beijing 100013, PR China

Abstract
The grafting of methyl methacrylate (MMA) onto polybutadiene rubber latex by the direct radiation method was carried out. The effects of monomer concentration, absorbed dose and dose rate of gamma rays on the grafting yield were investigated. The graft copolymers were characterized by transmission electron microscopy (TEM), FTIR spectroscopy, and differential scanning calorimetry. TEM photographs revealed that the core–shell structures of latex particles are formed at low MMA content, and with the increasing of MMA content, the semi-IPN-like structure with core–shell could be developed due to the high gel fraction of polybutadiene (PBD) seed particles. In addition, infrared analysis confirmed that MMA could be grafted onto PBD molecular chains effectively under appropriate irradiation conditions. The interfacial adhesion between PBD rubber (core) and PMMA (shell) phases could be enhanced with the increase of MMA concentration.

The writer can be reach by email : gswei@pku.edu.cn



Tuesday, February 26, 2008

The Printed Polyethylene Package-Degradable in Soil

By Dr. Rabindra Nath Ghosh

POLYMERS IN THE ROLE OF POLLUTION CREATOR

Biodegradation of natural macromolecules, e.g., celluloses and proteins was a concern during the 1930s. At the time, polymer research concentrated on prevention and retardation of attack on polymers by bacteria, fungi, insects and various atmospheric parameters like moisture, heat, etc. However from the late eighties, use of synthetic inert and bioresistant polymers reached such a high level that their disposal became a concern. It is realized that use of long-lasting polymers for short-lived applications can cause problems toward preservation of living systems. In the seas, plastic rubbish-ropes, nets, packs, etc.-chokes and entangles marine mammals. Plastic debris has a costly impact on waste management for municipalities. Recycling of conventional plastics is one way of reducing the problems associated with plastic waste. However, many packaging materials made of plastics do not lend themselves to recycling, owing to contamination with the contents of the pack along with the ink, and the necessary cleaning prior to recycling is expensive. Furthermore, reprocessing often leads to a downgrading of the polymer used and an increased hold-up in the system. A lack of markets for recycled polymers (mostly lower quality) has led to large stock piles and the dumping of waste products.


More....


The polyolefin-based plastics materials namely LDPE, HDPE, LLDPE, PP, etc., are widely used for packaging purposes in the rigid and flexible forms. An overview of current consumption level of polyethylene polymers in the world is given in Table 1



Out of 154 million tons of various polymers used, 54 million tons is from the polyethylene family, which is the largest share. More than 60% of 54 million. tons polyethylene polymer are consumed in making film to produce various flexible packages. There is already an explosion in environmental regulations, especially in the area of solid waste.2 The issue is not as much space to put the solid waste, but acceptable locations for the disposal. Legislation like "it should be the manufacturer's responsibility" does not solve the problem. We need plastic's properties, but it should not be at the cost of a burden to society and living.

POLYMER DEGRADATION
The history of developing biodegradable plastics to replace indestructible and landfill squatting plastics has been full of expectations and disappointments along with some success over the last 20 years. There are at least 15 companies worldwide who are engaged in commercial development of degradable plastics. The polyvinyl alcohol (PVOH) based plastic Depart from Environmental Polymers (EPG) USA, Polylactic acid (PLA) in the name of Chronopol from Monsanto, copolyesters Ecoflex from BASF, Biomax from DUPONT, Biopol from ICI, (a copolymer of polyhydroxybutyrate) and valeric acid (PHB/V), Eastar Bio from Eastman Mater-Bi (starch with PVA) and Novon (starch with additive) are some of the known commercial grades of biodegradable plastics.

The bioplastics industry suffers from two major obstacles. One is the product's much higher cost than that of petroleum derived plastics. The second one is lack of transparency in the nature of biodegradation. Although these PVOH, PLA, polyesters, PHB/V, cellophane etc. meet the requirements for biodegradability, they could not meet the required permeability to moisture, oxygen and other barrier properties besides the higher cost element of the film. Natural polymers or biopolymers are largely based on renewable resources such as starch, cellulose, proteins and pectins. Synthetic polymers are made from petroleum and other feedstocks. Conventional petrochemical-based materials are not easily degraded in the environment because of their high molecular weight and hydrophobic character-hence the need of recycling, incineration etc. With no real relief from recycling and incineration, biodegradation remains the ultimate goal. In general, naturally occurring polymers are more biodegradable than synthetic polymers. Polymers containing ester functionality, particularly aliphatic polyesters are potentially biodegradable. It is believed that biodegradation of these polymers proceeds by attack of the ester groups by nonspecific esterases produced by ground micro flora combined with hydrolytic attack. Products of the degradation can be quickly metabolized by microorganisms.

Polyethylene film, when blended with starch as a natural filler, biodeteriorates on exposure to a soil environment. The microbial consumption of the starch component leads to increased porosity, void formation and the loss of integrity of the plastic matrix.3,4 However, applications of starch blended polyethylene films were limited to trash or carry bags, etc. A multicolored printed plastic pack remains at a distance. Standards on biodegradable films have been developed or are under development by ASTM (USA), CEN (European), DIN (German), JIS (Japan) etc. to evaluate and quantify biodegradability under different environmental/disposal conditions like composting, soil, marine, etc.5,6 Toward printing and packaging these standards are yet to be developed in most cases.

USE OF POLYETHYLENE IN FLEXIBLE PACKAGING
Among the various plastics-both rigid containers and flexible packs, we have seen over the past four decades, the rapid penetration of LDPE (low-density polyethylene), HDPE (high-density polyethylene) and LLDPE (linear low-density polyethylene) in the carry bag market and flexible pouches. We are aware of huge day-to-day use for polyethylene films in the form of:

  • Colored and uncolored polybag for groceries, stationery shops and vegetable market
  • Black garbage bags
  • Bread bags
  • Hosiery/textile bags
  • Woven sacks
  • Household wrap film
  • Poly pouches, etc.

Besides above, there is industrial use of polyethylene film as lamination film, agriculture film, construction film, heavy-duty sacks, stretch/shrink films, etc.

All these applications of polyethylene have derived from excellent techno-commercial features of polyethylene family and improvements in film extrusion technology. Development in catalyst and polymerization process technology continues unabated with metallocene systems and the anticipation of "new generation" linear polyethylene's combining improved processability and physical properties. These developments created new product and market opportunities for the polyethylene converter.

OPTIONS FOR BIODEGRADABLE POLYETHYLENE
Though the general belief is in favor of using paper as an environmentally friendly biodegradable packaging material over plastic, the paper suffers from two-and-a-half time energy loss in its manufacturing, loss of trees from environment, hence spoiling soil bank and gaseous imbalance in atmosphere. On the above account, polyethylene is the choice, provided it can be made biodegradable and here comes starch blended LDPE film.

Out of the three major manufacturing routes of producing starch blended polyethylene film,(1) modified starch incorporation into polyethylene, (2) starch incorporation into modified polyethylene, and (3) blending of polyethylene and starch in presence of a coupling agent, the third method is reported to be cost effective. Some of the worldwide known manufacturers of such starch-LDPE biodegradable films are AMCO Plastics, USA; Novamont, Italy; Exxon Chemicals, Belgium, etc. Using low-density polyethylene (60 %), cornstarch (30 %) and additives (10%), the starch-blended polyethylene film has been produced. The novel proprietary coupling system developed by Maiti and coworkers7 resulted promising cost effective LDPE-starch blend film. Starch will be eaten by soil microorganisms in a landfill and therefore, the plastic matrix will be broken down into smaller particles.8 Such starch blended polyethylene film though produced in commercial scale, the film had inadequacy for printing and packaging applications. The ink anchorage on the starch blended polyethylene film is poor and inadequate. The regular practice of corona treating the LDPE-starch film surface did not result in ink anchorage onto the film.

GRAFTING AND CHARACTERIZATION OF GRAFTED LDPE - STARCH FILM
Grafting on LDPE - Starch Film LDPE-starch film under a stream of nitrogen gas was soaked with Ceric Amonium Nitrate (CAN) in acidic solution. After the excess CAN solution was drained out from the reaction flask and vinyl acetate was added dropwise on the film surface under constant sparging of nitrogen gas into the flask.9 The graft copolymerization was continued for three hours at 30 °C. After 3 hours, the film was washed thoroughly with water and acetone. The homopolymer, if formed, was removed completely with hot acetone (45 - 50 °C) for two to three hours. Finally, the grafted films were dried and weighed.

CHARACTERIZATION OF GRAFTED FILM
Characterization of the vinyl acetate grafted LDPE-starch film was done by measurement of percent grafting, haziness and color development on the film, UV-VIS Spectroscopy, X-ray diffraction, ATR-IR and Scanning Electron Microscope (SEM). Up to a maximum of 12% vinyl acetate grafting was carried out, when CAN concentration was at 0.912 moles/ litre. Since the objective is to develop better anchorage/printability without affecting the biodegradability of the LDPE-starch film, higher or extra-amount grafting was unwanted. Greater grafting is supposed to pile on the film surface, thereby decreasing the biodegradability. At 12% vinyl acetate grafting, the film has provided satisfactory printability and ink anchorage (which is reported in a subsequent part).

The UV-VIS spectra of the vinyl acetate grafted LDPE-starch film with absorption maxima at 209.5 nm is indicative of the extended coverage of vinyl acetate grafting onto starch-LDPE film. The ATR-IR spectra with the additional broad peak at 1747 cm-1 shows the presence of ester group of vinyl acetate grafted onto LDPE-starch film. From the X-ray diffractogram, it is seen that grafting of vinyl acetate onto LDPE-starch film does not change the overall shape of the diffraction pattern. The crystallinity of polyvinyl acetate grafted LDPE-starch film is higher than that of the ungrafted LDPE-starch film.

From the Scanning Electron Microscope (Figure 1), it is established that the surface of the LDPE-starch film becomes masked with grafted polymer. Thus grafting 10 of the vinyl acetate monomer onto starch blended LDPE film opened up the possibility of better surface characteristics of film to make it printable.

STUDIES OF POLYETHYLENE PRINT & LAMINATE PROPERTIES AND THEIR DEGRADATION IN SOIL
Polyethylene finds two major applications in making flexible packaging-one for surface printing where properties, e.g., printability, ink adhesion, gloss, solvent retention in the print, etc. have been studied. Besides surface printing properties, polyethylene films act as a sealable layer in polyethylene laminates for which laminate bond, heat sealability, solvent retention etc. have been studied.

Evaluation of film, print and laminate properties of vinyl acetate grafted LDPE-starch film (GBP) was done in comparison to that of prints on industrial standard corona-treated LDPE film (STP) and starch-blended LDPE film (SBP).

FILM SURFACE TENSION
Surface tension of the polyethylene films were measured by Visking solution using formamide and cellosolve mixture and contact angle following sessile drop method 11 with water and formamide as the probe liquids. The surface energy of GBP film, 40 dynes/cm was found to be as high as that of STP film, hence encouraging for printing purpose. Whereas the surface tension of SBP film is at 32 dynes/cm.


PRINT AND LAMINATE PROPERTIES
Two ink formulations were studied for surface printing on STP, SBP and GBP films. The print on STP was taken as an acceptable reference standard. Ink (1), which is predominantly based on co-solvent polyamide resin, phthalocyanine b blue pigment, and iso propyl alcohol, butyl alcohol solvents offers adhesion and satisfactory printability on GBP film. Whereas the SBP film does not provide the adequate anchorage. Proper adhesion ensures the color retention on the printed film. The improvement in ink adhesion is noticeable on print of GBP in comparison to print of SBP film, which shows the utility of vinyl acetate grafted surface. The ink (2), which is based on predominantly nitrocullulose resin, phthalocyanine b blue pigment, and ethyl alcohol, ethyl acetate solvents has shown satisfactory film surface wetting and printability. It is evident that the problem of poor adhesion on SBP film with ink (2) has been overcome by the vinyl acetate grafted surface of GBP.

Lower gloss level of both the inks (1) and (2) on SBP was caused by more porosity of the starch-blended surface of polyethylene, for penetration of resinous ink into the film. The higher gloss values 56.3 and 50.9 by Glossometer at 750 on prints of GBP film with inks (1) & (2), indicates the uniformity of film surface causing less penetration of ink resins into pores of the film and resulting in the desired higher gloss values. Comparison prints of SBP film had gloss values 29 & 32 of ink (1) & (2) respectively.

Higher solvent retention in the print is not a desirable packaging property. The lower the retained or entrapped value, the better it is. The very high solvent retention value 56.68 mgm/sm found in SBP is due to the presence of starch element in the film. However grafting with vinyl acetate in GBP caused lowering of solvent retention to a great extent at 29.97 mgm/sm, where solvent penetration was prevented by the grafted polyvinyl acetate layer on the film.

The polyester film was reverse printed with ink (3), based on vinyl chloride/vinyl acetate copolymer and ethlylene vinyl acetate copolymer resins, phthalocyanine b blue pigment and MEK & toluene solvents. The laminate made with polyester print and GBP film, had bond value of 500 g/15 mm, which is encouraging. The laminates of both SBP and GBP have shown higher solvent retention, which are attributed to starch and vinyl acetate components. The polyethylene films in both the laminates of SBP and GBP have shown sealability, which is a requirement for pouch making.

ISOLATION OF MICROORGANISMS FROM SOIL

The soil sample from the testing field was characterized for its types of microbes present. Microbial densities were determined by the dilution plate count technique.12 Soil (10 g) was suspended in sterile distilled water (90 ml) and shaken vigorously for 15 minutes. Appropriate series of 10 fold dilutions were performed and aliquots of 1ml were placed in petridishes containing different media. The plates were incubated at 30-32ÂșC for 10 days. Single isolated colonies were counted after 10 days of incubation and soil microbial population was calculated in terms of colony forming units per gram of soil. For bacteria, actinomycetes and fungi, nutrient agar, glycerol-asparagine agar and potato dextrose agar were used respectively. All media were sterilized by autoclaving at 15 psi for 15 minutes. The bacteria, microbes etc. present in the soil were thus evaluated (Table 2 ) by the culture of the soil.



SOIL BURIAL TESTS
What happens to plastics packaging that are dumped into landfill is very much debated. Landfill sites vary, and within any given site there can be considerable variation. Stories of 20-year-old newspapers still being legible and undecomposed carrots are still talked about and are attributable to low water availability. The various breakdown or degradation mechanism steps involving hydrolysis, solubilization, thermal degradation, oxidative degradation, mechanical degradation, photodegradation, biodegradation etc. are believed to operate simultaneously.
Microorganism, bacteria, fungi and algae are living catalysts, which help a large number of chemical processes to occur in water and soil. Fungi and bacteria decompose chemical compounds to simpler species and thereby drive the energy requirements for their growth and metabolism.

Krupp and Jewell studied biodegradability13 of following modified plastic films in controlled biological environments. Polyethylene with 6% ADM Starch, (AMCO Plastic Inc., USA), Biothene (Weisstech Corporation) with 6% starch in polyethylene matrix was reported to degrade in landfills. BIOPOL (Zeneca/ICI) and polyethylene with 10-12% starch (Eco-matrix Ltd.) are other examples. Their study concluded biodegradations in aerobic and anaerobic bioreactors.
Although biodegradation is rather simple and naturally occurring phenomenon, the various microorganisms, e.g., bacteria, fungi, actinomycetes etc., from natural sources (water, soil, air, etc.) are quite complex in their behavior and activity. Degradation of starch blended polyethylene in soil burial test have been studied and confirmed under various compost field environment.14,15 Hence there lies a necessity for the study of biodegradation of printed polyethylene films.

Similar to what happens in real life garbage, the printed films and laminates were put in soil burial test where soil based microorganisms and enzymes are active. A pit was dug and the soil of the pit was made free of dirts, stones, polymeric materials etc. The surface prints on STP, SBP and GBP of both the inks (1) and (2) and laminates of STP, SBP and GBP were kept at the bottom of the pit. The pit was filled up with loose, moist and soft soil. The prints and laminates were studied on their degradation at three months intervals for one year after digging the pit and taking out the prints and laminates.

Characterization of polymer degradation was done by studying the degree of degradation or loss in polyethylene. The photographs of the prints of ink (1) on STP, SBP and GBP after keeping in soil for three days and 12 months are shown in Figure 2 (STP/SBP/GBP). The STP prints do not show any loss of print color and polyethylene film. The prints on SBP show a number of pores, developed after six months and the pores have increased with time. The development of pores signals the disintegration of SBP film. The color of ink in general has been retained in the print. The prints on GBP also have shown the pores development, signaling the much-desired disintegration of the GBP film. The ink color of GBP print however has been retained like SBP print.

The physical changes on the prints of ink (2) on STP, SBP and GBP, after soil burial for three days and 12 months are shown in Figure 2. The ink (2) printed SBP and GBP films showed much removal or loss of colored print area in comparison to Ink (1) printed films. The cellulosic resin formulation of ink (2) has resulted in the desired greater loss of ink materials.

The polyester laminates with the three grades polyethylene films STP, SBP and GBP, after keeping in soil did not show any change and loss of laminate body. The ink color remained mostly unchanged in the laminates. However in the laminates of SBP and GBP, the polyethylene part have shown development of pores. The degradation of polyethylene in SBP and GBP prints and their laminates are significant which is a desired phenomenon. The soil burial test also clearly establishes the inertness of STP film toward degradation. In the laminates, the printed polyester film did not show any degradation.

CONCLUSION
The optimized nitrocellose based ink and grafted starch-LDPE combination lead to development of surface printed polyethylene package, where both ink resins and film degrade in soil burial conditions, whereas the conventional polyethylene and ink resins do not degrade. Since no degradation of polyester film (used in laminate of polyester and polyethylene) was noticed, work may be initiated to look into solution through alternative film, ink development and or newer packaging option for such laminates.

The novelty in the present investigation lies in the modification of the starch blended polyethylene film by vinyl acetate grafting and subsequent printing and biodegradability study of the printed film using optimized ink composition. There is tremendous scope for further investigation and development in this topic. The area of establishing the nature of degradation, identifying the microbe type and quantifying the degree of microbial attack demand special attention.

Dr. Rabindra Nath Ghosh can be reached via e-mai at rabin.ghosh@cal.coates.co.in

Correspondence: 49/1 P.B.SHAH ROAD, KOLKATA 700033, INDIA.

Biodegradation of polyethylene by the thermophilic bacterium Brevibacillus borstelensis

by. D. Hadad, S. Geresh, A. Sivan
Journal of Applied Microbiology Volume 98 Issue 5 Page 1093-1100, May 2005
Abstract

Aim: To select a polyethylene-degrading micro-organism and to study the factors affecting its biodegrading activity.

Methods and Results: A thermophilic bacterium Brevibaccillus borstelensis strain 707 (isolated from soil) utilized branched low-density polyethylene as the sole carbon source and degraded it. Incubation of polyethylene with B. borstelensis (30 days, 50°C) reduced its gravimetric and molecular weights by 11 and 30% respectively. Brevibaccillus borstelensis also degraded polyethylene in the presence of mannitol. Biodegradation of u.v. photo-oxidized polyethylene increased with increasing irradiation time. Fourier Transform Infra-Red (FTIR) analysis of photo-oxidized polyethylene revealed a reduction in carbonyl groups after incubation with the bacteria.

Conclusions: This study demonstrates that polyethylene – considered to be inert – can be biodegraded if the right microbial strain is isolated. Enrichment culture methods were effective for isolating a thermophilic bacterium capable of utilizing polyethylene as the sole carbon and energy source. Maximal biodegradation was obtained in combination with photo-oxidation, which showed that carbonyl residues formed by photo-oxidation play a role in biodegradation. Brevibaccillus borstelensis also degraded the CH2 backbone of nonirradiated polyethylene.Significance and Impact of the Study: Biodegradation of polyethylene by a single bacterial strain contributes to our understanding of the process and the factors affecting polyethylene biodegradation.

Monday, February 25, 2008

Miscellaneous biopolymers & biodegradation of synthetic polymers

STEINBUCHEL Alexander

Biopolymers. Volume 9

Publication date : 10-2002

Description
Biopolymers represent the most abundant organic compounds in the biosphere and constitute the largest fraction of cells. Seven main classes of biopolymers are distinguished according to their chemical structures. This encyclopedia provides a thorough overview of the occurrence and metabolism of biopolymers. In addition, processes for biotechnological production, isolation from organisms and modification, material properties and technical applications in various areas such as, for example, in daily life products, medicine, pharmacy, food industry, agriculture, textiles, chemical industry and packaging industry are provided. The future perspectives of biopolymers are outlined. In its first part Volume 9 focusses on biosynthesis, metabolism, biodegradation, functions, properties and applications of miscellaneous polymers such as hemozoin, thymine-containing styrene polymers, polythioesters, polyphosphate, polyhydroxymethionine, polyketides, natural polyacetals. The biodegradation of a wide range of synthetic polymers is treated in the second part of the volume, e.g. substituted cellulose, nylon, polycarbonate, polyvinyl alcohol, polyurethanes, polystyrenes, polyethylene, polyanhydrides.

Summary
Hemozoin: a Biopolymer Synthesized During the Degradation of Hemoglobin Thymine Containing Styrene Polymers as Environmentally Benign Photoresists Polythioesters Metabolism of Natural Polymeric Sulfur Compounds Polyphosphate Polyhydroxymethionine Polyketides Natural Polyacetals Biodegradation of Substituted Cellulose Biodegradation of Nylon and other Synthetic Polyamides Biodegradation of Polycarbonate Biodegradation of Polyethers of PHA synthesis Biodegradation of Polyvinyl Alcohol and its Copolymers Biodegradation of Polyacrylic Acid and Related Polymers Biodegradation of Polyurethanes Biological Susceptibility of Polystyrenes Biodegradation of Polyethylene and Related Polymers Biodegradation of Polyanhydrides Biodegradation of Silicon and Organosiloxanes Biodegradation of Poly(alkylcyanoacrylate) Biodegradation of Polyphosphazenes Biodegradation of Polydioxanone Biodegradation of Polysaccharides.

Biodegradable Polymers

Source: Materials World Vol. 7 no. 3 pp. 135-36 March 1999.

Background
There was a time no so long ago, when people would throw food scraps, peelings and the like into the compos heap in the back corner of their garden. The rest of the household rubbish went into the dustbin in plastic sacks. Since those days, things have changed. Now you can feed the compost heap with the plastic sacks too. British company Symphony Environmental is producing fully degradable bin bags, carrier bags and other plastic bags from polyethylene, using new additive technology to reduce the plastic to carbon dioxide and water in just a few weeks.

Degradable Polyethylene
Symphony's material is the first example of 100% degradable polyethylene. The plastic, known as SPITEK, has the same mechanical properties and processing characteristics as regular polyethylene and so can be used in the same way to make products. However, it has a special ingredient - up to 3% of a degradable compostable plastic (DCP) additive made under license from its developers EPI. This additive acts as a catalyst for the degradation of the polyethylene, kick starting the process when conditions dictate.

The Need for a Fully Degradable Plastic
The need for a fully degradable plastic is pressing. Millions of tonnes of plastic waste, including refuse sacks, carrier bags and packaging, are buried in landfill sites around the world each year. China generates about 16 million tonnes, India 4.5 million tonnes and the UK 1 million tonnes, of which more than 800,000 tonnes is waste polyethylene. Other disposal routes are possible for these materials, such as recycling and incineration, but as much of the waste plastic is mixed up with other materials in the domestic and industrial waste streams, separation is costly particularly for small items such as carrier bags.

Conventional Polyethylene
Conventional polyethylene products can take longer than 100 years to degrade, taking up valuable landfill space and potentially preventing the breakdown of biodegradable materials contained, say, in a refuse sack.

Effect on Landfill Sites
Symphony claims that its new plastic could effectively increase the capacity of landfill sites by as much as 20 to 30% by breaking down in a short time and allowing other materials to degrade.

Degradation Properties
The SPI-TEK material can be engineered to degrade in as little as 60 days or as long as 5 to 6 years, depending on the application. The level of the proprietary EPI DCP additive effectively determines the rate of degradation and the shelf life of products made from the polyethylene. Degradation is initiated by a number of factors - sunlight, heat and stress from pulling and tearing can all start the process, which then continues even if the material is in landfill or under water.

How the Degradation Process Works
The catalyst causes carbon-carbon bonds in the polyethylene backbone to be broken, reducing the molecular weight and durability of the material. Tests have shown a reduction in molecular weight from a quarter of a million to less than 4,000, at which point the material can be digested by microorganisms in the soil and water. The final products of the degradation process are simply carbon dioxide and water. The DCP additive is neither water soluble nor toxic, making the material safe for disposal in landfill sites such as the flushing bio-reactor systems that are widely used in the UK. These systems introduce pressurised water flows into the layers of waste material, feeding oxygen and microorganisms down to the degrading rubbish.

The material will also degrade under other conditions, not just in the composting-type conditions of a landfill site. Figure 1 shows the effect of photo and thermal degradation on a carrier bag made from the new polyethylene compared to standard plastic, The bag degrades to mulch in just 55 days. Extensive tests such as this one and tests on buried material were carried out on the new polyethylene to prove its degradability, including testing with Pira International.

Applications
Symphony intends to launch a wide range of products made from its new polyethylene, including everything from small produce bags and carrier bags to larger packaging items and products such as degradable plastic aprons for children. The possibilities are great for the new material because it has the same performance as conventional polyethylene and yet doesn't have any cost restrictions on its use. Refuse sacks are already on the market under the Tuffy brand name, promoting the material's environmental credentials. The bags come with a list of ‘do’s and 'don’ts’ on the label advising users how to store the bags and so prevent premature degradation. Apart from that, they are exactly the same as any other refuse sacks.

Biodegradable Polyester Amide
Of course, Symphony Environmental is not the only company producing new materials that could end their lives on the compost heap. Bayer is currently testing a new polyester amide biodegradable plastic that it claims is 100% biodegradable and recyclable, and yet also has excellent properties including a high tensile strength. The plastic has additional green credentials as it is produced without solvents, chlorine or any aromatic ingredients.

BAK 1095 is a semi-crystalline, largely transparent thermoplastic that breaks down into carbon dioxide, water and biomass under composting conditions. Its degradation rate is comparable to that of other organic materials that are composted, and yet its physical properties are similar to those of typical polyolefins such as LDPE. Bayer says that the plastic is suitable for a number of processes, such as film blowing, extrusion, thermoforming, spinning, injection moulding, blow moulding, colouring, printing, hot sealing and welding. It suggests that potential applications will be in areas such as horticulture, agriculture or the food sector, in which plastics must be used in conjunction with compostable waste.

Summary
Clearly there is some way to go before these new degradable materials gain a large enough share of the market to make a significant impact on the amount of waste plastic hanging around and therefore the space available in landfill sites. But Symphony sees huge potential for its products to replace polyethylene in traditional applications for the plastic, so consumers can expect to see more products boasting ‘full degradability’ in the coming months and years.All of which is good news for the environment and good news for owners of compost heaps, whose only problem in the future might be finding a garden big enough to take all their plastic degradables.

Saturday, February 23, 2008

Preliminary Degradation of Plastics:

Evaluation and Testing
W. Lamar Miller, PhD
University of Florida

State University System of Florida
FLORIDA CENTER FOR SOLID AND HAZARDOUS WASTE
MANAGEMENT
2207 NW 13 Street, Suite D
Gainesville, FL 32609

Report #9l-2, May 1991


EXECUTIVE SUMMARY
The primary objective of this study was to evaluate the degradation of commercial polyethylene and polystyrene as a function of their exposure to various environmental conditions selected to enhance photodegradation and biodegradation. The plastics selected for these studies were consumer products and were not classified as degradable by the manufacturers. The consumer products used were polyethylene freezer bags of 0.7 mils thickness and bags of 1.75 mils thickness. The foamed polystyrene products tested were hot drink cups and picnic plates. Samples from these products were exposed to environmental conditions at the following sites: IFAS roadside, IFAS wetlands, IFAS submerged, beach roadside, beachfront, beach intertidal, beach submerged, 35 degree anaerobic digester, 55 degree anaerobic digester, yard waste compost and municipal compost.

The amount of degradation which occurred in polystyrene samples was determined based on the loss of molecular weight of the sample, the loss of flexural strength of the material and the loss of tensile strength. Polyethylene degradation was measured by determining the loss of tensile strength of the material.

Degradation of the polyethylene bags varied with material thickness, orientation induced during manufacture and exposure site. The samples which showed the most significant loss in elongation to break were those exposed at the beachfront, beach roadside and IFAS roadside locations. At these sites, over 75% of the original elongation was lost after eight weeks of exposure for the 1.75 mil thickness, and over 98% for the 0.7 mil. Samples with the least amount of degradation had less than 40% loss of elongation at 120 days for the 1.75 mil material, and generally less than 55% loss for the 0.7 mil. These sites were the IFAS submerged and floating locations, beach submerged and digester exposures. The loss of elongation for the samples placed in anaerobic digesters averaged less than 10%. The 0.7 mil material showed a greater tendency to lose elongation ability than did the 1.75 mil. An edge effect appeared to be observed during the testing, but could not be correlated from available data. However, this effect could indicate that some portion of the observed tensile strength loss is a result of accelerated decomposition of the exposed edges of the polyethylene films.

Degradation of foamed polystyrene varied by type of product and exposure location. Gel permeation chromatographic analysis indicated that more than 20% of the average molecular weight value was lost after 120 days for picnic plates and cups at the IFAS roadside, beach intertidal, beachfront and IFAS floating locations. This was also true for cups at the beach roadside site.

The flexural strength of the foamed polystyrene materials was determined by utilizing four point bending analysis. The foamed polystyrene materials would rarely actually fracture or rupture prior to the ASTM specified strain value for test termination. For the plates, failure occurred by creases forming at or near the loading points. A significant loss in flexural strength was observed for the IFAS roadside, beach roadside and beachfront locations.

An 80% loss in flexural strength occurred after only 720 hours (30 days) of exposure for samples in each of these locations. For the cups, neither creasing or actual rupture of the material occurred frequently. None of the exposed samples showed a significant loss in flexural strength after 120 days.
The tensile strength of the polystyrene materials showed the most significant change at the beachfront, beach roadside and IFAS roadside locations. The plates and cups at these locations lost approximately 40% of their original tensile strength after 120 days. Other exposure sites did not show a significant loss in tensile strength.

This report concludes that the loss in tensile properties and molecular weight of foamed polystyrene consumer products of the nature tested did not occur at a rate that would result in degradation of the materials under common exposure conditions. Loss of tensile properties may occur sufficiently rapidly in very thin films of unstabilized polyethylene, but this rate of degradation diminishes rapidly with thicker materials.

No significant degradation was observed to take place in either polyethylene or foamed polystyrene by a biological pathway in this study. Essentially all of the tensile loss observed is attributed to either mechanical loss or photolytic degradation, but in no case is it concluded that the samples tested would qualify to be determined as environmentally degradable within the context of the Florida statutes.

Thin film polyethylenes and materials such as a sensitized foamed polystyrene are available in commercial quantities and may be sufficiently degraded by exposure to sunlight to meet degradability standards. The more important question, however remains, what is degradable.
The regulatory agencies will have to define the term in terms of physical and chemical parameters which can be reproducibility measured, and in terms which can result in reproducible exposures. Requiring outdoor exposures gives rise to many uncontrolled parameters. Relying on tensile properties results in too much variation as a function of manufacturers methods. These and other variables need to be addressed before the term "degradable plastic" will have real meaning.
At the time of the initiation of this study there were no promulgated rules governing exposure and testing of the materials. The Florida Department of Environmental Regulation has since that time issued rules on testing of polyethylene (FAC 17-707).

The limited term of this study did not allow development of appropriate test procedures or definitions of degradation. This study was expected to be a preliminary study in that effect.

Marketing Environmentally Degradable Plastic Products

Heritage Bag Company
by Frank Ruiz

The topic of degradable plastics in their various forms continues to be in the news. Oakland recently copied the San Francisco ordinance requiring bags to be reusable or compostable. Other cities around California specifically and the U.S. in general are considering similar legislation.

It is of concern to this author that these laws will serve as a “de-facto” ban on polyethylene bags as the volume of truly compostable plastics film-grade plastics currently is not sufficient to meet the demand should every municipality considering this type of legislation enact it.

As a general rule, whenever the demand for a product exceeds its supply, mayhem is the result. It will vary in degree depending on whether we are waiting in line to fill the gas tank of our automobile (for those of us who remember the 70’s), stocking up on bottled water, plywood, and batteries before a tropical storm, or trying to buy milk and bread before an ice storm here in Texas.

The “demand” for degradable plastics in the late 1980’s resulted in companies supplying resin, film, and bags made from cornstarch-filled polyethylene. We were assured these bags were biodegradable. Objective testing by independent researchers proved they were not.

Once again we are in a situation where there is a demand for degradable plastics. A variety of claims are being made about the ability of products to break down in different environments, whether it be in a compost pile, a landfill, or littered along the highway. Before buying into a supplier’s claim (and/or buying their product), it may be helpful to determine what problem you are trying to solve (other than a customer’s demands), what options you have, and what hazards may lie ahead if you are not careful.
California Law and ASTM Definitions
California law AB 2147 requires that any package labeled as degradable, biodegradable, or compostable unless the container meets the current American Society for Testing and Materials (ASTM) standard specification for the term used on the label. In ASTM D 6400 each of these terms is defined as follows:

Degradable plastic – a plastic designed to undergo a significant change in its chemical structure under specific environmental conditions, resulting in a loss of some properties that may be measured by standard test methods appropriate to the plastic and the application in a period of time that determines its classification.

Biodegradable plastic – a degradable plastic in which the degradation results from the action of naturally occurring microorganisms such as bacteria, fungi, and algae.

Compostable plastic – a plastic that undergoes degradation by biological processes during composting to yield carbon dioxide, water, inorganic compounds, and biomass at a rate consistent with other known compostable materials and leaves no visible, distinguishable or toxic residue.
In order to be identified as compostable, plastic products must also meet the following requirements detailed in ASTM D 6400:
  • be converted to carbon dioxide and water under the environmental conditions of temperature, oxygen, moisture, and biological activity measured using ASTM Test Method D 5338. For products consisting of a single polymer, 60% of the organic carbon must be converted to carbon dioxide within 180 days. For products consisting of more than one polymer, 90% of the organic carbon must be converted to carbon dioxide within 180 days.
  • fragment so that no more than 10% of its original dry weight remains after sieving on a 2-mm sieve,
  • pass the requirements of ASTM Guide D 6002 or OECD Guideline 208 which test its effect on plant seed germination, and
  • have concentrations of heavy metals less than 50% of those prescribed in 40 CFR Part 503.13.

If the plastic product does not meet all of these requirements, it cannot be labeled as “compostable.” Suppliers whose raw materials are compostable will have data that not only demonstrates the compliance of their products to these requirements, but will know the limitations of their technology, such as maximum thickness at which the requirements can be met, the maximum storage or service temperatures, its barrier properties, or if their material is safe for food contact.

U.S. Federal Trade Commission (FTC)
Other important considerations are the guidelines published by the U.S. Federal Trade Commission. The FTC became involved with this issue in the late 1980’s when a number of companies claims of biodegradability turned out to be bogus. The following information is taken from their website (http://www.ftc.gov/bcp/conline/pubs/buspubs/epaclaims.htm) on the application of the terms commonly used in descriptions of degradable plastics:


Excerpt from the Guides on use of terms "degradable," "biodegradable" and "photodegradable" It is deceptive to misrepresent, directly or by implication, that a product or package is degradable, biodegradable or photodegradable. An unqualified claim that a product or package is degradable, biodegradable or photo-degradable should be substantiated by competent and reliable scientific evidence that the entire product or package will completely break down and return to nature, that is, decompose into elements found in nature within a reasonable short period of time after customary disposal.
Claims of degradability, biodegradability or photodegradability should be qualified to the extent necessary to avoid consumer deception about: (a) the product or package's ability to degrade in the environment where it is customarily disposed; and (b) the rate and extent of degradation.

So merely claiming your bag is “degradable” without any qualification could land you “in the cross-hairs” of the FTC. If you do claim degradability, you should qualify your statements as to the environment required to effect product degradation, and have the scientific test data ready to back up your claims (saying “my supplier told me” probably won’t do).

The FTC goes on to give specific examples of allowable and deceptive claims. The following are taken from their website http://www.ftc.gov/bcp/grnrule/guides980427.htm and are fairly self-explanatory:

Claims of degradability, biodegradability or photodegradability should be qualified to the extent necessary to avoid consumer deception about: (1) the product or package's ability to degrade in the environment where it is customarily disposed; and (2) the rate and extent of degradation.


Example 1:
A trash bag is marketed as "degradable," with no qualification or other disclosure. The marketer relies on soil burial tests to show that the product will decompose in the presence of water and oxygen. The trash bags are customarily disposed of in incineration facilities or at sanitary landfills that are managed in a way that inhibits degradation by minimizing moisture and oxygen. Degradation will be irrelevant for those trash bags that are incinerated and, for those disposed of in landfills, the marketer does not possess adequate substantiation that the bags will degrade in a reasonably short period of time in a landfill. The claim is therefore deceptive.

Example 2:
A commercial agricultural plastic mulch film is advertised as "Photodegradable" and qualified with the phrase, "Will break down into small pieces if left uncovered in sunlight." The claim is supported by competent and reliable scientific evidence that the product will break down in a reasonably short period of time after being exposed to sunlight and into sufficiently small pieces to become part of the soil. The qualified claim is not deceptive. Because the claim is qualified to indicate the limited extent of breakdown, the advertiser need not meet the elements for an unqualified photodegradable claim, i.e., that the product will not only break down, but also will decompose into elements found in nature.

Example 3:
A soap or shampoo product is advertised as "biodegradable," with no qualification or other disclosure. The manufacturer has competent and reliable scientific evidence demonstrating that the product, which is customarily disposed of in sewage systems, will break down and decompose into elements found in nature in a short period of time. The claim is not deceptive.

Example 4:
A plastic six-pack ring carrier is marked with a small diamond. Many state laws require that plastic six-pack ring carriers degrade if littered, and several state laws also require that the carriers be marked with a small diamond symbol to indicate that they meet performance standards for degradability. The use of the diamond, by itself, does not constitute a claim of degradability.

So if you are going to claim your bag or packaging is going to break down in a landfill within two years, you or your supplier had better bury it in a landfill, go back two years later, dig into the area it was dumped, and conclusively prove it is gone! (May I suggest you bury a few newspapers along with the samples from the day you started the testing for an accurate date reference).

The FTC has also published more detailed guidelines for claiming compostability of your product. Merely meeting the requirements of ASTM D 6400 or AB 2147 is not sufficient.

(c) Compostable: It is deceptive to misrepresent, directly or by implication, that a product or package is compostable. A claim that a product or package is compostable should be substantiated by competent and reliable scientific evidence that all the materials in the product or package will break down into, or otherwise become part of, usable compost (e.g., soil-conditioning material, mulch) in a safe and timely manner in an appropriate composting program or facility, or in a home compost pile or device. Claims of compostability should be qualified to the extent necessary to avoid consumer deception. An unqualified claim may be deceptive if: (1) the package cannot be safely composted in a home compost pile or device; or (2) the claim misleads consumers about the environmental benefit provided when the product is disposed of in a landfill. A claim that a product is compostable in a municipal or institutional composting facility may need to be qualified to the extent necessary to avoid deception about the limited availability of such composting facilities.

Example 1:
A manufacturer indicates that its unbleached coffee filter is compostable. The unqualified claim is not deceptive provided the manufacturer can substantiate that the filter can be converted safely to usable compost in a timely manner in a home compost pile or device. If this is the case, it is not relevant that no local municipal or institutional composting facilities exist.

Example 2:
A lawn and leaf bag is labeled as "Compostable in California Municipal Yard Trimmings Composting Facilities.'' The bag contains toxic ingredients that are released into the compost material as the bag breaks down. The claim is deceptive if the presence of these toxic ingredients prevents the compost from being usable.

Example 3:
A manufacturer makes an unqualified claim that its package is compostable. Although municipal or institutional composting facilities exist where the product is sold, the package will not break down into usable compost in a home compost pile or device. To avoid deception, the manufacturer should disclose that the package is not suitable for home composting.

Example 4:
A nationally marketed lawn and leaf bag is labeled "compostable.'' Also printed on the bag is a disclosure that the bag is not designed for use in home compost piles. The bags are in fact composted in yard trimmings composting programs in many communities around the country, but such programs are not available to a substantial majority of consumers or communities where the bag is sold. The claim is deceptive because reasonable consumers living in areas not served by yard trimmings programs may understand the reference to mean that composting facilities accepting the bags are available in their area. To avoid deception, the claim should be qualified to indicate the limited availability of such programs, for example, by stating, "Appropriate facilities may not exist in your area.'' Other examples of adequate qualification of the claim include providing the approximate percentage of communities or the population for which such programs are available.

Example 5:
A manufacturer sells a disposable diaper that bears the legend, "This diaper can be composted where solid waste composting facilities exist. There are currently [X number of] solid waste composting facilities across the country.'' The claim is not deceptive, assuming that composting facilities are available as claimed and the manufacturer can substantiate that the diaper can be converted safely to usable compost in solid waste composting facilities.

Example 6:
A manufacturer markets yard trimmings bags only to consumers residing in particular geographic areas served by county yard trimmings composting programs. The bags meet specifications for these programs and are labeled, "Compostable Yard Trimmings Bag for County Composting Programs.'' The claim is not deceptive. Because the bags are compostable where they are sold, no qualification is required to indicate the limited availability of composting facilities.

In summary; before you market a “degradable” product,
1. have a firm understanding of the intended application,
2. under what environmental conditions it will have to degrade,
3. what use and storage temperatures to which it will be subjected,
4. what data your supplier has to support their claims, and
5. what you can claim without becoming the subject of unwanted inquiries by concerned government agencies.

Here’s to doing our part to protect the environment!


# # #

Frank Ruiz is technical director at the Heritage Bag Comopany in Carrolton, Texas. He began his career in the polyolefins industry as a film product development engineer at the Union Carbide Bound Brook Technical Center in October 1979. Frank joined the Heritage organization in May 1986, and serves as technical director for both the Heritage Bag can liner business and the Heritage Plastics compounding facility. He received a BS in chemistry from MIT in May 1976.

Biodegradable Polymers:

Past, Present, and Future

M. Kolybaba (1), L.G. Tabil (1), S. Panigrahi (1), W.J. Crerar (1), T. Powell (1), B. Wang (1)
(1) Department of Agricultural and Bioresource Engineering
University of Saskatchewan
57 Campus Drive, Saskatoon, SK, CANADA S7N 5A9


Written for presentation at the
2003 CSAE/ASAE Annual Intersectional Meeting
Sponsored by the Red River Section of ASAE
Quality Inn & Suites
301 3rd Avenue North
Fargo, North Dakota, USA
October 3-4, 2003


Abstract. In recent years, there has been a marked increase in interest in biodegradable materials for use in packaging, agriculture, medicine, and other areas. In particular, biodegradable polymer materials (known as biocomposites) are of interest. Polymers form the backbones of plastic materials, and are continually being employed in an expanding range of areas. As a result, many researchers are investing time into modifying traditional materials to make them more user-friendly, and into designing novel polymer composites out of naturally occurring materials. A number of biological materials may be incorporated into biodegradable polymer materials, with the most common being starch and fiber extracted from various types of plants. The belief is that biodegradable polymer materials will reduce the need for synthetic polymer production (thus reducing pollution) at a low cost, thereby producing a positive effect both environmentally and economically. This paper is intended to provide a brief outline of work that is under way in the area of biodegradable polymer research and development, the scientific theory behind these materials, areas in which this research is being applied, and future work that awaits.

Keywords: biopolymer, biodegradable, plastic, agricultural products, biomaterial, recycling, life cycle assessment, environmental impact, economic impact, compost

Introduction
The development of innovative biopolymer materials has been underway for a number of years,
and continues to be an area of interest for many scientists. In 1996, shipments from the Canadian Plastic Industry increased by 10.6% from 1995 levels (Charron 1999), to $9.1 billion. Fomin (2001) reported that the end of the 20th century saw the worldwide production of synthetic plastics reach 130 million t/year, while the demand for biodegradable plastics is reported to be growing by 30% each year (Leaversuch 2002). European countries have reported an estimated average usage of 100kg of plastic per person each year (Mulder 1998).

Synthetic plastics are resistant to degradation, and consequently their disposal is fuelling an international drive for the development of biodegradable polymers. As the development of these materials continues, industry must find novel applications for them. Material usage and final mode of biodegradation are dependent on the composition and processing method employed. An integrated waste management system may be necessary in order to efficiently use, recycle, and dispose of biopolymer materials (Subramanian 2000). Reduction in the consumption of sources, reuse of existing materials, and recycling of discarded materials must all be considered.

Polymer materials are solid, non-metallic compounds of high molecular weights. (Callister 2000). They are comprised of repeating macromolecules, and have varying characteristics depending upon their composition. Each macromolecule that comprises a polymeric material is known as a mer unit. A single mer is called a monomer, while repeating mer units are known as polymers. A variety of materials (both renewable and non-renewable) are employed as feedstock sources for modern plastic materials. Plastics that are formed from non-renewable feedstocks are generally petroleum-based, and reinforced by glass or carbon fibers (Williams et al. 2000). Renewable resource feedstocks include microbially-grown polymers and those extracted from starch. It is possible to reinforce such materials with natural fibers, from plants such as flax, jute, hemp, and other cellulose sources (Bismarck et al. 2002).

Economic concerns must be addressed objectively as biopolymer materials are developed, because the future of each product is dependent on its cost competitiveness, and society’s ability to pay for it. Many governments are introducing initiatives designed to encourage research and development of biologically based polymers. Most European and North American politicians and policy makers support work in this area, with the German government being particularly interested (Grigat et al. 1998).

The future outlook for advancement in the area of biodegradable plastics is ultimately promising.
Canada’s biotechnology infrastructure is world class, with the provinces of Ontario, Quebec, and Saskatchewan being particularly active and successful in research and development. Crawford (2001) explained that Canada’s long term goal on the international front is to develop technologies that are able to accept a diverse combination of raw materials, and produce multiple outputs, while releasing no emissions.

This literature review is intended to provide information regarding progress made in the development of biodegradable polymer materials. Biodegradability, constituent materials, applications, methods of biodegradation and environmental and economic implications of such materials will be examined. Finally, information regarding the future direction for biodegradable polymers will be objectively discussed.
BIODEGRADABILITY OF POLYMERS
The American Society for Testing of Materials (ASTM) and the International Standards Organization (ISO) define degradable plastics as those which undergo a significant change in chemical structure under specific environmental conditions. These changes result in a loss of physical and mechanical properties, as measured by standard methods. Biodegradable plastics undergo degradation from the action of naturally occurring microorganisms such as bacteria, fungi, and algae. Plastics may also be designated as photodegradable, oxidatively degradable, hydrolytically degradable, or those which may be composted. Between October 1990 and June 1992, confusion as to the true definition of “biodegradable” led to lawsuits regarding misleading and deceitful environmental advertising (Narayan et al. 1999). Thus, it became evident to the ASTM and ISO that common test methods and protocols for degradable plastics were needed.
There are three primary classes of polymer materials which material scientists are currently focusing on. These polymer materials are usually referred to in the general class of plastics by consumers and industry. Their design is often that of a composite, where a polymer matrix (plastic material) forms a dominant phase around a filler material (Canadian Patent #2350112-2002). The filler is present in order to increase mechanical properties, and decrease material costs.

Conventional plastics are resistant to biodegradation, as the surfaces in contact with the soil in which they are disposed are characteristically smooth (Aminabhavi et al. 1990). Microorganisms within the soil are unable to consume a portion of the plastic, which would, in turn, cause a more rapid breakdown of the supporting matrix. This group of materials usually has an impenetrable petroleum based matrix, which is reinforced with carbon or glass fibers.
The second class of polymer materials under consideration is partially degradable. They are designed with the goal of more rapid degradation than that of conventional synthetic plastics. Production of this class of materials typically includes surrounding naturally produced fibers with a conventional (petroleum based) matrix. When disposed of, microorganisms are able to consume the natural macromolecules within the plastic matrix. This leaves a weakened material, with rough, open edges. Further degradation may then occur.
The final class of polymer materials is currently attracting a great deal of attention from researchers and industry. These plastics are designed to be completely biodegradable. The polymer matrix is derived from natural sources (such as starch or microbially grown polymers), and the fiber reinforcements are produced from common crops such as flax or hemp. Microorganisms are able to consume these materials in their entirety, eventually leaving carbon dioxide and water as by-products.

Materials must meet specific criteria set out by the ASTM and ISO in order to be classified as biodegradable. In general, the likelihood of microbial attack on a material is dependent on the structure of the polymer. When examining polymer materials from a scientific standpoint, there are certain ingredients that must be present in order for biodegradation to occur. Most importantly, the active microorganisms (fungi, bacteria, actinomycetes, etc.) must be present in the disposal site. The organism type determines the appropriate degradation temperature, which usually falls between 20 to 60oC (Shetty et al. 1990). The disposal site must be in the presence of oxygen, moisture, and mineral nutrients, while the site pH must be neutral or slightly acidic (5 to 8).

Biodegradation of materials occurs in various steps (Aminabhavi et al. 1990). Initially, the digestible macromolecules, which join to form a chain, experience a direct enzymatic scission. This is followed by metabolism of the split portions, leading to a progressive enzymatic dissimilation of the macromolecule from the chain ends. Oxidative cleavage of the macromolecules may occur instead, leading to metabolization of the fragments. Either way, eventually the chain fragments become short enough to be converted by microorganisms (Stevens 2003).

Biodegradable polymers (those derived from plant sources) begin their lifecycle as renewable resources, usually in the form of starch or cellulose. As reported by Lorcks (1998), innovative polymer research and development leads to large scale production by plastic converters. The biopolymers are formed into the specific end products and used by a consumer. Ideally, the biopolymer will be disposed in a bio waste collection, and later composted. This process will ultimately leave behind carbon dioxide and water, which are environmentally friendly products.
BIOLOGICAL MATERIALS AND BIODEGRADABLE PLASTICS
Naturally occurring biopolymers are derived from four broad feedstock areas (Tharanathan 2003). Animal sources provide collagen and gelatine, while marine sources provide chitin which is processed into chitosan. However, the remaining two feedstock areas are the ones receiving the most attention from scientists, and are the sources thought to be the most promising for future development and expansion. Microbial biopolymer feedstocks are able to produce polylactic acid (PLA) and polyhydroxy alkanoates (PHA). The final category of agricultural feedstocks are the biopolymer source under consideration at the University of Saskatchewan, in Saskatoon, Canada. This variety of polymers falls into the categories of hydrocolloids, and lipids and fats.

Starch is an agricultural feedstock hydrocolloid biopolymer found in a variety of plants including (but not limited to) wheat, corn, rice, beans, and potatoes (Salmoral et al. 2000, Martin et al. 2001). Starch is usually utilized in the form of granules, and is actually formed by one branched and one linear polymer (Chandra et al. 1998). Amylose, the linear polymer, comprises approximately 20% w/w of starch, while Amylopectin, the branched polymer, constitutes the remainder. Natural filler materials may be incorporated into synthetic plastic matrices as a rapidly biodegradable component. Often, granular starch is added to polyethylenes in order to increase the degradation rate of the plastic material.
Starch can also be used in its gelatinized form (Verhooght et al. 1995). Heating the starch in the presence of water during extrusion or injection moulding causes the formation of a thermoplastic material that may be deformed during blending. This starch-based product is then blended with either natural or synthetic materials. Heating starch above its glass transition temperature breaks its molecular structure, allowing further bonding (Jopski 1993). Glycerol is often used as a plasticizer in starch blends, to increase softness and pliability. Starch granules that have been plasticized with water and glycerol are referred to as plasticized starches (Martin et al. 2001). Plastic materials that are formed from starch-based blends may be injection molded, extruded, lown, or compression molded.
Agricultural feedstocks for the biopolymer industry also include fibres that are used as reinforcing fillers. This classification includes cellulose, which is the highly polar, main structural component of flax and hemp fibres (Bismarck 2002). Natural cellulose fibres are low cost, biodegradable, and have strong mechanical properties. These characteristics make cellulose fibres the most common choice for natural fillers in plastic materials. Hornsby et al. (1997) concluded that the presence of 25% w/w of cellulose fibres in a polypropylene matrix causes a significant increase in tensile modulus. Cellulose has a very long molecular chain, which is infusible and insoluble in all but the most aggressive solvents (Chandra et al. 1998). Therefore, it is most often converted into derivatives to increase solubility, which further increases adhesion within the matrix.
Canadian researchers are particularly interested in expanding the area of fiber use in biopolymer products, as this would allow for value added processing of local agricultural waste products. Flax fibres continue to receive the majority of the consideration, as they are mechanically strong and readily available. Chemical treatment (acetylation) of the fibres is performed in order to modify the surface properties, without changing the fiber structure and morphology (Frisoni 2001). These modifications slow down the initiation of degradation of the fibres, and increase adhesion at the fiber and matrix interface. Bledzki et al. (1999) concluded that fibres that have been thoroughly dried prior to being added to the matrix show improved adhesion as opposed to fibres with a higher moisture content. Research has shown that polyvinyl alcohol is an appropriate polymer to use as a matrix in natural fiber reinforced composites, as it is highly polar and biodegradable (Chiellini et al. 2001).
Microbial biopolymer feedstocks produce biological polymers through microbial fermentation. The products are naturally degradable, environmentally friendly substitutes for synthetic plastics (Chau et al. 1999). A number of bacteria accumulate polyhydroxy alkanoates (PHAs) as intracellular carbon reserves when nutrient deficiencies occur. The biopolymers, which are microbially produced polyesters, have the same thermoplastic and water resistant qualities as synthetic plastics. It was concluded by Chau et al. (1999) that increasing the carbon to nitrogen (C:N) ratio in a chemical wastewater treatment system increased specific polymer yield (ie, the production of PHA’s increased). Researchers have long been aware that practically any type of biomass can be converted into sugars through chemical or biological treatments. Certain organisms are then capable of forming PHAs from the sugars. Such is the case at the University of Hawaii, where food waste is being converted into PHAs (Petkewich 2003). Work in these areas continues, as the issue constricting expansion in the development of industry-wide PHA use is the high cost of producing the material. PHAs are brittle and expensive when used alone, so researchers opt to blend them with less expensive polymers, which have complementary characteristics.

Polylactic acid is the second common biopolymer which is produced by microbial fermentation. It is produced by the condensation of lactic acid, which is obtained through fermentation processes (Jopski, 1993). Wilkinson Manufacturing Co. (Fort Calhoun, Nebraska, USA) has recently introduced a commercially available thermoformed all-natural plastic container using a corn-based PLA. The carbon stored in the plant starches is broken down to natural plant sugars. Fermentation and separation form the PLA. PHA and PLA are both considered synthetic polymers, as they are not found in nature. However, they are wholly biodegradable (Stevens 2003).

There are a number of other biological materials that have been examined and manipulated by biopolymer researchers. Wheat contains starch and gluten, both of which are employed by the biopolymer industry. Canola derivatives have potential as both polymers and plasticizers (Crawford 2001). Chitosan is obtained from the deacetylation of chitin, which is found in marine environments. Because it is insoluble in water, chitosan is dissolved in acidic solutions before being incorporated into biodegradable polymer films (Park et al. 2001). The structural characteristics of soy proteins give them potential for industrial applications in plastics and reinforced composite materials (Park et al. 2000). As a general conclusion, it can be stated that many naturally occurring organisms (plant and animal) have potential to be modified and employed as biopolymers.

APPLICATIONS FOR BIODEGRADABLE POLYMERS
Research and development is only a portion of the work that is done in order to introduce the use of biodegradable polymer materials. The design of such materials usually begins with a conceptual application. It may be expected to replace an existing material, or to complement one. Sectors where applications for biopolymers have introduced include (but are not limited to) medicine, packaging, agriculture, and the automotive industry. Many materials that have been developed and commercialized are applied in more than one of these categories.

Biopolymers that may be employed in packaging continue to receive more attention than those designated for any other application. All levels of government, particularly in China (Chau et al. 1996) and Germany (Bastioli 1998), are endorsing the widespread application of biodegradable packaging materials in order to reduce the volume of inert materials currently being disposed of in landfills, occupying scarce available space. It is estimated that 41% of plastics are used in packaging, and that almost half of that volume is used to package food products.
BASF, a world leader in the chemical and plastic industry, is working on further development of biodegradable plastics based upon polyester and starch (Fomin et al. 2001). Ecoflex is a fully biodegradable plastic material that was introduced to consumers by BASF in 2001. The material is resistant to water and grease, making it appropriate for use as a hygienic disposable wrapping, fit to decompose in normal composting systems. Consequently, Ecoflex has found a number of applications as a packaging wrap.

Environmental Polymers (Woolston, Warrington, UK) has also developed a biodegradable plastic material. Known as Depart, the polyvinyl alcohol product is designed for extrusion, injection molding, and blow molding. Depart features user-controlled solubility in water, which is determined by the formulation employed. Dissolution occurs at a preset temperature, allowing the use of Depart in a variety of applications. Examples include hospital laundry bags which are “washed away” allowing sanitary laundering of soiled laundry, as well as applications as disposable food service items, agricultural products, and catheter bags (Blanco 2002).

The renewable and biodegradable characteristics of biopolymers are what render them appealing for innovative uses in packaging. The end use of such products varies widely. For example, biodegradable plastic films may be employed as garbage bags, disposable cutlery and plates, food packaging, and shipping materials. Guan and Hanna (2002) documented how biodegradable loose-fill packaging materials may be developed from renewable biopolymers such as starch. The starch material is treated by an acetylation process, chemical treatments, and post-extrusion steaming. Mechanical properties of the material are adequate, and true biodegradability is achieved.

The biopolymer materials suited for packaging are often used in agricultural products. Ecoflex, in particular, sees use in both areas. Young plants which are particularly susceptible to frost may be covered with a thin Ecoflex film. At the end of the growing season, the film can be worked back into the soil, where it will be broken down by the appropriate microorganisms. Li et al. (1999) concluded that the use of a clear plastic mulch cover immediately following seeding increases the yield of spring wheat if used for less than 40 days. Therefore, plastic films that begin to degrade in average soil conditions after approximately one month are ideal candidates as crop mulches.

Agricultural applications for biopolymers are not limited to film covers. Containers such as biodegradable plant pots and disposable composting containers and bags are areas of interest (Huang 1990). The pots are seeded directly into the soil, and breakdown as the plant begins to grow. Fertilizer and chemical storage bags which are biodegradable are also applications that material scientists have examined. From an agricultural standpoint, biopolymers which are compostable are important, as they may supplement the current nutrient cycle in the soils where the remnants are added.

The medical world is constantly changing, and consequently the materials employed by it also see recurrent adjustments. The biopolymers used in medical applications must be compatible with the tissue they are found in, and may or may not be expected to break down after a given time period. Mukhopadhyay (2002) reported that researchers working in tissue engineering are
attempting to develop organs from polymeric materials, which are fit for transplantation into humans. The plastics would require injections with growth factors in order to encourage cell and blood vessel growth in the new organ. Work completed in this area includes the development of biopolymers with adhesion sites that act as cell hosts in giving shapes that mimic different organs.

Not all biopolymer applications in the field of medicine are as involved as artificial organs. The umbrella classification of bioactive materials includes all biopolymers used for medical applications. One example is artificial bone material which adheres and integrates onto bone in the human body. The most commonly employed substance in this area is called Bioglass (Kokubo 2003). Another application for biopolymers is in controlled release delivery of medications. The bioactive material releases medication at a rate determined by its enzymatic degradation (Sakiyama-Elbert et al. 2001) PLA materials were developed for medical devices such as resorbable screws, sutures, and pins (Selin 2002). These materials reduce the risk of tissue reactions to the devices, shorten recovery times, and decrease the number of doctor visits needed by patients.

The automotive sector is responding to societal and governmental demands for environmental responsibility. Biobased cars are lighter, making them a more economical choice for consumers, as fuel costs are reduced. Natural fibres are substituted for glass fibres as reinforcement materials in plastic parts of automobiles and commercial vehicles (Lammers and Kromer 2002). An additional advantage of using biodegradable polymer materials is that waste products may be composted. Natural fibres (from flax or hemp) are usually applied in formed interior parts. The components do not need load bearing capacities, but dimensional stability is important. Research and development in this area continues to be enthusiastic, especially in European countries.

There are a number of novel applications for biopolymers, which do not fit into any of the previous categories. One such example is the use of biopolymer systems to modify food textures. For example, biopolymer starch (gelatin-based) fat replacers possess fat-like characteristics of smooth, short plastic textures that remain highly viscous after melting. Research continues into high pressure being used to manipulate biopolymers into food products. The eventual goal is improved physical characteristics such as foaming, gelling, and water- or fat-binding abilities (Ledward 1993). Biopolymer materials are currently incorporated into adhesives, paints, engine lubricants, and construction materials (Fomin et al. 2001). Biodegradable golf tees and fishing hooks (Canadian Patent # 2198680-1997) have also been invented. The attraction of biopolymers in all of these areas is their derivation from renewable sources, slowing the depletion of limited fossil fuel stores.
METHODS OF BIODEGRADATION
Just as important as the way in which a material is formed is the way in which it is degraded. A general statement regarding the breakdown of polymer materials is that it may occur by microbial action, photodegradation, or chemical degradation. All three methods are classified under biodegradation, as the end products are stable and found in nature. Many biopolymers are designed to be discarded in landfills, composts, or soil. The materials will be broken down, provided that the required microorganisms are present. Normal soil bacteria and water are generally all that is required, adding to the appeal of microbially reduced plastics (Selin 2002). Polymers which are based on naturally grown materials (such as starch or flax fiber) are susceptible to degradation by microorganisms. The material may or may not decompose more rapidly under aerobic conditions, depending on the formulation used, and the microorganisms required.
In the case of materials where starch is used as an additive to a conventional plastic matrix, the polymer in contact with the soil and/or water is attacked by the microbes. The microbes digest the starch, leaving behind a porous, spongelike structure with a high interfacial area, and low structural strength. When the starch component has been depleted, the polymer matrix begins to be degraded by an enzymatic attack. Each reaction results in the scission of a molecule, slowly reducing the weight of the matrix until the entire material has been digested (Shetty et al. 1990).

Another approach to microbial degradation of biopolymers involves growing microorganisms for the specific purpose of digesting polymer materials. This is a more intensive process that ultimately costs more, and circumvents the use of renewable resources as biopolymer feedstocks. The microorganisms under consideration are designed to target and breakdown petroleum based plastics (Andreopoulos et al. 1994). Although this method reduces the volume of waste, it does not aid in the preservation of non-renewable resources.
Photodegradable polymers undergo degradation from the action of sunlight (ASTM 883-96). In many cases, polymers are attacked photochemically, and broken down to small pieces. Further microbial degradation must then occur for true biodegradation to be achieved. Polyolefins (a type of petroleum-based conventional plastic) are the polymers found to be most susceptible to photodegradation. Proposed approaches for further developing photodegradable biopolymers includes incorporating additives that accelerate photochemical reactions (e.g. benzophenone), modifying the composition of the polymers to include more UV absorbing groups (e.g. carbonyl), and synthesizing new polymers with light sensitive groups (Andreopoulos et al. 1994). An application for biopolymers which experience both microbial and photodegradation is in the use of disposable mulches and crop frost covers.
Some biodegradable polymer materials experience a rapid dissolution when exposed to particular (chemically based) aqueous solutions. As mentioned earlier, Environmental Polymer’s product Depart is soluble in hot water. Once the polymer dissolves, the remaining solution consists of polyvinyl alcohol and glycerol. Similar to many photodegradable plastics, full biodegradation of the aqueous solution occurs later, through microbial digestion. The appropriate microorganisms are conveniently found in wastewater treatment plants (Blanco 2002). Procter & Gamble has developed a product similar to Depart, named Nodax PBHB. Nodax is alkaline digestible, meaning that exposure to a solution with a high pH causes a rapid structural breakdown of the material (Leaversuch 2002). Biopolymer materials which disintegrate upon exposure to aqueous solutions are desirable for the disposal and transport of biohazards and medical wastes. Industrial “washing machines” are designed to dissolve and wash away the aqueous solutions for further microbial digestion.
ENVIRONMENTAL IMPACTS OF BIOPOLYMERS
Engineers are attempting to integrate environmental considerations directly into material selection processes, in order to respond to an increased awareness of the need to protect the environment (Thurston et al. 1994). The use of renewable resources in the production of polymer materials achieves this in two ways. First of all, the feedstocks being employed can be replaced, either through natural cycles or through intentional intervention by humans. The second environmental advantage of using renewable feedstocks for biopolymer development is the biodegradable nature of the end products, thereby preventing potential pollution from the disposal of the equivalent volume of conventional plastics. At the end of their useful period, biopolymer materials are generally sent to landfills or composted.
Recycling of plastic materials is encouraged and well advertised, but attempts at expanding this effort have been less than effective. In the United States, currently less than 10% of plastic products are recycled at the end of their useful life (Chiellini et al. 2001). Recycling must be recognized as a disposal technique, not a final goal for material development. A complacent attitude regarding recycling processes ignores the fact that advanced infrastructure is needed to properly house recycling. As Mulder (1998) discovered, in underdeveloped countries plastics are almost completely recycled, as the return on investment is positive in their economic situation. This appears to be positive at the onset, but the open systems by which the plastics are recycled allow the emission of toxic gases at crucial levels.
Recycling appeared to be a viable way to reduce pollution and environmental damage when it was first introduced as a waste reduction technique. However, as time has passed, it is now obvious that the use of plastics based on renewable feedstocks which are biodegraded is a more sensible choice than recycling conventional plastics, as the end products are organic matter, and toxic emissions are avoided. Therefore, growth of plastics which are compostable or easily degraded must be encouraged.
In recent years, concern about a perceived garbage crisis has grown. Landfills have reached capacity, and sites for new landfills are difficult to find. When biopolymers are disposed in landfill environments, the hope is that the necessary microorganisms will be present. Unless the soil is inoculated with them, this may not always be the case. As reported by Petkewich (2003), carrots have been found to remain orange, and grass clippings green, after years in a landfill. Inoculation with bacteria, fungi, and actinomycetes is effective in encouraging biopolymer breakdown within soil (Orhan et al. 2000). However, if the appropriate microorganisms are present, the disposal (and consequential breakdown) of biodegradable (or partially biodegradable) plastic materials will lead to an increase of available space in current landfills as the volume of waste is reduced through biodegradation (Simon et al. 1998).
Compostable plastics undergo biological degradation during composting to yield carbon dioxide, ater, inorganic compounds, and biomass at a rate consistent with other known compostable materials, and leave no visually distinguishable or toxic residues (ASTM 1996). Many of the biodegradable plastic materials discussed thus far were designed to be compostable. For instance, the purpose of designing disposable plastic cutlery and plates is that they can be thrown into a compost heap with leftover food. The requirements of biopolymers to be included in industrial composters are complete biodegradation and disintegration, and that there be no effect on compost quality as a result of biopolymer degradation (Wilde and Boelens 1998).
As an added benefit, Nakasaki et al. (2000) concluded that odor emissions from compost piles are reduced when biodegradable plastic is included in the mix. Ammonia, a noxious gas, is produced by the decomposition of compost. The degradation of biodegradable plastics produces acidic intermediates, which neutralize the ammonia content, thus reducing odor problems.

The 1970’s began an era of increased factual thinking processes by researchers and industry officials. As such, the technique of life cycle analysis (LCA) emerged. This modeling exercise is based on a simple idea; it is necessary to look at the complete life cycle for the production, use, and disposal of a product in order to obtain a clear picture of the true environmental implications of its development (Boustead 1998). Performing an LCA demonstrates whether or not further development of a product is a viable option. There are three steps to an LCA, beginning with the inventory, where inputs and outputs of the system are quantitatively described. The interpretation step follows, which links the inputs and outputs with observable environmental effects. Finally, the improvement step is carried out. Here, the system is redesigned to remain functional, while showing increased environmental awareness. The cycle is repeated until an objective decision can be made as to the environmental efficiency of the system.

The technique of life cycle analysis is a good way to examine the practicality of further development of biopolymer materials. Only by exploring all implications of the product can its true environmental responsiveness be judged. As society continues to become more aware of environmental issues, the procedure of LCA will continue to be used more often. On the other hand, further acceptance of integrated waste management techniques for biodegradable plastic materials, involving efficient material use and disposal must also continue (Subramanian 2000).
ECONOMIC IMPACTS OF BIOPOLYMERS
From the viewpoint of industry, the greatest advantage of using biopolymers derived from renewable feedstocks is their low cost. At a first glance, biopolymers appear to be a win-win opportunity for the economy and the environment. However, as is the situation with environmental issues, a closer look at the cost-performance ratio of biopolymers must be taken in order to make sound economic decisions (Swift 1998).
According to Leaversuch (2002), cost is a stumbling block for synthetically derived biodegradable plastic materials when they are directly compared with their conventional counterparts. As the case with any new material, manufacturers must expect a minimum of two years of losses before a profit is returned. Leaversuch also indicated that a key factor restricting growth of biopolymer industries is that the infrastructure for sorting and composting organic waste is developing more slowly than was initially expected.
Many reports paint a more optimistic picture for the economic promise of biopolymers. As Salmoral et al. (2000) reported, a number of major chemical companies are gaining interest in developing biopolymer technologies used to manufacture products from renewable resources. Tharanathan (2003) reported that synthetic plastics will never be totally replaced by biodegradable materials. However, he believes that in niche markets where the development is feasible, there exists an opportunity for manufacturers to find a large profit.
One sector in which economic benefits exist from the use of biopolymer materials is in the automotive industry. With respect to fiber reinforcements, widely employed traditional glass fibres are abrasive, and quickly wear down processing equipment. The texture of flax fibres is less coarse, prolonging the life of processing equipment (Stamboulis et al. 2000). Williams and Pool (2000) identified that natural fibres are advantageous over synthetic ones because they are less expensive and more readily available. The expansion of flax fiber incorporation into automobile parts is a positive development for Canada’s agriculture industry, particularly in its diversification efforts.
Another application of natural fiber reinforcement has been developed in the use of China reed fiber to reinforce transport pallets. This was an economically sound decision, as the China reed pallets are as mechanically stable as conventional pallets, but they are less expensive to create, and need a shorter lifespan for cost recovery. Logistically, the China reed pallets are also more economic than the conventional type because their lighter mass requires less fuel for transport (Corbiere-Nicollier et al. 2001).
Work continues in the development of the biopolymer industry to a point where it is completely economically competitive with the conventional plastic industry. Synthetic plastics are produced on a large scale, while for the most part biopolymers are currently produced on a small scale. The inexpensive nature of the renewable resource feedstocks is encouraging researchers and industry officials to invest time to further develop these processes.
As the production of biopolymers expands, so too will the services associated with it. For example, facilities where flax straw is decorticated and processed into fibers are necessary for further expansion of flax fiber incorporation as material reinforcements (Lammers and Kromer 2002). In the case of microbially-grown polymers, large fermentation and separation facilities are needed for the further use of such materials. As a general summary, it may be stated that time will lead to greater economic strength for the incorporation of biopolymer materials into society.
THE FUTURE OUTLOOK FOR BIODEGRADABLE PLASTICS
There is room for growth and expansion in many areas of the biodegradable plastic industry. Chau et al. (1999) estimates that plastic waste generation will grow by 15% per year for the next decade. Carbon dioxide emissions from the formation and disposal of conventional plastics are reaching epic levels. The complete substitution of petroleum-based feedstock plastics by renewable resource-based feedstock ones would lead to a balanced carbon dioxide level in the atmosphere (Dahlke et al. 1998). However, it is ludicrous to expect a full replacement of conventional polymers by their biodegradable counterparts any time soon. Expansion into particular niche markets seems to be the most viable option.
Researchers worldwide are interested in the area of biopolymer development. The German government has stringent regulations in place regarding acceptable emission levels. In 1990, the German government published a call for research and development of biodegradable thermoplastics (Grigat et al. 1998). For this reason, many German material scientists and engineers have focused their work on environmentally stable biodegradable plastics. Various materials have been created by these researchers, including the Bayer BAK line which was introduced in extrusion and injection moulding grades in 1996. Novamont, an Italian company, introduced the Mater-Bi line for similar reasons. Queen Mary University in London, England has a plastics department which is actively working on biocomposite development (Hogg 2001). As a whole, all European nations are expected to follow the European Packaging directive, which expects a material recovery of packaging waste. Organic recovery (composting spent materials) is the most commonly applied waste reduction method (Schroeter 1998). European nations are also expected to incorporate 15% w/w of recycled plastics into the manufacture of packaging materials. Germany aims to better that level, as they set tier goal in 2001 for a 60% incorporation of recycled plastics into new packaging materials (Fomin et al. 2001).
European nations are the front runners of biopolymer research, but impressive developmental work has occurred, and continues to occur, in other geographical areas. The Chinese government is responsible for a large population on a small land base. Therefore, the preservation of space, and responsible disposal of waste are key considerations. For these reasons, Chinese researchers are focussing on refinement of microbially produced PHA (Chau et al. 1996). North American researchers, including those at the University of Saskatchewan, are also interested in biopolymer development, as the agricultural industry will benefit from the potential value added processing. The acceptance of the Kyoto Accord by the Government of Canada is fueling a need for the reduction of use of fossil fuel feedstocks, and an increase in the use of renewable resource feedstocks. Biodegradable plastics fulfill this requirement.
As the biopolymer industry grows, issues with production will be worked out. There are some eas of concern that researchers are aware of, and are consequently focussing on. Multilayer films containing starch and/or natural fibres tend to have adhesion problems (Frisoni et al. 2001, Martin et al. 2001). The search for an ideal processing technique to circumvent this problem continues. In this regard, Verhoogt and co-workers (1995) have concluded that additional starch content in thermoplastic blends increases flexibility, but decreases mechanical strength. As reported by Van Soest and Kortleve (1999), direct relations between processing, structure, and properties of starch based materials are inconclusive.
Standards organizations such as the ASTM and ISO have published methods for material tests on biodegradable plastic materials. A need for reviews and improvements of these tests has come to light as industry expands its use of biopolymers. In particular, non-homogenities are created in polymer materials by the clamps used for tensile tests (Nechwatal et al. 2003). The nature of natural materials requires different considerations than those for synthetic materials.
The biopolymer industry has a positive future, driven mainly by the environmental benefits of using renewable resource feedstock sources. The ultimate goal for those working in development is to find a material with optimum technical performance, and full biodegradability.
CONCLUSIONS
There are a seemingly limitless number of areas where biodegradable polymer materials may find use. The sectors of agriculture, automotives, medicine, and packaging all require environmentally friendly polymers. Because the level of biodegradation may be tailored to specific needs, each industry is able to create its own ideal material. The various modes of biodegradation are also a key advantage of such materials, because disposal methods may be tailored to industry specifications.
Environmental responsibility is constantly increasing in importance to both consumers and industry. For those who produce biodegradable plastic materials, this is a key advantage. Biopolymers limit carbon dioxide emissions during creation, and degrade to organic matter after disposal. Although synthetic plastics are a more economically feasible choice than biodegradable ones, an increased availability of biodegradable plastics will allow many consumers to choose them on the basis of their environmentally responsible disposal.
The processes which hold the most promise for further development of biopolymer materials are those which employ renewable resource feedstocks. Biodegradable plastics containing starch and/or cellulose fibres appear to be the most likely to experience continual growth in usage. Microbially grown plastics are scientifically sound, and a novel idea, but the infrastructure needed to commercially expand their use is still costly, and inconvenient to develop.
Time is of the essence for biodegradable polymer development, as society’s current views on environmental responsibility make this an ideal time for further growth of biopolymers.
Acknowledgements
The authors gratefully acknowledge the financial support for this project provided by the Agriculture Development Fund (ADF) of SK Agriculture, Food, & Rural Revitalization, and the University of Saskatchewan Summer Student Employment Program.