Inhalt

Introduction

Bioplastic

INTRODUCTION

From recent past, the world is becoming cognizant about the hazardous effect of plastic bags on the environment. To support this, researchers have come up with natural option of Bioplastics. Plastics are being used all over the world. Right from drinking cups to parts for automobiles. Plastics are extremely important to the job market as well as for packaging throughout the world. Since plastics are involved with peoples everyday lives. Therefore production of biodegradable plastics to make plastics more compatible with environment has become necessary.

Option of Bioplastics focus on performance and price to become viable packaging alternatives in future. It is better than the alternate bio fuel which is adopted in partial manner mainly in U.S.A., and is based on the corn crops in order to utilize excess land and food products and same can be utilized for the alternate plastic instead of wasting it. Currently, the bioplastics industry is in its infancy and, as a result, does not require a significant proportion of land for feedstock supply. Approximately 2.5 kg of maize produced on 2.5 square metres of land is required to produce 1 kg of PLA. In the USA around 36 million hectares of maize is grown annually and around 17 thousand hectares is required to produce 70 thousand tonnes of PLA. This land use equates to 0.1% of the total US maize land area. In UK the most likely crop feedstock for bioplastic manufacture is wheat. A plant producing 132,000 tonnes of PLA per annum would only require a small percentage of the wheat produced in the UK. This slight increase in demand could be met through use of some of our exported wheat, through improved crop yields and more efficient use of farmland. Considering this data we can predict that with improved crop yields and efficient use of farming we can meet the demand of crops used in the manufacturing of bioplastics without any diversion of land and on food availability. It is also safe in manifolds than conventional plastic because bioplastics are very much safe, and they contain no toxins at all. With traditional plastics harmful chemicals and by-products can be released during the breakdown and decay period, but this is not the case with plastic that is biodegradable. This all natural plastic breaks down harmlessly and is absorbed back into the earth. There is no chemical leaching into rain water or the ground to threaten the health and safety of people or animals nearby. It biodegrade and break down into carbon dioxide, water, biomass at the same rate as cellulose (paper). Bioplastic when disintegrate is indistinguishable in the compost and is not visible. Its biodegradation does not produce any eco-toxic material and the compost can also support plant growth. Biodegradable Plastic is plastic which degrades from the action of naturally occurring microorganism, such as bacteria, fungi etc. over a period of time. Considering the above faces of its productivity and properties of non-toxicity and biodegradability about 90% within one year depending upon the environmental conditions, this can also be used as food for fishes and other marine species.

Bioplastics packaging is being slowly adopted by food service companies and grocery store delis for use as film for sandwich wraps or for clamshell packaging for fresh products such as vegetables, fruits, salads, pasta or bakery goods. In view of this it becomes important to find durable plastic substitutes especially in short- term packaging and disposable applications. The continuously growing concern of the public and government for the problems related to plastic has stimulated research interest in bioplastics as alternative to conventional plastics; so, bioplastic packaging has a great potential in a country like ours where we have land, water and energy resources and we cannot rely on landfill or recycling of packaging wastes particularly when the non- biodegradable packaging materials are becoming a visible nuisance and eyesore in big cities. It seems, in the age where sustainability is one of the biggest issues facing the packaging and bulk packaging industry, its application will spread like wildfire.

Bio-Plastics are not a single class of polymers but rather a family of products which can vary considerably.
Bio-Plastics consist of

– Biobased plastics, based on renewable resources

– Biodegradable polymers, which meet all criteria of scientifically recognized norms for biodegradability and compostability.

From recent past, the world is becoming cognizant about the hazardous effect of plastic bags on the environment. To support this, researchers have come up with natural option of Bioplastics. Plastics are being used all over the world. Right from drinking cups to parts for automobiles. Plastics are extremely important to the job market as well as for packaging throughout the world. Since plastics are involved with peoples everyday lives. Therefore production of biodegradable plastics to make plastics more compatible with environment has become necessary.

Bio-Plastics are not a single class of polymers but rather a family of products which can vary considerably.
Bio-Plastics consist of

– Biobased plastics, based on renewable resources

– Biodegradable polymers, which meet all criteria of scientifically recognized norms for biodegradability and compostability.

From recent past, the world is becoming cognizant about the hazardous effect of plastic bags on the environment. To support this, researchers have come up with natural option of Bioplastics. Plastics are being used all over the world. Right from drinking cups to parts for automobiles. Plastics are extremely important to the job market as well as for packaging throughout the world. Since plastics are involved with peoples everyday lives. Therefore production of biodegradable plastics to make plastics more compatible with environment has become necessary.

What are bio plastics?

When someone hears the word plastics, he or she usually automatically thinks of a kind of matter made from oil that can be used in making almost anything. If the person was asked whether or not it is good for the enviroment, the answer would probably be negative. But that is not necessarily the case. There are other ways of making plastics which are far more friendly to the environment. The main protagonists of one of these processes are bacteria. Plastics created this way are called bioplastics. They are one of the most perspective materials for future mankind.

How does it work?

In a way, these bacteria act similarly to humans. They want food and if they are getting a lot of it, they start to store it in their bodies as a reserve for a rainy day. As it happens, this reserve is also a material with physical and chemical properties similar to our everyday plastics. All we need to do then is just separate this material from the rest of the body and we are good to go. Basically, we just feed our bacteria and they will do most of the work for us. What do we feed them with then? Luckily for us, they are not picky and accept almost anything liquid with carbon in it. One of the examples would be waste oil which is used abundantly because of its incredibly cheap price. We let the bacteria live on their own, only regulate the amounts of food, oxygen and other necessities they are getting to make them produce as much plastic as possible. After some time, we are ready to collect the results.

Now another question arises. How do we get the plastic out of the body? First thing we must do is separate the cells from the medium in which they lived. We achieve that by centrifuging it. This isolates the liquid part – medium – from the solid part – cells. When we are done with that, we probably want to know how much plastic stored there really is. There are two main methods of gaining this information. The first one is based on the material’s ability to absorb light cast inside of a special machine. The second one, which is used the most, is very sophisticated and hard to catch the grasp of without diving too deep into the problem. We basically change the state of the plastic to gas and run it through a big expensive machine which then tells us what we want to know – what components the compound consists of and what are their respective masses.

All that remains is getting the desired material out of its shell. This can be done by either dissolving the shell and getting the material in a solid state or doing exactly the opposite – dissolving the material and then breaking the shell. Both have their pros and cons, the first mentioned being generally somewhat faster while using the latter brings better purity of the plastic.

What is the point of all of this?

All things set aside, why would we go through this horrendous time-consuming process when we can just continue synthesizing our materials from oil? There is a number of reasons. Oil is not a renewable source of energy and when we run out of it, not only we will have to deal with the lack of fuel for our cars and other vehicles, but we would also be unable to make materials that are essential for our everyday lives. Pressing this research forward reduces our reliance on oil and thus gives us more options for the future.

Another advantage that bioplastics hold over their synthetic counterparts is that they fall apart in nature far more quickly. This means that they do not pose a problem to our environment and as such present a nifty alternative to wrapping and other nonecological waste-producing materials.

Last but not least, they can be used in medicine, namely in tissue engineering. That means using external factors to improve or replace certain biological functions. An example could be a heart valve made of bioplastics to ensure no harm would come to the body.

If it is so great, why are we not using it everywhere?

As it often is, the biggest problem here is the money. Or more precisely, the lack of it. Major investors have not yet fully committed to this field of industry because it is simply not worth it. Making the same amount of bioplastic is about ten times more expensive than that of an oil-made synthetic. However, this gap is slowly shrinking and it is only a matter of time before the much awaited breakthrough finally comes. Decreasing this price was also the main goal of the experimental part of this work.

BIOPLASTICS

Bioplastics are a form of plastic derived from renewable biomass source, such as vegetable oil, corn-starch, potato-starch or microbia, rather than fossil-fuel plastics which are derived from petroleum.

History: - Bioplastics are not new, in the 1850s, a British chemist created plastics from cellulose, a derivative of wood pulp. Later in the early 20th century, Henry ford experimented with soy-based plastics in his automobiles. After that, biodegradable plastics began being sparking interest during the oil-crisis in seventies. The 1980's brought items such as biodegradable films, sheets and mold-forming materials. As prices of petroleum products are increasing day by day and therefore the need of bioplastic appeared and research started in this context.

Composition: - Bioplastics can be made from many different sources and materials. They are produced from renewable biomass sources, such as vegetable oil, corn-starch, potato-starch or microbiota, a number of fibers including those obtained from pineapple and henequen leaves and banana stems. Corn is the primary source of starch for bioplastics, although more recent global research is evaluating the potential use in bioplastics for starches from potato, wheat, rice, barley, oat and soy-sources.

Also, bioplastics can be made using bacterial micro-organisms or natural fibers such as jute, hemp & Kenaf. Sometimes various nanometer-sized particles especially carbohydrate chains called polysaccharides or other biopolymers that don't dissolve in water, with clay are added to add certain properties like, low water- vapour and gas permeability, increased shelf-life with better strength. But there is a need to identify the other suitable plants available for this specific purpose.

Polylactic acids (PLA)
Polyhydroxyalkanoic acids (PHAs)
Polyhydroxybutyrate-co-valerate (PHBVs)
Polyols
- Plant oil
Variety of other Bioplastics
Extracted or Used
- oil, starch, sugars, lactic acid, fatty acids, proteins, bacteria, fibers

Bio-Plastic

Bio Plastic

Classification

Polycaprolactones: - It is a biodegradable thermoplastic polymer derived from the chemical synthesis of crude oil. Polycaprolactones has good water, oil, solvent and chlorine resistance. It is mainly in thermoplastic polyurethanes, resins for surface coatings adhesives and synthetic leather and fabrics.

BULK PACKAGING

Packaging is system of preparing goods for transport, distribution storage, retailing and end use. It is means of safe delivery to ultimate consumer in sound condition at economic cost. There are basically three different kind of packages categorized on the basis of use, function, containment of the package.

The first kind of package is unit package, it contain product for one shot is for family requirement, it provides all information related to the product, it also provides aesthetic values and convenience factors to support sales. Intermediate packaging facilitates distribution in the overall marketing system. Bulk, the most important one helps in the complete containment of product or product groups. It facilitates inventory and bulk distribution of package product and also protects them during transportation. To define Bulk Packaging, we can use one of two approaches. The most obvious way is to lay down a basic minimum unit content threshold which is 25 kgs. or 25 liters but this poses certain limitations. The other is to look at the packaging system that what basic function it performs. Using the latter approach, it would be logical to assume that we would want to look at all major applications or packages that are not meant for retail consumption but are only targeted at consumption by manufacturing and processing industries or by organization who are „bulk‟ consumers. In other words, we are looking at packages that contain products which are meant for large-scale or industrial consumption as intermediate inputs for further processing, distribution and re-sale in smaller denominations.

Classification based on basic guidelines there is different bulk packaging systems:

Metal packaging (steel drums and barrels, large cans)
Rigid plastic packaging (Plastic barrels, IBC‟s, large bottles)
Flexible packaging systems (Sacks, woven sacks, FIBC‟s, films for stretch wrapping, shrink wrapping)
Paper-based packaging (corrugated fiberboard, multiwall layer sacks, fiber drums)
Bag-in-box and bag-in-drum systems
Aseptic bulk packaging
Wooden packaging (pallets and cases)

Our primary focus will be on the rigid plastic packaging and flexible packaging systems because they have to be replaced in recent future by bioplastics. The need of replacement for the petroleum based plastic with bioplastics is just because

Producing conventional plastics consumes 65% more energy than producing
Conventional plastic are mostly
Plastics last a long time and do huge damage to Therefore, plastic is absolutely unsustainable and bioplastic is more sustainable.
Bioplastics saves 30-80% of the greenhouse gas emissions and provide longer shelf-life than normal

Bi- Polymer

Bulk packaging systems related with conventional plastics are as follows:-

Intermediate bulk containers (IBC): An Intermediate bulk container is a container used for transport and storage of fluids and bulk materials. The construction of the IBC container and the materials used are chosen depending on the application. They are generally cubic in shape and therefore can transport more material in the same volume than cylindrically shaped containers and far more may be shipped in the same space if packaged in consumer quantities. IBCs range in size but are generally between 700 and 2,000 mm or 1,168 to 1,321mm in height. IBCs may ship and store Bulk chemicals including hazardous materials if the IBC is proven suitable. The plastic used in the manufacturing of IBC‟s are basically polyethylene, polypropylene these are plastics are used because they have lower impact strength, high tensile strength, High compressive strength, excellent dielectric properties, resists to alkalis and acids, resists stress cracking, retains stiffness, low moisture absorption, non- toxic, non-staining, easily fabricated, and high heat resistance.

of

Gas barrier properties: In most packaging applications the gas mixture inside the package consists of carbon dioxide, oxygen and nitrogen or combinations. Biobased materials have quite same oxygen permeability that of conventional mineral-oil-based materials and it is possible to select from a range of barriers among the present biobased materials. The conventional approach to introduce high-barrier films for packaging of food is to use multi-layers of different films in order to obtain the required properties. A laminate that is often used in packaging consists of an layer of EVOH or PA6 combined with LDPE for mechanical strength and the excellent sealing properties. A similar multi-layer approach for biobased materials may be used to produce materials with the required properties. Starch-based materials could provide cheap alternatives to presently available gas barrier materials like EVOH and PA6 and an equivalent biobased laminate would be an outer- layer of plasticized chitosan, a protein or starch-derived film combined with PLA or PHA. PLA and PHA will protect the moisture-sensitive-gas-barrier made of polysaccharide and protein. Developments have made it possible to improve water vapour and gas properties of biobased materials many-fold by using plasma deposition of glass- like SiOx coatings on biobased materials or the production of nano-composites out of a natural polymer.

In general, the oxygen and other gases permeability of a specific material are closely interrelated, petroleum based polymers have a fixed ratio between the oxygen and carbon dioxide permeabilities. This relation is also observed for biobased materials. However, for some biobased materials,like PLA and starch, the permeability of carbon dioxide in comparison to oxygen is much higher than for petroleum based plastics.

Barrier

Gas barriers, humidity and microbial growth
As many of these biobased materials are hydrophilic in nature therefore their gas barrier properties are very much dependent on the humidity conditions for the measurements and its gas permeability may increase many times with when increase in humidity. Same is the phenomenon with conventional polymers. Gas barriers based on PLA and PHA is not expected to be more dependent on humidity. According to the study microbial contamination levels of packages made from conventional and biobased materials are relatively below the standard of 1 organism/cm2. A microbial study of cellulose triacetate, a type of bioplastic shows that after years of storage under ambient conditions mostly Pseudomonas bacteria is found in the film. Different tests for fungal growth (ASTM G21-96, G22-76, G21-70) has been conducted on the bioplastics, after many years of storage it was found that a low growth of selected food related fungi like Penicillium ocured in the same.

Bioplastics

Starch based plastics: - Starch the storage polysaccharide of cereals, legumes and tubers is a renewable and widely available raw material for bioplastics. Flexibiliser and plasticizer such as sorbitol and glycerin are added so that starch can also be processed. As a packaging material starch alone does not form films with adequate and required s mechanical properties of high percentage elongation, tensile and flexural strength unless it is treated by either plasticization, blending with other materials, genetic or chemical modification or combinations of different approaches. For which corn is the primary source of starch, although considerable amounts of starch are produced from potato wheat and rice starch.

Bioplastics produced from classical chemical synthesis from biobased monomers: - Using classical chemical synthesis for the production of polymer gives a wide spectrum of possible “bio-polyesters”. Polylactic acid is the polymer with the highest potential for a commercial production of renewable packaging materials. However, a wide range of other bio polyesters can be made. Theoretically, all the conventional packaging materials derived from mineral oil today in coming future can be produced from renewable monomers gained by fermentation. Today, this approach is not feasible due to the cost of the production of the monomers has economical constraint.

Polylactic Acid (PLA) plastics: - Polylactic acid, PLA is a biodegradable, thermoplastic, aliphatic polyester derived from lactic acid. The lactic acid source of PLA is itself produced from the fermentation of agricultural by-products such as corn-starch or other starch-rich substances like maize, sugar or wheat. PLA has high potential for packaging applications. The properties of the PLA material are highly related to the ratio between the two mesoforms of the lactic acid monomer. Using 100% L-PLA results in a material with a very high melting point and high crystallinity. A 90%/10% D/L co-polymers gives a material which can be polymerized in the melt, oriented above its Tg and is easily processable showing very high potential of meeting the requirements of bulk packaging. PLA may be formed into blown films, injection moulded objects and coatings. PLA is the first novel biobased material produced on large scale.

Bioplastics produced directly by natural or genetically modified organisms: - Poly Hydroxy alkanoates (PHA's) and Poly Hydroxy butyrate (PHB) is the most common polyester produced by certain bacteria processing glucose or starch. The properties of PHA's are dependent and relates upon the composition of monomer unit, the microorganisms used in fermentation, as well as the nature of the carbon source used during the fermentation process. It is a typical highly crystalline thermoplastic PHA are elastomers with low-milting points and a relatively lower degree of crystallinity. A very interesting property of PHA's with respect to food packaging applications is their low water-vapour permeability which is close to that of LDPE. The renewable resource-based plastic has similar properties to polystyrene. PHB resembles isotactic polypropylene (iPP) in relation to melting temperature (175-180°C) and mechanical behaviour. PHBs Tg is around 9°C and the elongation to break of the ultimate which is very important in bulk packaging application especially in flexible intermediate bulk containers and bulk shrink packaging. It has been reported in the literature

that annealing can dramatically improve the mechanical properties of PHB by changing its lamellar morphology while subsequent ageing is prevented to a large extent. Incorporation

of 3HV or 4HB co-monomers produces remarkable changes in the mechanical properties. Stiffness and tensile strength decrease with increase of toughness with increasing fraction of the respective co-monomer. Medium chain length PHAs, unlike PHB or its copolymers, behave as elastomers with crystals therefore, can be regarded as a class of its own with respect to mechanical properties. Elongation to break up to 250-350% has been reported and a Young‟s modulus up to 17 MPa.

Polyamides 11: - PA11 is a biopolymer derived from natural oil. It is also known under the trade name Rilson B commercialized by Arkoma. It is used in high-performance application like automotive fuel lines, pneumatic airbrake tubing and flexible goods means they too have good mechanical properties as they are used in automotive and electrical stuffs.

Broad Range of Bioplastics

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

Easy to mold due to lower melting temperat

We showed DARPA that we could make a new plastic from plant oils that has remarkable properties, which includes being tougher and more durable than typical polyethylenes. Additionally, the bioplastic can be placed in a simple container where it is safely broken down to liquid fuel.
—Prof. Gross

Military units generate substantial quantities of packaging waste when engaging in stationary field operations. If we can turn this waste into fuel, we will see a double benefit—we will reduce the amount of waste that we have to remove, and we will reduce the amount of new fuel that we must deliver to the units.
—Khine Latt, program manager for DARPA’s Mobile Integrated Sustainable Energy Recovery program

properties

Water vapour transmittance: While comparing the water vapour transmittance of various biobased materials to conventional plastics it comes out that it is possible to produce biobased materials with water vapour transmittance rates comparable with some conventional plastics. Research are currently focusing on this problem and future biobased materials will be compatible in terms of water vapour barriers with conventional conventional pastic materials known today.

Thermal and mechanical properties: The thermal and mechanical properties of the materials are important for processing and for use of the products derived from these materials. Most biobased polymer materials act in a similar fashion to conventional polymers. This indicates that both polystyrene, polyethylene and PET-like materials can be found among the available biobased polymers.The mechanical properties in terms of modulus and stiffness are not much different compared to conventional polymers.

The modulus of most biobased and petroleum derived polymers can be tailored to meet the required mechanical properties by plasticizing, blending, crosslinking. A polymer like bacterial cellulose could be used in materials to meet special mechanical properties

BULK

PROPERTIES OF BIOPLASTICS (ASTM standard)

Physical properties
Mold shrinkage	0.0125-0.0155 in/in
Density	1.4g/cm³
Apparent viscosity(180ºC, 100 sec¯ ¹)	950 Pa-s
Thermal properties
Melting point	160-165ºC
Heat distortion temperature	143ºC 78ºC
Vicat softening temperature	147ºC
Mechanical properties
Tensile strength	26 MPa(3800psi)
Shrinkage	0.93% caliper
Tensile modulus	3400 MPa(494,000psi)

Mechanical Properties

PROPERTIES OF BIOPLASTICS (ASTM standard)

Physical properties
Mold shrinkage	0.0125-0.0155 in/in
Density	1.4g/cm³
Apparent viscosity(180ºC, 100 sec¯ ¹)	950 Pa-s
Thermal properties
Melting point	160-165ºC
Heat distortion temperature	143ºC 78ºC
Vicat softening temperature	147ºC
Mechanical properties
Tensile strength	26 MPa(3800psi)
Shrinkage	0.93% caliper
Tensile modulus	3400 MPa(494,000psi)

PACKAGING

Classification based on basic guidelines there is different bulk packaging systems:

Metal packaging (steel drums and barrels, large cans)
Rigid plastic packaging (Plastic barrels, IBC‟s, large bottles)
Flexible packaging systems (Sacks, woven sacks, FIBC‟s, films for stretch wrapping, shrink wrapping)
Paper-based packaging (corrugated fiberboard, multiwall layer sacks, fiber drums)
Bag-in-box and bag-in-drum systems
Aseptic bulk packaging
Wooden packaging (pallets and cases)

Producing conventional plastics consumes 65% more energy than producing bioplastic.
Conventional plastic are mostly toxic.
Plastics last a long time and do huge damage to environment. Therefore, plastic is absolutely unsustainable and bioplastic is more sustainable.
Bioplastics saves 30-80% of the greenhouse gas emissions and provide longer shelf-life than normal plastic.

Bulk packaging systems related with conventional plastics are as follows:-

Intermediate bulk containers (IBC): An Intermediate bulk container is a container used for transport and storage of fluids and bulk materials. The construction of the IBC container and the materials used are chosen depending on the application. They are generally cubic in shape and therefore can transport more material in the same volume than cylindrically shaped containers and far more may be shipped in the same space if packaged in consumer quantities. IBCs range in size but are generally between 700 and 2,000 mm or 1,168 to 1,321mm in height. IBCs may ship and store Bulk chemicals including hazardous materials if the IBC is proven suitable. The plastic used in the manufacturing of IBC‟s are basically polyethylene, polypropylene these are plastics are used because they have lower impact strength, high tensile strength, High compressive strength, excellent dielectric properties, resists to alkalis and acids, resists stress cracking, retains stiffness, low moisture absorption, non- toxic, non-staining, easily fabricated, and high heat resistance.

ASTM or UL test

Property

LDPE

HDPE

POLYPROPYLENE

NYLON

PVC

PHYSICAL

D792

Density (g/cm³)

(lb/in³)

0.033

0.92

0.035

0.95

1.22-1.23

1.12 - 1.14

0.051

1.41

D570

Water Absorption, 24 hrs (%)

<0.01

0.09-0.1

2.9

MECHANICAL

D638

Tensile Strength (psi)

1,800-2,200

4,600

58 - 104

9.4

7500

D638

Tensile Modulus (psi)

195,000

411,000

D638

Tensile Elongation Yield (%)

600

900

D790

Flexural Strength (psi)

72-15

NO YEILD

12800

D790

Flexural Modulus (psi)

200,000

6555-6900

1.5

481000

D695

Compressive Strength (psi)

7,000

D695

Compressive Modulus (psi)

D785

Hardness, Shore D

D41-D50

D69

92R

104(R)

115(R)

D256

IZOD Notched Impact (ft-lb/in)

No Break

1.9

2.2

1.0

THERMAL

D696

Coefficient of Linear Thermal Expansion (x 10-5 in./in./°F)

6.2

6.1

D648

Heat Deflection Temp

120 / 105 / 36

170 / 150 / 40

210

125/52

340

176/80

(°F / °C)

at 66 psi

at 264 psi

D3418

Approx. Melting Temperature (°F / °C)

230 / 110

260 / 125

327 / 164

Max Operating Temp (°F

/ °C)

160 / 71

180 / 82

175

140/60

C177

Thermal Conductivity

0.76-0.81

0.90

(BTU-in/ft²-hr-°F)

(x 10-4 cal/cm-sec-°C)

2.6-2.8

3.1

UL94

Flammability Rating

n.r.

H-B

V-O

ELECTRICAL

D149

Dielectric Strength (V/mil) short time, 1/8" thick

460-700

450-500

500-660

544

D150

Dielectric Constant at 1 kHz

2.25-2.30

2.30-2.35

2.25

3.7

3.2

D150

Dissipation Factor at 1 kHz

0.0002

0.0005-0.0008

0.12

.0096

D257

Volume Resistivity (ohm-cm) at 50% RH

1015

8.5×1014

10-12

5.4 x 1015

D495

Arc Resistance (sec)

135-160

200-250

160

Plastics

Water vapour

transmission rate g/m²,38ºC, 90% RH

Gas transmission rate cc/m², 24h/atm at 25ºc

Heat seal rate, ºC

O²

CO²

LDPE

18.6

7750

41850

158-176

HDPE

4.6-100

2868

8990

162-169

Polypropylene

6.2-100

2325-

3720

7750

170-188

PVC

124-465

310-465

158-176

Nylon

388

40.3

155-186

176-220

Thermal properties: Melting temperature
Biopolymers comparable with conventional plastics

Oxygen transmission rate
Biopolymers in the midfield

Transmission of UV-light

Gas barrier properties: In most packaging applications the gas mixture inside the package consists of carbon dioxide, oxygen and nitrogen or combinations. Biobased materials have quite same oxygen permeability that of conventional mineral-oil-based materials and it is possible to select from a range of barriers among the present biobased materials. The conventional approach to introduce high-barrier films for packaging of food is to use multi-layers of different films in order to obtain the required properties. A laminate that is often used in packaging consists of an layer of EVOH or PA6 combined with LDPE for mechanical strength and the excellent sealing properties. A similar multi-layer approach for biobased materials may be used to produce materials with the required properties. Starch-based materials could provide cheap alternatives to presently available gas barrier materials like EVOH and PA6 and an equivalent biobased laminate would be an outer- layer of plasticized chitosan, a protein or starch-derived film combined with PLA or PHA. PLA and PHA will protect the moisture-sensitive-gas-barrier made of polysaccharide and protein. Developments have made it possible to improve water vapour and gas properties of biobased materials many-fold by using plasma deposition of glass- like SiOx coatings on biobased materials or the production of nano-composites out of a natural polymer.

Gas barriers, humidity and microbial growth

As many of these biobased materials are hydrophilic in nature therefore their gas barrier properties are very much dependent on the humidity conditions for the measurements and its gas permeability may increase many times with when increase in humidity. Same is the phenomenon with conventional polymers. Gas barriers based on PLA and PHA is not expected to be more dependent on humidity. According to the study microbial contamination levels of packages made from conventional and biobased materials are relatively below the standard of 1 organism/cm2. A microbial study of cellulose triacetate, a type of bioplastic shows that after years of storage under ambient conditions mostly Pseudomonas bacteria is found in the film. Different tests for fungal growth (ASTM G21-96, G22-76, G21-70) has been conducted on the bioplastics, after many years of storage it was found that a low growth of selected food related fungi like Penicillium ocured in the same.

Water vapour transmittance: While comparing the water vapour transmittance of various biobased materials to conventional plastics it comes out that it is possible to produce biobased materials with water vapour transmittance rates comparable with some conventional plastics. Research are currently focusing on this problem and future biobased materials will be compatible in terms of water vapour barriers with conventional conventional pastic materials known today.

Thermal and mechanical properties: The thermal and mechanical properties of the materials are important for processing and for use of the products derived from these materials. Most biobased polymer materials act in a similar fashion to conventional polymers. This indicates that both polystyrene, polyethylene and PET-like materials can be found among the available biobased polymers.The mechanical properties in terms of modulus and stiffness are not much different compared to conventional polymers.

The manufacturing processes which can be used for a bioplastic bulk packaging are extrusion, co-extrusion, blow moulding, injection blow moulding and thermoforming. Bioplastics can be processed in all of these process to a potential bulk package.

PROPERTIES

PROPERTIES OF BIOPLASTICS (ASTM standard)

Physical properties
Mold shrinkage	0.0125-0.0155 in/in
Density	1.4g/cm³
Apparent viscosity(180ºC, 100 sec¯ ¹)	950 Pa-s
Thermal properties
Melting point	160-165ºC
Heat distortion temperature	143ºC 78ºC
Vicat softening temperature	147ºC
Mechanical properties
Tensile strength	26 MPa(3800psi)
Shrinkage	0.93% caliper
Tensile modulus	3400 MPa(494,000psi)

Polymer

Bioplastics also provides very good printability, without any pre-treatment. Apart from this PLA have particularly high glossiness, high transparency, and good aroma or fat barriers, high oxygen barrier properties, antistatic properties.

Now comparing with the petro-based plastic we find that bioplastics have enough potential that it can be implemented in the IBC, FIBC, Shrink wrapping, and as liners in the bulk packages.

Biological derived polymers may be used for the production bulk packages with the same technology used for conventional materials. These data proves that they are no where less in any physical, thermal, mechanical and barrier properties than conventional plastics.

Bioplastics have following several other important advantages over conventional plastics in bulk packaging which are as follows:

Compost derived in part from bioplastics increases the soil organic content as well as water and nutrient retention, with reducing chemical inputs and suppressing plant
Starch-based bioplastics have been shown to degrade 10 to 20 times quicker than conventional
On burning traditional plastics, create toxic fumes which can be harmful to people's health and the If any biodegradable films are burned, there is little, if any, toxic chemicals or fumes released into the air.
Safe Biodegradability: In degradation test it was found that more than 90% of samples degrade in 10 months, according to the measurements of weight loss and CO2 There are water soluble biocomposites with solubility depending on the amount and the molecular weight and its crystallinity. Bioplastics like PHBV, PHB are biodegradable in soil, river, water, sea-water aerobic and anaerobic sewer sludge and compost. For example PHBV mineralizes in anaerobic sewer sludge to CO2, water and some percentage of methane to the extent of nearly 80% in 30 days. Another example is application of a special biocomposite in making of laundry bags for hospital and other institutions, where the bag dissolve during the washing and biodegrade after disposal into sewage. Samples of bioplastic compost, obtained by mixing the test material with organic waste, are compared with samples of a reference compost produced only with organic waste and was found that the effect of compost samples on the plant growth is assessed and during degradation, does not release substances toxic for the plants and environment. Composting is not the only environment in which the degradation of the biobased materials can occur. Soluble biobased material can be flushed in the sewage system and can be biodegraded in waste water treatment plants. Bioplastic materials can also be used in agriculture where the degradation takes place in soil.

Starch-based bioplasticsare important not only because starch is the least expensive biopolymer but because it can be processed by all of the methods used for synthetic polymers, like film extrusion and injection moulding. Eating utensils, plates, cups and other products have been made with starch-based plastics.
Interest in soybeanshas been revived, recalling Ford's early efforts. In research laboratories it has been shown that soy protein, with and without cellulose extenders, can be processed with modern extrusion and injection moulding methods.
Many water soluble biopolymerssuch as starch, gelatin, soy protein, and casein form flexible films when properly plasticized. Although such films are regarded mainly as food coatings, it is recognized that they have potential use as nonsupported stand-alone sheeting for food packaging and other purposes.
Starch-protein compositionshave the interesting characteristic of meeting nutritional requirements for farm animals. Hog feed, for example, is recommended to contain 13-24% protein, complemented with starch. If starch-protein plastics were commercialized, used food containers and serviceware collected from fast food restaurants could be pasteurized and turned into animal feed.
Polyestersare now produced from natural resources-like starch and sugars-through large-scale fermentation processes, and used to manufacture water-resistant bottles, eating utensils, and other products.
Poly(lactic acid)has become a significant commercial polymer. Its clarity makes it useful for recyclable and biodegradable packaging, such as bottles, yogurt cups, and candy wrappers. It has also been used for food service ware, lawn and food waste bags, coatings for paper and cardboard, and fibers-for clothing, carpets, sheets and towels, and wall coverings. In biomedical applications, it is used for sutures, prosthetic materials, and materials for drug delivery.
Triglycerideshave recently become the basis for a new family of sturdy composites. With glass fiber reinforcement they can be made into long-lasting durable materials with applications in the manufacture of agricultural equipment, the automotive industry, construction, and other areas. Fibers other than glass can also be used in the process, like fibers from jute, hemp, flax, wood, and even straw or hay. If straw could replace wood in composites now used in the construction industry, it would provide a new use for an abundant, rapidly renewable agricultural commodity and at the same time conserve less rapidly renewable wood fiber.

The widespread use of these new plastics will depend on developing technologies that can be successful in the marketplace. That in turn will partly depend on how strongly society is committed to the concepts of resource conservation, environmental preservation, and sustainable technologies. There are growing signs that people indeed want to live in greater harmony with nature and leave future generations a healthy planet. If so, bioplastics will find a place in the current Age of Plastics.

Safe for Medicinal Use: Quite a number of applications are suggested or tested or used in Most of the bioplastics like PLA, PHB, PHBV are non-toxic and compatible with living cells, producing an extremely mild foreign body response and the biodegradation rate is excellent. Applications such as controlled drug, surgical equipments, surgical swab, wound dressings and even blood compatible membranes can be quoted as typical applications for considerations in hospitals. These materials unlike cotton, small pieces of material from swab or dressing can be left in wound without danger of inflammation. These applications especially in medicine is considered by their optical activity and piezoelectric properties.
Compared to conventional plastics derived from petroleum, bio-based polymers have more diverse stereochemistry and architecture of side chains which enables research scientists a great number of opportunities to customize the properties of the final packaging

Thus with this added advantages and almost similar properties of LDPE, PVC, Nylon, HDPE, PP we can implement bioplastics in the bulk packaging industry at the places of these petroleum based plastics which are creating environmental pollution by its non degradability and harmful gas emission.

OF

APPLICATIONS

Category

Advantages
Use

Advantages

Properties

Disadvantages

Evaluation

Medical

Dissolvable Sutures (Stitches)

Coatings for drugs

Non-toxic, biodegradable, bio-compatible, strong material

Cost of production
Long time to produce
Ethics of bacteria conditions (physiological stress)

Using biopolymer in the medical industry has reduced the quantity of invasive internal surgery, as the biopolymer implantations dissolve over time. This brings greater comfort and lower cost to the patient. However, with this better comfort also comes greater cost, a major issues with this product.

General disposable products

Bottles, Bags, nappies, wrapping, packaging etc..

Strength/hardness, high melting point, biodegradable

Cost of production
Long time to produce
Ethics of bacteria conditions (physiological stress)

Using biopol/PHB for disposable mass produced products ensure the impact society has upon the environment is reduced. Due to its biodegradable nature PHB products lessen the pressure on land fills and further pollution released from landfills, such as methane. Despite these positive uses, the high cost of production of PHB and biopol makes the polyerms still less favorable to use in the commercial market, when cheaper materials are on the market.

Application

APPLICATIONS

Category

Advantages
Use

Advantages

Properties

Disadvantages

Evaluation

Medical

Dissolvable Sutures (Stitches)

Coatings for drugs

Non-toxic, biodegradable, bio-compatible, strong material

Cost of production
Long time to produce
Ethics of bacteria conditions (physiological stress)

General disposable products

Bottles, Bags, nappies, wrapping, packaging etc..

Strength/hardness, high melting point, biodegradable

Cost of production
Long time to produce
Ethics of bacteria conditions (physiological stress)

BIOPLASTICS

MARKET AND PRICE OF BIOPLASTIC

The world currently utilises approximately 260 million tonnes of plastics per year. Europe uses approximately 53 million tonnes of plastics and the UK utilises approximately five million tonnes of plastics in a year. Bioplastics make up about 0.1% of the global market at an approximate consumption volume of 300,000 tonnes per year and experts predict that this market will grow six-fold by 2011 reaching over 1.5 million tonnes per year. In Europe, bioplastic consumption is approximately 60-100,000 tonnes per year and the UK utilises an estimated 15,000 tonnes per year.

The otherwise nominal bioplastics sector is all set to take a leap in the coming years. According to European Bioplastics Association, the global production capacity for bioplastics is projected to grow four times by 2020. The factors in favour of the bioplastics are the hefty packaging taxes introduced in the Europe and the US , surging oil and feedstock prices that are making conventional polymers more expensive and the European directives designed to establish an infrastructure for compostable bioplastics collection. Conventional plastics have scored over bioplastics in terms of price. In the past, bioplastics packaging has cost roughly 20% to 100% more than the petroleum-based plastic. However, stringent packaging taxes imposed in Europe and US combined with the escalating oil and feedstock prices are leveling the field for bioplastics with petroleum-based plastics. According to Plastics Exchange in Chicago, as a result of the rising oil prices the price of resins like polypropylene (PP) has risen about 45%.

The prices of any biopolymer are likely to be high when it is only produced on a small scale. The scale of production is likely to have a greater influence on the price than the costs of the raw material source and of the chemistry involved. Today prices are bit high but at higher scales of production the price will fall to a range of 1 to 10USD per kg.

market

MARKET AND PRICE OF BIOPLASTIC

(ASTM

MARKET AND PRICE OF BIOPLASTIC

More About

standard)

Physical properties

Mold shrinkage

0.0125-0.0155 in/in

Density

1.4g/cm³

Apparent viscosity(180ºC, 100 sec¯ ¹)

950 Pa-s

Thermal properties

Melting point

160-165ºC

Heat distortion temperature

143ºC

78ºC

Vicat softening temperature

147ºC

Mechanical properties

Tensile strength

26 MPa(3800psi)

Shrinkage

0.93% caliper

Tensile modulus

3400 MPa(494,000psi)

Tensile elongation brake

Compressive yield Stength

65MPa (approx)

Compressive Modulus

2GPa (approx)

Flexural strength

44 MPa(6390psi)

Izod impact strength

26 J/m(0.5 ft lbs/in)

Hardness

54 shore D(90ºC,2.16kg)

Bending module

387 MPa

Moisture absorption

0.16% (23ºC, 50% RH)

Transparency

High

Oxygen barrier

Medium-high

Other Properties

Stackability

Fair

Puncture Resistance

Excellent

Crystallinity

Now comparing with the petro-based plastic we find that bioplastics have enough potential that it can be implemented in the IBC, FIBC, Shrink wrapping, and as liners in the bulk packages.

Bioplastics have following several other important advantages over conventional plastics in bulk packaging which are as follows:

Compost derived in part from bioplastics increases the soil organic content as well as water and nutrient retention, with reducing chemical inputs and suppressing plant diseases.
Starch-based bioplastics have been shown to degrade 10 to 20 times quicker than conventional plastics.
On burning traditional plastics, create toxic fumes which can be harmful to people's health and the environment. If any biodegradable films are burned, there is little, if any, toxic chemicals or fumes released into the air.
Safe Biodegradability: In degradation test it was found that more than 90% of samples degrade in 10 months, according to the measurements of weight loss and CO2 production. There are water soluble biocomposites with solubility depending on the amount and the molecular weight and its crystallinity. Bioplastics like PHBV, PHB are biodegradable in soil, river, water, sea-water aerobic and anaerobic sewer sludge and compost. For example PHBV mineralizes in anaerobic sewer sludge to CO2, water and some percentage of methane to the extent of nearly 80% in 30 days. Another example is application of a special biocomposite in making of laundry bags for hospital and other institutions, where the bag dissolve during the washing and biodegrade after disposal into sewage. Samples of bioplastic compost, obtained by mixing the test material with organic waste, are compared with samples of a reference compost produced only with organic waste and was found that the effect of compost samples on the plant growth is assessed and during degradation, does not release substances toxic for the plants and environment. Composting is not the only environment in which the degradation of the biobased materials can occur. Soluble biobased material can be flushed in the sewage system and can be biodegraded in waste water treatment plants. Bioplastic materials can also be used in agriculture where the degradation takes place in soil.

Starch-based bioplastics are important not only because starch is the least expensive biopolymer but because it can be processed by all of the methods used for synthetic polymers, like film extrusion and injection moulding. Eating utensils, plates, cups and other products have been made with starch-based plastics.
Interest in soybeans has been revived, recalling Ford's early efforts. In research laboratories it has been shown that soy protein, with and without cellulose extenders, can be processed with modern extrusion and injection moulding methods.
Many water soluble biopolymers such as starch, gelatin, soy protein, and casein form flexible films when properly plasticized. Although such films are regarded mainly as food coatings, it is recognized that they have potential use as nonsupported stand-alone sheeting for food packaging and other purposes.
Starch-protein compositions have the interesting characteristic of meeting nutritional requirements for farm animals. Hog feed, for example, is recommended to contain 13-24% protein, complemented with starch. If starch-protein plastics were commercialized, used food containers and serviceware collected from fast food restaurants could be pasteurized and turned into animal feed.
Polyesters are now produced from natural resources-like starch and sugars-through large-scale fermentation processes, and used to manufacture water-resistant bottles, eating utensils, and other products.
Poly(lactic acid) has become a significant commercial polymer. Its clarity makes it useful for recyclable and biodegradable packaging, such as bottles, yogurt cups, and candy wrappers. It has also been used for food service ware, lawn and food waste bags, coatings for paper and cardboard, and fibers-for clothing, carpets, sheets and towels, and wall coverings. In biomedical applications, it is used for sutures, prosthetic materials, and materials for drug delivery.
Triglycerides have recently become the basis for a new family of sturdy composites. With glass fiber reinforcement they can be made into long-lasting durable materials with applications in the manufacture of agricultural equipment, the automotive industry, construction, and other areas. Fibers other than glass can also be used in the process, like fibers from jute, hemp, flax, wood, and even straw or hay. If straw could replace wood in composites now used in the construction industry, it would provide a new use for an abundant, rapidly renewable agricultural commodity and at the same time conserve less rapidly renewable wood fiber.

Safe for Medicinal Use: Quite a number of applications are suggested or tested or used in medicine. Most of the bioplastics like PLA, PHB, PHBV are non-toxic and compatible with living cells, producing an extremely mild foreign body response and the biodegradation rate is excellent. Applications such as controlled drug, surgical equipments, surgical swab, wound dressings and even blood compatible membranes can be quoted as typical applications for considerations in hospitals. These materials unlike cotton, small pieces of material from swab or dressing can be left in wound without danger of inflammation. These applications especially in medicine is considered by their optical activity and piezoelectric properties.
Compared to conventional plastics derived from petroleum, bio-based polymers have more diverse stereochemistry and architecture of side chains which enables research scientists a great number of opportunities to customize the properties of the final packaging material.

APPLICATIONS

Category

Advantages
Use

Advantages

Properties

Disadvantages

Evaluation

Medical

Dissolvable Sutures (Stitches)

Coatings for drugs

Non-toxic, biodegradable, bio-compatible, strong material

Cost of production
Long time to produce
Ethics of bacteria conditions (physiological stress)

General disposable products

Bottles, Bags, nappies, wrapping, packaging etc..

Strength/hardness, high melting point, biodegradable

Cost of production
Long time to produce
Ethics of bacteria conditions (physiological stress)

Type

MARKET AND PRICE OF BIOPLASTIC

Conclusion

CONCLUSION

Comparing the properties of biobased polymeric materials with the conventional synthetic petroleum derived polymers shows a major potential of these polymers for the production of well-performing bulk packages. The biobased materials have an inherent potential of being compostable which must help the commercialization of these materials. As with any emerging technology, continued innovation and global support is essential for bioplastics too for fully demonstrate for its socio-economic benefits and further challenge the status of traditional petroleum based plastics in the field of bulk packaging. In social context biodegradable plastics call for a re-examination of life-styles. They will require separate collection, involvement of the general public, greater community responsibility in installing recycling systems, etc. On the question of cost, awareness may often be lacking of the significance of both disposal and the environmental costs, which are to be added to the processing cost. The developments in the fields of bioplastics looks very promising given the fact that compositions of bioplastics are inexpensive, available annually biodegradable in several environments and incinerable. Thus we can use the bioplastics in our bulk packaging systems where conventional plastic is basically used and save our environment.

Polymer market

CONCLUSION

CONCLUSION Comparing the properties of biobased polymeric materials with the conventional synthetic petroleum derived polymers shows a major potential of these polymers for the production of well-performing bulk packages. The biobased materials have

CONCLUSION

MARKET

CONCLUSION

CONCLUSION Comparing the properties of biobased polymeric materials with the conventional synthetic petroleum derived polymers shows a major potential of these polymers for the production of well-performing bulk packages. The biobased materials have

CONCLUSION

AND

CONCLUSION

MARKET AND PRICE OF BIOPLASTIC The world currently utilises approximately 260 million tonnes of plastics per year. Europe uses approximately 53 million tonnes of plastics and the UK utilises approximately five million tonnes of plastics in a year.

MARKET AND PRICE OF BIOPLASTIC

PRICE

MARKET AND PRICE OF BIOPLASTIC

MARKET AND PRICE OF BIOPLASTIC The world currently utilises approximately 260 million tonnes of plastics per year. Europe uses approximately 53 million tonnes of plastics and the UK utilises approximately five million tonnes of plastics in a year.

MARKET AND PRICE OF BIOPLASTIC

OF

MARKET AND PRICE OF BIOPLASTIC

MARKET AND PRICE OF BIOPLASTIC The world currently utilises approximately 260 million tonnes of plastics per year. Europe uses approximately 53 million tonnes of plastics and the UK utilises approximately five million tonnes of plastics in a year.

MARKET AND PRICE OF BIOPLASTIC

BIOPLASTIC

APPLICATIONS Category Advantages Use Advantages Properties Disadvantages Evaluation Medical Dissolvable Sutures (Stitches) Coatings for drugs Non-toxic, biodegradable, bio-compatible, strong material Cost of production Long time to produce Ethics

APPLICATIONS

Category

Advantages
Use

Advantages

Properties

Disadvantages

Evaluation

Medical

Dissolvable Sutures (Stitches)

Coatings for drugs

Non-toxic, biodegradable, bio-compatible, strong material

Cost of production
Long time to produce
Ethics of bacteria conditions (physiological stress)

General disposable products

Bottles, Bags, nappies, wrapping, packaging etc..

Strength/hardness, high melting point, biodegradable

Cost of production
Long time to produce
Ethics of bacteria conditions (physiological stress)

CONCLUSION

REFERENCES:

www.science.org.au
www.rfsung.org
www.zerowaste.co.nz
www.greenplastics.com
www.eng.iastate.edu
www.packaging-gateway.com
www.bioplastics24.com
Biodegradable Plastics by Dr. A. K. Mohanty
Weber, C.J. (Ed.). (2000). Biobased Packaging Materials for the Food Industry.
www.packagingknowledge.com\degradable&biodegradable bags.html
Technical Data Sheets. Novamont, www.novamont.com/ing/html/home.html
http://www.plastictechnology.com/articles/200209fa3.html
P. Halley. Biodegradable packaging for food industry. Package bottling int. vol 4, no4, pp
Plastics in packaging by A. S. Athalye, pp 61-75, pp 183-210
Handbook Of Package Engineering (2nd edition) by Joseph F. Hanlol, pp 8-1 8-83
www.nia.or.th/bioplastics.
www.azocleantech.com/details.asp?news
www.biomatnet.org/secure/Air/s235.htm
www.researchandmarket.com/reprtinfo.asp?
www.biodeg.net
Green Plastic: an introduction to the new science of biodegradable plastics (2002) by E.S. Stevens, pp 118-126
Degradable Polymers (Principles and Applications), 2nd edition by Gerald Scott, pp 295-316 pp 379- 400
Article on Biodegradable Packaging for food industry by I.P. Paltani & G.K. Goyal, NDRI, Karnal
Innovations in Food packaging by Jung H. Han, pp 240-243
Article on Biodegradable polymers: A rebirth of plastic by Shellie Berkesch, MSU, March
Article on Innovative Technologies for Biodegradable Packaging by Lillian Liu, SJSU, Feb
Processing & Characterization of Bio-Plastics (Presentation) by Yanir Shaked, UOM, Massachutes

Sudesh, K., Abe, H., Doi, Y

30.Methods for Analysis of Poly(3-hydroxyalkanoate) (PHA) Composition“. Biopolymers

31. The encyclopedia of bioprocess technology – Fermentation, biocatalysts anbioseparation.

32.http://www.nec.co.jp/eco/en/annual2006/02/2-1.html

33.http://biopact.com/2007_09_25_archive.html

34.http://www.greencarcongress.com/2007/03/researchers_dev_1.html

35.http://www.european-bioplastics.org

36.http://www.environmentalleader.com/2007/10/23/bioplastics-carve-out-niche/

37.http://www.epo.org/topics/innovation-and-economy/emerging-technologies/article-6.html

38.http://www.thenakedscientists.com/HTML/articles/article/bioplastics/

39.http://www.waste-management-world.com/display_article/273126/123/ARTCL/none/BIOTR/1/Beauty-of- bioplastics/

40.http://www.biobasics.gc.ca/english/View.asp?x=790

41http://www.immnet.com/articles?articl

Impressum

Texte: Rahul yadav
Bildmaterialien: rahul yadav
Lektorat: RAHUL YADAV
Übersetzung: PREETI YADAV
Tag der Veröffentlichung: 15.08.2016

Widmung:
All Polymer Industries

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