Umer Project Final

Introduction Ch-1 Recycling of mixed plastics waste
CHAPTER-1
INTRODUCTION
It would be hard to imagine a modern society today without plastics. Plastics have found a
myriad of uses in fields as diverse as household appliances, packaging, construction, medicine,
electronics, and automotive and aerospace components. As can be seen from this list, plastic
technology can be applied with great success in a variety of ways. So what makes plastic such a
versatile material? The reason for its success in replacing traditional materials such as metals,
wood and glass in such a diverse range of applications, is the ability to modify its properties to
meet a vast array of designers’ needs. This, plus the ease with which plastics can be processed,
makes them ideal materials for the production of a variety of components. Management of waste
is one of the major problems facing modern society and is not just limited to plastics. However, a
combination of legislative measures and government initiatives, the increasing cost of landfill
disposal and public interest in support of recycling has meant that plastics recycling must
increase. Generally, plastics are made from crude oil. Recycling of plastics therefore helps to
conserve this natural resource.
Any strategy for waste management is based around three guidelines.
• Avoidance, i.e., reducing and, if possible, avoiding producing waste at source. No waste = no
problem.
• Reclamation, the recovery of materials from the waste stream for recycling.
• Elimination, the disposal of non-recyclable materials, for example by landfill.
The second point can be applied to the problems of plastic waste by reclaiming material that is
destined for landfi ll. Hence, plastic material recovered from the waste stream is termed
‘reclaim’. A summary of the terms introduced so far is given in Table 1.1.
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A substantial part of public solid waste (MSW) streams is composed of mixed polymers. High-
density polyethylene (HDPE), polypropylene (PP) and polyvinyl chloride and PET
(Polyethylene terephthalate) are among the most common plastics waste, since they are the
most frequently used commercial plastics in our daily lives as well as in industries [1]. A number
of approaches are currently being investigated for dealing with post consumer resin. Incineration
for the purpose of waste-to-energy recovery is used in a number of countries, which are feared of
pollution. Another solution that is currently being developed is pyrolysis. A number of
companies are now introducing low levels of plastics waste into hydrocrackers that produce
Naphtha, which can then be used as part of feedstock for other applications, including
polymerization. A popular solution is the reuse of plastic parts, such as PET drinking bottles in
many countries.
The mixed plastics waste can be recycled in the form of blends [2-5]. The processing of plastics
mixtures for recycling has been attempted with some success [6-11]. But the plastics fraction
obtained by sorting municipal solid wastes often contains substantial quantity of paper. The
reprocessing of such material is very difficult even at paper levels as low as 10% [12], beside
this, the product’s appearance is unacceptable due to the inhomogeneity of the mixture, and the
mechanical properties are unsatisfactory [13].
1.1 Polymers
Polymers take their name from two Greek words: poli which means many and meros which
means parts. This is because they are made up of a number of repeat units, called monomers. The
simplest and most commonly used monomer is ethylene. Plastics can be subdivided into three
main categories: thermoplastics, thermosets and elastomers. This distinction is based on both the
molecular structure and the processing routes that can be applied. It also relates to recycling
routes, as each of the categories needs a different approach to utilise recovery potential.
Elastomers are beyond the scope of this book and will not be dealt with here. Thermoplastics and
thermosets will now be introduced.
1.1.1. Thermoplastics
These materials melt and fl ow when heated and solidify as they cool. On subsequent reheating
they melt and regain the ability to fl ow. This means they can be reprocessed and hence recycled
by remelting them. Thermoplastics are used to make consumer items such as drinks containers,
carrier bags and buckets. The most common thermoplastic materials and their applications are
shown in Table 1.2.
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1.1.2. Thermosets
Thermoset materials are melt processed, often in a similar manner to thermoplastics. However,
once formed and cooled they cannot be reprocessed, they decompose before they can melt.
Therefore, they cannot be reprocessed in the same way as thermoplastics. This is because they
are chemically crosslinked by a process termed ‘curing’. The result is a highly dense molecular
network making the material stiff and brittle. Thermosets are often used where their strength and
durability can be utilised. Common thermosets and their applications are shown in Table 1.3
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1.2 Effects of Processing on Thermoplastics

Processing in its simplest form is the act of melting, forming and then solidifying the melt.
During this procedure three things need to be considered [14].
• Deformation processes, which enable the product to be formed.
• Heat and heat transfer, which enable the polymer to melt, fl ow and then solidify.
• Changes to structure and properties as a result of processing.
We will begin with a study of deformation processes and for this, we need to consider rheology.
1.2.1. Rheology
Rheology is the study of deformation and fl ow. Consider the following examples of flow:
1. Squeezing toothpaste through a tube,

2. Tipping honey from a spoon, and
3. Pouring water into a glass.
In viscous flow, a material continues to deform as long as a stress is applied. polymers combine
both viscous and elastic properties and demonstrate what is called a viscoelastic response to
stress. Polymers are more viscous than most liquids. Polymers are more elastic than most solids.
The interaction between viscosity and elasticity frequently determines the success of any
processing operation. Processing must take into account not only how the polymers flow in their
molten state but also how they change as the temperature goes up and down and the polymers
melt and solidify. A cheap and simple method of determining and comparing the fl ow of melts
under standard conditions is a Melt Flow Indexer. This works in a similar way to squeezing
toothpaste from a tube. A vertical load is applied to a piston and the polymer melt is squeezed
through a die. The amount of polymer that is extruded in a fi xed time gives a measure of the
flow as a melt fl ow index (MFI). A highly viscous material will have a low MFI, a low viscosity
material will have a high MFI.
1.2 2. Heat
A thermoplastic cannot fl ow in its solid state. To enable it to fl ow it needs to be heated above
its melting point (Tm). Some melting points of common plastics are shown in Table 1.4. Just
from these examples, a wide range of melting points can be clearly seen. Once a polymer is
heated above the melting point the viscosity will decrease as the temperature increases. The rate
of this change varies, according to the particular type of material. Eventually the polymers will
reach a point where they become thermally unstable and start to degrade. Generally, this shows
itself as a discolouration with the melt turning yellow or brown. This can be a problem when
processing mixed plastic fractions, because of the difference in processing temperature required
to melt the various fractions contained in a heterogeneous mixture.
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1.3 Reprocessing of Thermoplastic Recyclates

For reclaiming used material or recyclate outside of this scenario, the situation is slightly
different and greater effort may be required on the part of the reprocessor. This type of
mechanical recycling is termed secondary recycling (Table 1.5).
The material from external sources may be received in a variety of forms such as bales,
mouldings or large lumps. It will probably need to be reduced in size, cleaned, separated and
possibly recompounded and regranulated before it can be reprocessed in production. Often little
is known about the history of the material to be recycled, for example: [15]
• How many times it has been reprocessed previously?

• How much thermal degradation it has already undergone?
• Is it in-house or external waste?
• Is it a single material or a combination of plastics (commingled)?
• Is it contaminated or uncontaminated?
• What it was used for previously?
• Has it been damaged due to outdoor exposure, weathering, etc?
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The characteristics of plastics can change depending on the exposure to thermal, mechanical
(shear), oxidative and photochemical degradation processes. The characteristics of the recyclate
may be quite different from those of the original virgin plastic.
Ideally, to produce high quality products, high quality materials are required. For this,
consideration must be given to a number of factors. It must be determined as to whether the
material is pure or commingled and whether it is contaminated, for example, with metal or wood.
For ease of feeding into the processing machines be they injection moulding, extrusion or blow
moulding, the size and shape of the regrind (i.e., the bulk density) must be suitable. If the
material is hygroscopic (water absorbing), for example polyamide, it may require pre-drying.
Finally, should the recyclate be reprocessed on its own, mixed with other virgin material or
modified with additives?
1.4 Recycling Techniques

Despite increasing research efforts it is not yet economical to separate the wide variety of
plastics that end up in the waste stream. The ideal is streams of single, clean and homogeneous
recyclates, which present little technical effort for recycling. Of course, streams of this type,
mainly industrial, can and are recycled. However, mixed waste streams present more of a
technical and economic challenge to recover. Mixed plastic fractions reduce the quality of the
products made from them quite considerably. This is due to differences in melting and
processing temperatures and the lack of compatibility [16]. However the properties of mixed
plastics waste is improved by using additives.
A typical recycling route for waste plastics can be split into two types of processes:
1. Physical/mechanical treatment to prepare and homogenise the waste, and
2. Melt processing.
Examples of stage one processes could include storage, size reduction, washing and sorting of
the waste. Stage two would include regranulation and reprocessing.
An outline of the various stages of the waste cycle is shown in Figure 1.1. These will now be
discussed.
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Figure 1.1 A process stream for recycled plastic material
1.4 .1 Size Reduction

Size reduction is necessary, because the material particles must be a suitable size for further
processing. This may involve a two-stage process, the fi rst using a shredder to produce large
particles of about 25-50 mm. These materials can then be fl aked. Rotary cutters are most
commonly employed for the latter, as they can be used for comminuting (breaking down the size
of) virtually any plastic.
1.4.2 Washing
Washing is required to remove any dirt and residues adhering to the waste plastic. It increases
the purity of the plastics and in some cases improves the effi ciency of other processes such as
sorting. The principles are the same as those applied to any household washing detergent. The
contaminants must adhere more strongly to the cleaning medium than the plastic to allow for
removal. Washing also removes labels and water soluble glue residues. Once the materials are
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away. Thermal methods use hot air to dry the plastic fl akes. washed they then need to be dried.
This can be done mechanically simply using gravity and a conveyor to allow any liquid to drain
away. Thermal methods use hot air to dry the plastic flakes.
1.4.3 Identification and Sorting of Plastics
One way to allow easy identification of plastics is to mark the mouldings. This is mandatory in
the packaging industry, so turning over a plastic bottle or container should reveal a plastics
identity code such as that shown in Figure 1.2. This allows the plastics to be sorted manually.
Figure 1.2 Society of Plastics Industry (SPI) packaging codes
Manual sorting is a very labour intensive process requiring equipment. FTIR can be used to
identify the mixed plastics waste.
1.4.4 Agglomeration
Agglomeration is a process stage to be carried out after the material is sorted into a fairly
homogeneous stream. The aim of the agglomeration is to increase the bulk density of the waste,
which is necessary to ensure good feeding for some plastication units. It finds most application in
waste plastics with film flake, which can have a bulk density of just 100 to 150 kg/m3. This can
make both feeding and storage cumbersome. Examples of fi lm waste before and after
agglomeration are shown in Figure 1.3.
Figure 1.3 Film waste before and after agglomeration
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Agglomeration can be differentiated from processing as here the aim is simply to bond the flakes
together at their surfaces and therefore only the surfaces of the plastics are affected. Pressing or
fusion is used for this, with the material being thermally stressed on the surface particles only for
a relatively short time.
1.5 Additives for Recyclates

The two biggest problems associated with plastics recycling of post consumer products are
1. The degradation of the plastics as a result of both processing and service life.
2. The difficulties associated with getting acceptable material properties when processing
mixed plastics [17].
To slow down the degradation of plastics, stabilisation additives are employed. Other additives
such as fi llers or modifi ers can be incorporated to improve the properties of the recyclates.
These modifi ers can also be of benefi t in mixed plastic fractions. First the issues associated with
the degradation of materials will be discussed.
1.5.1 The Degradation of Plastics
Due to their chemical make-up, most plastics are susceptible to damage from the influence of the
environment due to the action of light, heat and weathering. This ageing process is accompanied
by a drop in both the visual (commonly seen in a yellowing of white carrier bags) and
mechanical properties of the plastic, and it affects both virgin and recyclate materials alike.
Plastics are also susceptible to damage from the shear force that can arise during standard
manufacturing processes and granulation. This action is accelerated by the high temperatures
involved. The result is chemical degradation due to molecular damage in the form of chain
cleavage, crosslinking or the formation of a series of double bonds. Waste plastics, therefore,
will have degraded to some degree following their original usage. The level of this degradation
depends on the polymer type, on thermal and shear stress history and on the initial stabilization.
Additives are commonly added to plastics to inhibit or slow down these reactions.
1.5.2 Restabilization of Recyclates

Most plastics processors will reprocess their waste as a matter of course. It reduces their raw
material costs as well as the cost of waste disposal. Often this material is simply fed back into the
system along with virgin material. This presents few problems providing attention is paid to
cleanliness and the reprocessed material has not been contaminated with dirt, oil or other types of
material. The amount of degradation undergone by these materials will be dependent on the
processing conditions that they were subjected to and the levels of stabilisers present. If these
materials are to be used for a second application, it is possible to restabilise them. For this,
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knowledge of the type and amount of stabiliser originally used is required. Some stabilisers are
consumed in the process of protecting the plastic and these materials need to be kept at optimum
levels to ensure continued protection. Further testing may be required to assess the stability (both
processing and long-term).
a) Stabilizers
I. Thermal Stabilization
A combination of heat and oxygen will cause oxidation in the polymer, resulting in degradation.
The mechanism is the formation of free radicals, which are highly reactive chemical species.
This reaction can be observed, as the products will tend to show a discoloration to yellow or
brown. Additives called antioxidants can be used to interrupt this mechanism. The chemicals
most commonly employed are hindered phenols, which act as peroxide radical decomposers.
Other additives can also be employed in addition to hindered phenols. Additives called
phosphites combined with hindered phenols have a synergetic effect. This combination is
especially effective for polyolefins. Perhaps the most well known example of the use of additives
to prevent thermal degradation is in the thermal stabilization of polyvinyl chloride. The free
radicals produced in this case are chlorine, leading to the formation of hydrochloric acid. The
stabilisers must stop these reactions which lead to acid corrosion of the processing equipment.
II. Light Stabilization
Light, especially in the ultraviolet range can induce photooxidation causing degradation and
cleavage of the polymer chains. To deter this effect, three classes of additives can be employed.
These additives are usually termed UV absorbers, quenchers (scavengers) and radical traps.
b) Compatibilisers
The major problem with mixing plastics is the fact that they are generally immiscible with each
other. However useful combinations of immiscible materials are not uncommon. Blending of
existing. polymers to create new ones is a cost effective method to create new materials, since
synthesizing new polymers is both expensive and difficult. A common commercial example of a
blend is high impact polystyrene, which is a blend of polystyrene and polybutadiene particles.
Polybutadiene is a type of rubber that gives the blend greater impact resistance than could be
achieved with polystyrene alone. Polystyrene has a high modulus. The combined result is a
material that is both reasonably strong and has good impact resistance.
10

Literature Survey Ch-2 Recycling of mixed plastics waste

Chapter-2
LITERATURE SURVEY
Since the beginning of the plastics industry it has been recognized that blending yields materials
with property profiles superior to the features of the individual components. The blending of
polymers provides a means of producing new materials, which combine the useful properties of
all of the constituents (Utracki, 2000). The technology of blending is now advancing at a rapid
pace [18]. The ability to combine existing polymers into new compositions with commercial
utilities offers the advantage of reduced research and development expense compared to the
development of new monomers and polymers to yield a similar property profile [19]. An
additional advantage is the much lower capital expense involved with scale-up and
commercialization. Another specific advantage of polymer blends versus new monomer/polymer
compositions is that blends often offer property profile combinations not easily obtained with
new polymeric structures [20]. Blending technology is more useful in the field of plastics
recycling. It is estimated that about one third of all commercially produced polymer materials are
blends of two or more polymers.
Recycling of plastics discard is one method of reducing municipal solid waste. It is difficult,
however, to expand plastics recycling because of the variety of plastics wastes, the difficulty of
sorting different typed plastics, the low density of post-consumer plastics wastes in comparison
to other recyclables and the limited history of plastics recycling. Because of its heterogeneous
nature and the amount of contaminants present, separation of post-consumer mixed plastics
waste is the most difficult. The term “mixed plastics,” a mixture of plastics types or a mixture of
package types which may or may not be the same plastics type or color category, has been used
to describe broad scale processing of post-consumer plastic waste. It is possible to recycled
mixed plastics waste with limited separation.

The two main alternatives for treating municipal and industrial polymer wastes are energy
recycling, where wastes are incinerated with some energy recovery and mechanical recycling.
The incineration of polymer waste meets with strong Kyoto Protocol to consider, as the UK
moves towards societal opposition [21] and, there is the its domestic goal of reducing carbon
dioxide emissions by 20% by 2011 [22]. Mechanical recycling (the conversion of ‘‘scrap’’
polymer into new products) is a popular recovery path for manufacturers and is carried out on
single-polymer waste streams as a market for recycled products can only be found if the quality
is close to that of the original. Unfortunately these products are often more expensive than virgin
plastic [23, 24]. In 2002 in the UK, only 17% of 3.8 million tones of was recycled by these
methods, the remainder was polymer waste land-filled or incinerated (without energy recovery)
[25].
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In1978 Ghaffar A. and Scott, G studied the Morphology and mechanical properties of virgin and
recycled polyethylene/polyvinyl chloride blends. They prepared blends of virgin and recycled
polyethylene (PE) and poly(vinyl chloride) (PVC), with a methylmethacrylate-ethylacrylate
copolymer as a processing aid in a molten state. The blends' morphologies, tensile properties,
and impact properties were studied. For blends with low copolymer concentration (below 3 wt
%) the mechanical test data indicated a good performance. In the case of blends with ethylene
methacrylic acid ionomer, improvements in the mechanical properties were obtained also at
higher additive concentrations. Of the two peroxides, better results were obtained using the
dibenzoyl one. The morphological studies indicated that the blends that showed good mechanical
properties were better dispersed and had improved interphase adhesion.

Recycling of waste plastics as a blend of generic types is attractive since a difficult separations
problem is avoided. However, blends of incompatible polymers are frequently very brittle and
cannot be considered for many applications. Additives which modify the blend to give it ductility
may provide a solution to this problem. In 1972 Paul D.R., Vinson C.E. and Locke C.E
suggested that addition of CPE (chlorinated PE) to such a blend generally increases the
elongation at break and the energy to break very dramatically with ordinarily some loss in
strength and modulus. This approach worked most effectively in blends of high polyethylene and
poly (vinyl chloride) content. Three grades of CPE were studied here which revealed that the
specific structure of the CPE molecule is a factor.

Guowei Ma, Zhengping Fang and Chengwei Xu inquired the co-crosslinked products and the
entrapping phenomenon that may exist in a poly(vinyl chloride)/ low density
polyethylene/dicumyl peroxide (PVC/LDPE/ DCP) blend were investigated. The results of
selective extraction show that unextracted PVC was due to not being co-crosslinked with LDPE
but being entrapped by the networks formed by the LDPE phase. SBR, as a solid-phase
dispersant, can promote the perfection of networks of the LDPE phase when it is added to the
PVC/LDPE blends together with DCP, which leads to more PVC unextracted and improvement
of the mechanical properties of PVC/ LDPE blends.

The mechanical properties of blends of isotactic polypropylene and high-density polyethylene

with a postconsumer resin (recycled dairy containers) were investigated by Blom H.P., Teh J.W.,
and Rudin A. (1998) over the entire composition range. Modification of these blends with an
ethylene/propylene/diene copolymer or an ethylene/vinyl acetate copolymer was also
investigated. Isotactic polypropylene/postconsumer resin blends have satisfactory impact and
tensile properties at postconsumer resin contents of less than 50% for certain applications. At
higher postconsumer resin contents, the tensile properties were adversely affected. The impact
properties remained satisfactory. Addition of an ethylene/propylene/diene copolymer improved
the mechanical properties of these blends to levels equal to or greater than those for neat isotactic
12


polypropylene. Ethylene/vinyl acetate copolymers were also able to improve the mechanical
properties, but not as efficiently as did the ethylene/propylene/diene copolymer. Blends of high-
density polyethylene and a postconsumer resin had poor impact and tensile properties. Although
the ethylene/propylene/diene copolymer and ethylene/vinyl acetate copolymers were able to
improve these properties, the improvement was insufficient for general recycling, except at lower
(≤25%) postconsumer resin contents.
A mixture of seven immiscible “virgin” plastics, namely low and high density polyethylene
(LDPE and HDPE), polypropylene (PP), polyvinyl chloride (PVC), crystal and high impact
polystyrene (PS and HIPS), and polyethylene terephthalate (PET), in proportions representative
of those currently found in post-consumer plastics containers, was compounded in a corotating
twin-screw extruder. The mechanical properties of the blend were improved through the addition
of relatively high concentrations of a dialkyl peroxide which was also found to drastically affect
the blend morphology. The results are interpreted in terms of improved dispersive mixing
favored by the similarity in the rheological behavior of the modified blend components,
improved physical properties of certain blend components upon peroxide modification, and,
possibly, enhanced intefacial adhesion [26].
Klason C., Gatenholm P., Kubat J., Mathiasson A., and Abom J., in 1991 executed the work on
Recycling of Mixed Plastics Using Cellulosic Reinforcement. Their research demonstrated that
the effect of combining chemithermomechanical pulp (CTMP) fibers and MAH-SEBS
compatibilizer (maleic acid anhydride-grafted styrene-ethylene/butylene-styrene block
copolymer) with a simulated waste plastic fraction composed of LDPE and HIPS (70:30)
improve the mechanical properties of blend [27]. Experimental work demonstrated that an
essential improvement of the mechanical properties of waste plastics can be obtained by the
presence of cellulose fibers.

Great attention has been paid to the toughening of isotactic polypropylene (PP) in recent years in
order to make full use of this plastic. Yang D., Zhang B., Yang Y., Fang Z., and Sun G., studied
on the compatibility of PP with ethylene-propylene-diene rubber (EPT), polybutadiene rubber
(PB) or styrene-butadiene rubber (SBR) through characterization of the blends' morphology, and
on. the morphology and properties of binary blends of PP with EPT (EPT/PP) and ternary blends
of PP, EPT, and polyethylene (PE) (EPT/PE/PP) [28]. Addition of EPT to EPT/PP made
interesting changes in morphology but no effect on properties was observed.

13

Experimental Setup Ch-3 Recycling of mixed plastics waste

CHAPTER-3
Experimental Setup
Before any recycling methodology is adopted, the techniques to acquire the following data have
to be developed.
• The number of times the selected waste has been reprocessed previously?
• The degradation it has already undergone
• Classification of waste
• Nature of the waste i.e. Single or a combination of plastics
• Degree of contamination
• Effect due to environmental exposure
• Use history.
3.1 Objectives of research

• Characterization of polymer waster
• To improve the quality of products made from recycled material and to make these
properties comparable to those obtained from the virgin polymer.
• To study the thermal and rheological behavior of recycled polymer blends
• To study the morphological structure of recycled polymer blends
• To find the optimum concentration of each component of waste in recycled polymer

blends that give better properties at reduced cost
• To find the optimum concentration of filler, plasticizer and stabilizer in recycled polymer
blends that give better properties at reduced cost
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3.2 Methodology
Brief description of how research was conducted
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3.3 Experimental set up.
Experimental set up consists of:
• Size reduction crusher
• Plasticoder
• Universal testing machine
• Compression molding machine
• FTIR
• DSC
• Melt flow indexer
• Scanning electron microscope (SEM)
3.4 Experimentation.
Three commonly used plastics such as Polyethylene (PE), Polyvinylchloride (PVC) and
Polyethylene terephthalate (PET) were selected for mixing.These polymers were crushed by
using size reduction crusher. The blends of PP/PVC/PET were prepared by using Brabender
plasticoder. The mixing time, rotation speed and temperature for the preparation of blend was 7
min, 80 rpm and 220 OC respectively. Additives were added during processing of blends. FTIR
spectroscopy technique was executed to ascertain the nature of cross linking among three
polymers. DSC was performed for thermal analysis of recycled. The compression moulding
technique was used for preparation of testing bars. Tensile testing was performed on TIRA test
2810 machine, according to ASTM D-638. Impact property was determined using a falling
weight impact tester, according to ASTM D-4224. Rheological properties were accomplished by
melt flow indexer. To observe the morphology of various blends, compression moulded samples
was sputtered with gold in vacuum. These samples were examined by scanning electron
microscope (SEM)
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3.5 Recipe Ingredients
• Total weight of material 40 gm
• Polymer 70% and additives 30%
• Weight of polymer 28 gm
• Weight of additives 12 gm
Additives were used to enhance the mechanical, thermal and rheological properties of recycled
polymer blends, For example
Sr. No Additives Function

1 EPDM Act as a compatiblizer and enhance the flow
properties as well as impact strength of recycled
blends
2 Clay To enhance the tensile properties of blends
3 Amines To enhance thermal properties of recycled blends
When PET is variable
Sr .No PET% & gm PVC PE EPDM Clay AMINES

1 10% =2.8 45%=12.6 45%=12.6 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
2 20%= 5.6 40%=11.2 40%=11.2 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
3 30% =8.4 35%=9.8 35%=9.8 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
4 40%=11.2 30%=8.4 30%=8.4 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
5 50%=14 25%=7 25%=7 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
6 60%= 16.8 20%= 5.6 20%=5.6 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
7 70%= 19.6 15%=4.2 15%=4.2 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
When PE is variable
Sr .No PE% & gm PVC PET (EPDM) Clay AMINES

1 10% =2.8 45%=12.6 45%=12.6 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
2 20%= 5.6 40%=11.2 40%=11.2 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
3 30% =8.4 35%=9.8 35%=9.8 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
4 40%=11.2 30%=8.4 30%=8.4 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
5 50%=14 25%=7 25%=7 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
6 60%= 16.8 20%= 5.6 20%=5.6 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
7 70%= 19.6 15%=4.2 15%=4.2 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
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When PVC is variable
Sr .No PVC% & PET PE (EPDM) Clay AMINES

gm
1 10% =2.8 45%=12.6 45%=12.6 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
2 20%= 5.6 40%=11.2 40%=11.2 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
3 30% =8.4 35%=9.8 35%=9.8 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
4 40%=11.2 30%=8.4 30%=8.4 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
5 50%=14 25%=7 25%=7 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
6 60%= 16.8 20%= 5.6 20%=5.6 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
7 70%= 19.6 15%=4.2 15%=4.2 60% (7.2)gm 30% (3.6)gm 10% (1.2 gm)
18

IR-Analysis of recycled blend Ch-4 Recycling of mixed plastics waste

Chapter-4
IR-Analysis of recycled Blend
4.1 Infrared spectroscopy

Infrared spectroscopy (IR spectroscopy) is the spectroscopy that deals with the infrared region of
the electromagnetic spectrum, that is light with a longer wavelength and lower frequency than
visible light. It covers a range of techniques, mostly based on absorption spectroscopy. As with
all spectroscopic techniques, it can be used to identify and study chemicals. A common
laboratory instrument that uses this technique is a Fourier transform infrared (FTIR)
spectrometer.
The infrared portion of the electromagnetic spectrum is usually divided into three regions; the
near-, mid- and far- infrared, named for their relation to the visible spectrum. The higher energy
near-IR, approximately 14000–4000 cm−1 (0.8–2.5 μm wavelength) can excite overtone or
harmonic vibrations. The mid-infrared, approximately 4000–400 cm−1 (2.5–25 μm) may be used
to study the fundamental vibrations and associated rotational-vibrational structure. The far-
infrared, approximately 400–10 cm−1 (25–1000 μm), lying adjacent to the microwave region, has
low energy and may be used for rotational spectroscopy. The names and classifications of these
subregions are conventions, and are only loosely based on the relative molecular or
electromagnetic properties.
4.2 Fourier transform

The Fourier transform is a mathematical operation that decomposes a signal into its constituent
frequencies. Thus the Fourier transform of a musical chord is a mathematical representation of
the amplitudes of the individual notes that make it up. The original signal depends on time, and
therefore is called the time domain representation of the signal, whereas the Fourier transform
depends on frequency and is called the frequency domain representation of the signal. The term
Fourier transform refers both to the frequency domain representation of the signal and the
process that transforms the signal to its frequency domain representation.
FTIR is a measurement technique that allows one to record infrared spectra. Infrared
light is guided through an interferometer and then through the sample (or vice versa). A
moving mirror inside the apparatus alters the distribution of infrared light that passes
through the interferometer. The signal directly recorded, called an "interferogram",
represents light output as a function of mirror position. A data-processing technique
called Fourier transform turns this raw data into the desired result (the sample's spectrum):
Light output as a function of infrared wavelength (or equivalently, wavenumber). As
described above, the sample's spectrum is always compared to a reference.
19


4.3 Principle of FTIR
In a Michelson interferometer adapted for FTIR, light from the polychromatic infrared source,
approximately a black-body radiator, is collimated and directed to a beam splitter. Ideally 50% of
the light is reflected towards the fixed mirror and 50% is transmitted towards the moving mirror.
Light is reflected from the two mirrors back to the beam splitter and (ideally) 50% of the original
light passes into the sample compartment. There, the light is focused on the sample. On leaving
the sample compartment the light is refocused on to the detector. The difference in optical path
length between the two arms to the interferometer is known as the retardation. An interferogram
is obtained by varying the retardation and recording the signal from the detector for various
values of the retardation (as shown in fig 4.1)
The interference pattern is converted into an electrical signal by the detector, and after being
amplified by the main amplifier, is converted into signal. The spectrum in which the horizontal
axis represents the light path difference between the moving mirror and fixed mirror and vertical
axis represent light intensity is called interferogram. The intensity distribution with respect to
wave number can be obtained by subjecting the interferogram to Fourier transformation.
Therefore, the digital signal is subjected to Fourier transformation and the resulting spectrum is
displayed on the PC monitor screen (as shown in Fig 4.2)
Fig- 4.1 Optical System
20


Fig-4.2 Signal flow
4.4 Common Applications

• Identification of compounds by matching spectrum of unknown compound with reference
spectrum (fingerprinting)
• Identification of functional groups in unknown substances
• Identification of reaction components and kinetic studies of reactions
• Identification of molecular orientation in polymer films
• Detection of molecular impurities or additives present in amounts of 1% and in some

cases as low as 0.01%
• Identification of polymers, plastics, and resins
• Analysis of formulations such as insecticides and copolymers

21


4.5 FTIR Spectra of pure components (collection from waste)
4.5 (a) FTIR spectrum of PET
22


Classification: Aromatic Polyester-Polymer IR (Group: Poly (ethylene terephthalate)
Bond Range Mode

p-DISUBST 3090-3070 CH STR
CH2 2970-2940 ASYM_STR
CH2 2900-2850 SYM_STR
C=O 1730-1710 STR
p-DISUBST 1615-1590 Ring
CH2 1470-1440 DEF
CH2 1370-1330 DEF_WAG
CO 1270-1240 STR
Poly (ethylene terephthalate), PET, is manufactured as a polycondensation between ethylene

glycol and terephthalic acid or dimethyl terephthalate. The relative intensities of the weak-
medium intensity bands, in particular, can differ significantly depending on whether the sample
is amorphous or crystalline and/or oriented, and consequently the spectrum can change quite
markedly according to a sample’s morphology and processing history. The first overtone of the
C=O near 1725 cm-1 can be observed as weak absorption band near 3410 cm-1.
In PET, the -CH2-CH2- unit, arising from the ethylene glycol monomer, can exist in either a
trans or a gauche conformation, and while the trans can be present in both the crystalline and
amorphous phases, the gauche form is only found in the amorphous phase. These conformers can
have distinct bands, for instance, deformation bands associated with the trans conformer occur at
ca. 1466, 1335 and 847 cm-1; while, the gauche conformer has bands at ca. 1449, 1368 and 896
cm-1.
23


4.5 (b) FTIR spectrum of PE
24


Classification: Saturated Aliphatic Hydrocarbon-Polymer IR (Group: Polyethylene)
Bond Range Mode

CH 2920-2880 STR
CH3 2885-2865 SYM_STR
CH2 2870-2840 SYM_STR
CH2 1480-1440 DEF
CH3 1465-1440 DEF
CH3 1390-1370 DEF
CH 1360-1320 DEF
CH3 1170-1160 DEF_WAG
CH3 1000-950 DEF_ROCK
Syndiotactic form, which have different infrared spectra. Isotactic PE coils up into a 31 helical
structure. The spectrum shown here is for crystalline isotactic PE, which is the most common
form used in industry; syndiotactic PE has no commercial interest. To the low wavenumber side
of the strong CH3 deformation mode band near 1375 cm-1, the mid-infrared spectrum of
crystalline isotactic PP has many weak characteristic bands, many sharp, which includes bands
with maxima near 1330, 1310, 1255, 1220, 1166, 1103, 999, 975, 900, 841 and 809 cm-1. The
relative intensity of bands within the infrared spectrum of crystalline, isotactic PP will be
affected to small extents by both the degree of crystallinity and molecular orientation. PE is also
commonly copolymerized with ethylene, which gives rise to additional absorption features in the
740 to 710 cm-1 region. A weak -C=O band observed near 1725 cm-1 is usually indicative of the
presence of an additive.
25


4.5 (c) FTIR spectrum of PVC
26


Classification: Halogenated-Polymer IR (Group: Poly (vinyl chloride)
Bond Range Mode

CH 2975-2950 STR
CH2 2920-2900 SYM_STR
CH2 1435-1425 DEF
CH 1340-1310 DEF
CH 1260-1240 DEF
CC 1100-1080 STR
C-Cl 700-680 STR
Poly (vinyl chloride), PVC, is relatively hard, and is often plasticized. Common plasticizers are
ortho-dialkyl phthalates, for example, di-n-butyl phthalate, di-(2-ethhyl-hexyl) phthalate. The
most readily identifiable mid-infrared absorption features of these phthalates in PVC are the
C=O (C=O stretch) near 1725 cm-1 and the C-O bands near 1280 cm-1 and 1125 cm-1, which
are accompanied by a weak sharp, doublet at 1605 and 1575 cm-1. In plasticized PVC the C=O
and the C-O bands may be the most intense in the spectrum. The absorptions in the CH
stretching region will also be much more intense than in unplasticized PVC.
The C-Cl (C-Cl stretch) region of poly (vinyl chloride), PVC, is complex and involves the
overlap of several absorption bands arising from differing conformational and configurational
forms. VC units may be present in both isotactic and syndiotactic sequences. A Cl atom may
exist in either a trans conformation to a H atom or to a C atom across the common C-C bond;
both conformations are possible in both isotactic and syndiotactic PVC. Atactic sequences may
also be present. Syndiotactic PVC may also be crystalline, and the amorphous to crystalline ratio
will also affect the relative intensities of these overlapping C-Cl bands.
27


4.6 FTIR Spectrum of recycled blend
28


When blend formation takes place at 275oC, there may be formation of different types of
copolymers and complex products owing to side reactions. FTIR analysis of recycled blend
shows the possibility the formation of following complex compounds,
• Poly (n-butyl acrylate)

• Ethylene/Vinyl Acetate Copolymer
• Vinyl chloride/Vinyl acetate Copolymer
• Vinyl Chloride/Ethylene Copolymer
• Poly (vinyl benzoate)
4.6 (a) Aliphatic Polyester-Polymer IR (Group: Poly (n-butyl acrylate)
Bond Range Mode

CH 2890-2880 STR
CH3 2885-2865 SYM_STR
CH2 2870-2840 SYM_STR
C=O 1750-1725 STR
-CH2- 1480-1440 DEF
CH3 1465-1440 ASYM_DEF
CH3 1390-1370 SYM_DEF
C-O 1275-1240 STR
The pair of C-O stretching bands near 1270 cm-1 and 1170 cm-1 is a characteristic of most
acrylate resins. The lower wavenumber band component is the most intense. The ester C=O
occurs near 1725 cm-1, and its first overtone can be observed as a weak absorption band near
3450 cm-1. The weak broad band near 733 cm-1 is indicative of three contiguous CH2- units,
that is (CH2)3-; this rocking mode vibration originating from the n-butyl group in the side-chain.
The band pattern between 1500 cm-1 and 450 cm-1 is the mid-infrared absorption ‘fingerprint’
that essentially characterizes poly (n-butyl acrylate). Acrylate esters are frequently
copolymerized.
29


4.6 (b) Copolymer-Polymer IR (Group: Ethylene/Vinyl Acetate Copolymer)
Bond Range Mode

CH 2890-2880 STR
CH3 2885-2865 SYM_STR
CH2 2870-2840 SYM_STR
CH2 2870-2840 SYM_STR
C=O 1750-1725 STR
CH2- 1480-1440 DEF
CH2 1480-1440 DEF
CH3 1390-1370 SYM_DEF
Copoly vinyl actetate; The infrared spectrum associated with this Note is that of an
ethylene/vinyl acetate (EVA) copolymer containing 18% copolymerized VA. EVA copolymers
used commercially may cover a wide range of compositions from; at least, 1% to 70%
copolymerized VA. The relative values (e.g. S, M, W, etc) listed in the Intensity column relate to
those expected within the spectrum of the homopolymer; the relative intensities listed in the
Relative Intensity column (e.g. 9, 8, 7, etc.) indicate the relative intensities expected for
absorption bands within an infrared spectrum of a copolymer similar to that associated with this
Note. Homopolymer spectra may be found as: polyethylene, Aliphatic Saturated Hydrocarbon 2
class; poly (vinyl acetate), Aliphatic Ester 1 class.
30


4.6 (c) Copolymer-Polymer IR (Vinyl chloride/Vinyl acetate Copolymer)
Bond Range Mode

CH 2975-2950 STR
CH2 2920-2900 SYM_STR
CH 2890-2880 STR
CH3 2885-2865 SYM_STR
CH2 2870-2840 SYM_STR
C=O 1750-1725 STR
-CH2- 1480-1440 DEF
CH2 1435-1425 DEF
CH3 1390-1370 SYM_DEF
CH 1340-1310 DEF
CH 1260-1240 DEF
C-O 1245-1225 STR
CC 1100-1080 STR
C-O 1040-1000 STR
C-Cl 700-680 STR
Copoly vinyl chloride; the infrared spectrum associated with this Note is that of a vinyl
chloride/vinyl acetate (VC/VA) copolymer containing 17% copolymerized VA. VC/VA
copolymers may cover a wide range of compositions. The relative values (e.g. S, M, W, etc)
listed in the Intensity column relate to those expected within the spectrum of the homopolymer;
the relative intensities listed in the Relative Intensity column (e.g. 9, 8, 7, etc.) indicate the
relative intensities expected for absorption bands within an infrared spectrum similar to that
associated with this Note. Homopolymer spectra may be found as: poly (vinyl chloride),
Halogenated 1 class; poly (vinyl acetate), Aliphatic Ester 1 class
31


4.6 (d) Copolymer-Polymer IR (Vinyl Chloride/Ethylene Copolymer)
Bond Range Mode

CH 2975-2950 STR
CH2 2870-2840 SYM_STR
CH2 1480-1440 DEF
CH2 1435-1425 DEF
CH 1340-1310 DEF
CH 1260-1240 DEF
CC 1100-1080 STR
CCl 700-680 STR
Copoly vinyl chloride; The infrared spectrum associated with this Note is that of a vinyl
chloride/ethylene copolymer containing ca. 39 mol-% copolymerized ethylene. The relative
values (e.g. S, M, W, etc) listed in the Intensity column relate to those expected within the
spectrum of the homopolymer; the relative intensities listed in the Relative Intensity column (e.g.
9, 8, 7, etc.) indicate the relative intensities expected for absorption bands within an infrared
spectrum of a copolymer similar to that associated with this Note. Homopolymer spectra may be
found as: poly(vinyl chloride), Halogenated 1 class; polyethylene, Aliphatic Saturated
Hydrocarbon 2 class. The very weak band near 1750 cm-1 indicates the presence of a low
concentration of a carbonyl containing material, which could arise from either an additive or
contamination, or indicate presence of a low concentration of a copolymerized ester.
The absorption band near 750 cm-1 may be attributed to the methylene rocking mode vibration
for a sequence of -CH2-CH2-CH2-. This indicates the ethylene is largely present as isolated
copolymerized units. At higher ethylene concentrations then an absorption band at ca. 720 cm-1
becomes more pronounced, arising from longer methylene sequences, such as -(CH2)5-, -
(CH2)7-, etc.
32


4.6 (e) Aromatic Polyester-Polymer IR Poly (vinyl benzoate)
Bond Range Mode

Ph-R 3095-3070 CH STR
Ph-R 3065-3045 CH STR
Ph-R 3040-3020 CH STR
CH 2890-2880 STR
CH2 2870-2840 SYM_STR
C=O 1740-1715 STR
Ph-R 1615-1590 Ring
Ph-R 1590-1575 Ring
Ph-R 1510-1485 Ring
CH2 1480-1440 DEF
Ph-R 1465-1440 Ring
CH2 1350-1300 DEF
CO 1290-1250 STR
The infrared spectrum of poly (vinyl benzoate) is dominated by the two strong ester bands near
1710 cm-1 (-C=O) and 1270 cm-1 (-C-O) and the aryl ring out-of-plane deformation band near
710 cm-1.
33

Morphological Characterization Ch-5 Recycling of mixed plastics waste

Chapter-5
Morphological Characterization
The morphology of the samples was studied using Scanning Electron Microscope in order to
investigate the evolution of morphology generated during processing. The samples were
fractured in liquid nitrogen, in specific directions in order to probe the morphology changes that
occurring during flow in different directions. The surface of the specimen was coated with gold
thin film by sputter coater for good conductivity. This scanning electron microscope has a
magnification range from 15x to 200,000x and a resolution of 5 nanometers.

5.1 Scanning Electron Microscope (SEM)

SEM stands for scanning electron microscope. The SEM is a microscope that uses electrons
instead of light to form an image. Since their development in the early 1950's, scanning electron
microscopes have developed new areas of study in the medical and physical science
communities. The SEM has allowed researchers to examine a much bigger variety of specimens.
The scanning electron microscope has many advantages over traditional microscopes. The SEM
has a large depth of field, which allows more of a specimen to be in focus at one time. The SEM
also has much higher resolution, so closely spaced specimens can be magnified at much higher
levels. Because the SEM uses electromagnets rather than lenses, the researcher has much more
control in the degree of magnification. All of these advantages, as well as the actual strikingly
clear images, make the scanning electron microscope one of the most useful instruments in
research today.
5.2 How does a SEM work?

The SEM is an instrument that produces a largely magnified image by using electrons instead of
light to form an image. A beam of electrons is produced at the top of the microscope by an
electron gun. The electron beam follows a vertical path through the microscope, which is held
within a vacuum. The beam travels through electromagnetic fields and lenses, which focus the
beam down toward the sample. Once the beam hits the sample, electrons and X-rays are ejected
from the sample
34


.
Fig 5.1: Rays rejected from the sample
Detectors collect these X-rays, backscattered electrons, and secondary electrons and convert
them into a signal that is sent to a screen similar to a television screen. This produces the final
image.
Fig. 5.2: Internal Layout of SEM
35


5.3 How is a sample prepared?
Because the SEM utilizes vacuum conditions and uses electrons to form an image, special
preparations must be done to the sample. All water must be removed from the samples because
the water would vaporize in the vacuum. All metals are conductive and require no preparation
before being used. All non-metals need to be made conductive by covering the sample with a
thin layer of conductive material. This is done by using a device called a "sputter coater."
The sputter coater uses an electric field and argon gas. The sample is placed in a small chamber
that is at a vacuum. Argon gas and an electric field cause an electron to be removed from the
argon, making the atoms positively charged. The argon ions then become attracted to a
negatively charged gold foil. The argon ions knock gold atoms from the surface of the gold foil.
These gold atoms fall and settle onto the surface of the sample producing a thin gold coating.
5.4 SEM Micrograph of PE/PET/PVC recycled blend
Fig. 5.3: Scanning Electron Microscopy of PP/PET/PVC recycled blend
The fracture surfaces of PP/PET/PVC blend were observed by electron microscope. As shown in
fig. 5.3, the dispersed phase is easy to be pulled from the blend and leaves uneven surface,
indicating low immiscibility among three polymers. Because of the high interfacial tension, the
morphology of recycled blend is not stable. Coalescence readily occurs in the molten state. As
36


suggested by Macosko et al., in melt mixing of immiscible polymer blends, the disperse phase is
first stretched into threads and then breaks into droplets, which can coalesce together into large
droplets. The balance of these processes determines the final dispersed particle sizes.
The crosslinking and the entrapping phenomenon may exist in a poly (vinyl chloride)/
polyethylene/ Polyethylene terephthalate (PVC/PE/ PET) blend as shown in fig 5.4. The results
of selective extraction show that PVC was due to not being crosslinked with PE but being
entrapped by the networks formed by the PE and PET phase as shown in fig 5.5. Fig 5.6 shows
that EPDM, as a solid-phase dispersant, can promote the perfection of networks of the PE phase
when it is added to the PVC/PE blends together with PET, which leads to more PVC unextracted
and improvement of the mechanical properties of PVC/ PE blend.
Fig. 5.4: Entrapping phenomenon
37


Fig. 5.5: Non crosslinked PVC entrapped in PE and PET
Fig. 5.6
38

Rheological Properties of recycled blends Ch-6 Recycling of mixed plastics waste

Chapter-6
Rheological Properties of recycled blends
Rabinowitsch and Begley corrections
39


40


1. Results and discussion
1.1. Melt flow rate
The melt flow rate is an indication of the flow ability of a polymer melts, one would; naturally,
imagine it to increase with load and increasing temperature, since the molecular layers will
become more slippery with increasing heat and shear stress. The net effect is that the molten
polymer will flow more readily, the experimental results obtained in thiswork, as shown in
Figures 1–3, having coordinated withthis expectation. The temperature rangeused in the current
work was, from 260 to290°C.
The MFRs of the blends measured with L/D=5circular die at different temperatures plotted as a
function of load are shown in Figs. 1 and 2.
120
100
MFR (g/10min)
80
60
40
20
0
0 20 40 60
PE Composition( %)
20 Kg 2.1 Kg 4 Kg 7 Kg 12 Kg
Fig. 1. Melt flow rate (g/10min) as a function of PE compositions at different Loads
41


120
100
MFR (g/10min)
80
60
40
20
0
0 20 40 60
PVC Composition( %)
20 Kg 2.1 Kg 4 Kg 7 Kg 12 Kg
Fig. 2Melt flow rate (g/10min) as a function of PVC compositions at different Load
100
90
80
70
MFR (g/10min)
60
50
40
30
20
10
0
0 20 40 60
PET Composition( %)
20 Kg 2.1 Kg 4 Kg 7 Kg 12 Kg
Fig. 3Melt flow rate (g/10min) as a function of Temperature (oC) for PET at different Load
42


From Figures 1-3, it is obvious that melt flow rate for all three samples increases with increasing
load. This is due to the fact that as load increases, force that is being applied on the melt present
in the heated barrel increases that pushes the melt rapidly through the barrel and hence the melt
flow rate is increased. Melt flow rate shows similar dependence (direct relationship) upon the
temperature as show in figures 1-3.
1.2. Pseudo-plasticity
To confirm the prediction made by the Figures 4-6: Flow curves has been drawn for all three
blends for different die sizes.Polynomial curve fitting has been applied. It is clearly observed that
for all die sizes, the behavior of all three samples is shear thinning (Pseudo-plastic).
600
500 PE 14%
PE 28%
Pressure (KPa)
400
PE 21%
300 PE 7%
200 PE 35%
100 PE 42%
PE 49%
0
0 200 400 600
Strain Rate (1/s)
(a)
600
500 PE 14 %
Pressure (KPa)
400 PE 28 %
PE 21 %
300
PE 7 %
200
PE 35 %
100 PE 42 %
0 PE 49%
0 100 200 300 400
Apparent Shear Rate (1/s)
43


(b)
600
500 PE 14%
Pressure (KPa)
400 PE 28%
PE 21%
300
PE 7%
200
PE 35%
100
PE 42%
0 PE 49%
0 100 200 300
Strain Rate (1/s)
(c)
600
PE 14%
500
Pressure (KPa)
PE 28%
400
PE 21%
300
PE 7%
200
PE 35%
100
PE 42%
0 PE 49%
0 30 60 90 120 150
Strain Rate (1/s)
(d)
Figure4. Curves demonstrating Pseudo-plasticity of Blend having variable composition of PE using capillary dies of
various lengths
(a) 4mm (b) 10 mm and (c) 20mm (d) 30 mm.
44


600
PVC 14%
500
PVC 28%
Pressure (KPa)
400 PVC 21%
PVC 7%
300
PVC 35%
200 PVC 42%
PVC 49%
100
0
0 200 400 600 800
Strain Rate (1/s)
(a)
600
PVC 14%
500
PVC 28%
PVC 21%
Pressure (KPa)
400
PVC 7%
300 PVC 35%
PVC 42%
200
PVC 49%
100
0
0 200 400 600
Strain Rate (1/s)
(b)
45


600
PVC 14%
500
PVC 35%
Pressure (KPa)
400
PVC 21%
300 PVC 7%
200 PVC 35%
PVC 42%
100
PVC 49%
0
0 100 200 300 400
Strain Rate (1/s)
(c)
600
PVC 14%
500
PVC 28%
Pressure (KPa)
400 PVC 21%
PVC 7%
300
PVC 35%
200 PVC 42%
100 PVC 49%
0
0 100 200 300
Strain Rate (1/s)
(d)
Figure5. Curves demonstrating Pseudo-plasticity of PVC using capillary dies of various lengths
(a) 4mm (b) 10 mm (c) 20mm (d) 30 mm
46


600
500
PET 14%
Pressure (KPa)
400
PET 28%
300 PET 21%
PET 7%
200
PET 35%
100 PET 42%
PET 49%
0
0 200 400 600 800
Strain Rate (1/s)
(a)
600
500
400
Pressure (KPa)
PET 14 %
PET 28 %
300
PET 21 %
PET 7 %
200
PET 35 %
PET 42 %
100
PET 49%
0
0 200 400 600
(b)
47


600
500
Pressure (KPa)
400
300
200
100
0
0 100 200 300
Strain Rate (1/s)
PET 14% PET 28% PET 21% PET 7%

PET 35% PET 42% PET 49%
(c)
600
500
Pressure (KPa)
400 PET 14%
300 PET 28%
PET 21%
200
PET 7%
100 PET 35%
0 PET 42%
0 30 60 90 120 150 PET 49%
Strain Rate (1/s)
Figure6. Curves demonstrating Pseudo-plasticity of PETusing capillary dies of various lengths

(a) 4mm (b) 10 mm (c) 20mm (d) 30 mm
48


1.3. Apparent viscosity
Figures 7-9 demonstrate apparent viscosity as a function of apparent shear rate over range of
temperature for various compositions of blends. Rise in temperature causes shear rate to increase
due to higher melt flow rate. As both samples exhibit pseudoplastic behavior (shear thinning),
increase in shear rate causes the viscosity to decrease. At constant temperature, increase in shear
rate is due to increase in applied load that pushes the melt through the capillary.

30
Apparent Viscosity (KPa‐sec)
25
20 PE 28 %
PE 14 %
15
PE 21 %
PE 35 %
10
PE 7 %
5 PE 42%
PE 49%
0
0 100 200 300 400
Figure 7 Apparent Viscosity (KPa-sec) as a function of apparent shear rate (1/sec) for Blends having various
compositions of PE
49


14
PVC 14%
12
PVC 28%
10 PVC 21%
PVC 7%
8 PVC 35%
PVC 42%
6
PVC 49%
4
0
0 200 400 600
compositions of PVC
35
30 PET 14%
PET 28%
25 PET 21%
PET 7%
20 PET 35%
PET 42%
15
PET 49%
10
0
0 200 400 600
compositions of PET
50


1.4. Bagley correction
The excess pressure losses due to end effects in the capillary flow of all blends were studied.
The "entrance pressure" (Bagley correction) is the pressure drop associated with the flow of the
polymer in the converging entry to the capillary die as well as at the exit (but mainly it is the
former). These losses were determined experimentally by extrapolating experimental data of
pressure drop versus length-to-radius ratios (L/D) to zero capillary length. These data were
plotted on a Bagley plot (pressure drop versus capillary length for several values of apparent
shear rate and consequently were extrapolated to obtain the pressure at zero L/D. By this method,
one effectively subtracts out he viscous pressure drop (corresponding to fully developed flow)
from the total pressure.
3000
2500
Pressure(KPa)
2000
1500
1000
500
0
0 10 20 30 40
L/R
Strain rate 01 Strain Rate 100
Strain rate 200 Strain rate 600
(a)
51


4.85
4.8
4.75
Log (Shear stress)
4.7
4.65 y = 0.609x + 3.589
4.6 R² = 0.990
4.55
4.5
4.45
4.4
4.35
4.3
0 1 2 3
Log (Shear Rate)
(b)
4.85
4.8
4.75
Log (Shear stress)
4.7
4.65 y = 0.609x + 3.589
4.6 R² = 0.990
4.55
4.5
4.45
4.4
4.35
4.3
0 1 2 3
Log (Shear Rate)
(c)
52


4.85
4.8
4.75
Log (Shear stress)
4.7
4.65 y = 0.576x + 3.440
4.6
4.55
4.5
4.45
4.4
4.35
4.3
0 1 2 3
Log (Shear Rate)
(d)
4.85
4.8
4.75
Log (Shear stress)
4.7
4.65 y = 0.641x + 3.218
4.6
4.55
4.5
4.45
4.4
4.35
4.3
0 1 2 3
Log (Shear Rate)
(e)
53


4.85
4.8
4.75
Log (Shear stress)
4.7
4.65
4.6 y = 0.703x + 2.952
4.55
4.5
4.45
4.4
4.35
4.3
0 1 2 3
Log (Shear Rate)
(f)
4.85
4.8
4.75
Log (Shear stress)
4.7
4.65 y = 0.692x + 2.918
4.6
4.55
4.5
4.45
4.4
4.35
4.3
0 1 2 3
Log (Shear Rate)
(g)
Figure 12 (a) Bagley correction plot (b, c, d, e, f) Determination of power law index and
consistency parameter at various compositions (PE 7%, PE 14% ,PE 21% ,PE 28% ,PE 35% ,PE
42% , PE 49% ) respectively
54


1.4. Viscosity Plots
To take into account the pseudoplastic nature of once recycled and twice recycled PET,
correction has been made in the apparent viscosity and apparent shear rate values.

40
True Viscosity (KPa‐sec)
35
30
25
20
15
10
5
0
0 50 100 150 200
True Strain Rate (1/s)
PE 28% PE 14% PE 21%

PE 35% PE 7% PE 42%
PE 49%
(a)
14
12 PVC 14%
PVC 28%
10 PVC 21%
PVC 7%
8 PVC 35%
PVC 42%
6
PVC 49%
4
0
0 200 400 600
(b)
55


35
PET 14%
30
PET 28%
25 PET 21%
PET 7%
20 PET 35%
PET 42%
15
PET 49%
10
0
0 200 400 600
(c)
Figure 10 True Viscosity (KPa-sec) as a function of True shear rate (1/sec):
(a) PE (b) PVC (c) PET
Curves of elongational viscosity for once and twice recycled PET at different temperatures are
shown in Figure 14. As shear rates increases, the viscosities decrease in a non linear fashion. But
it is evident from the curves that the viscosity decreases by increasing temperatures. Elongational
viscosities maintained the similar temperature dependence to that ofshear viscosities i.e.,
decreasing by increasing the temperature.

56


60
Elongational Viscosity(Kpa.s)
50
PE 35%
40
PE 28%
30 PE 21%
PE 14%
20
PE 7%
10 PE 42%
PE 49%
0
0 200 400 600
Shear Rate(1/sec)
(a)
60
50 PVC 35%
40 PVC 28%
PVC 21%
30
PVC 14%
20 PVC 7%
PVC 42%
10
PVC 49%
0
0 200 400 600
Shear Rate(1/sec)
(b)
57


60
50
PET 35%
40 PET 28%
PET 21%
30
PEt 14%
20 PET 7%
PET 42%
10
PET 49%
0
0 200 400 600
Shear Rate(1/sec)
Figure 11 Elongational viscosities vs. shear rate at different temperatures for 10mm die
(a) PE (b) PVC (c) PET

1.5. Power Law Fluid model parameters
The power law index increases with increasing temperature for all blends samples. It is very
clear from the Figure 12 that power law index for blend having varying composition of
polyethylene increases with increasing composition. As composition of polyethylene increases,
the composition of PVC and PET is decreased in the blend, and the material approaches to the
Newtonian fluids behavior due to increase in power law index values.
0.75
0.7
Power Law Index 'n'
0.65
0.6
0.55
0.5
0 10 20 30 40 50 60
Composition %
Figure 13 Effect of Temperature on power law index ‘n’
58


0.56
0.54
0.52
Power Law Index 'n'
0.5
0.48
0.46
0.44
0.42
0.4
0 0.5 1 1.5 2
Composition %
Figure 15Effect Of temperature on Consistency index
It is observed in Figure 14 that with increase in temperature, consistency index shows a

decreasing trend. The reason behind is the fact that as composition of polyethylene increases
melt flow rate increases (less viscosity) as shown in Figures1-3. As melt flow rate increases melt
behavior shifts towards Newtonian fluids. Power law index moves towards unity and consistency
index (intercept of log (shear stress) vs.log (shear rate) plot) approaches zero value.Consistency
index of Newtonian fluids is zero. At higher polyethylene compositions, viscosity decreases so
both melts approach towards Newtonian fluids.
59

Mechanical Properties of recycled blends Ch-7 Recycling of mixed plastics waste

Chapter-7
Mechanical Properties of recycled blends
The mechanical properties measurements were done on a TIRA Testing machine 2810 E6 using
dumb-bell shaped specimens at crosshead of 10mm min-1 with ASTM D-638. The samples for
mechanical testing were cut from the films produced by standard dies.
7.1 Results and discussion
The results obtained from the mechanical testing are indicated in the figures below. Fig.1
indicates that tensile strength of recycled blends increases with increase of respective component
in each blend. But this effect is more prominent in case of PET/PE/PVC blends and least
prominent in case of PET/PV/PE recycled blends. Similar observations has been observed in
case of modulus as shown in fig.2 But elongation at break decreases with increase of polymer
contents in each recycled blends. This phenomena is more salient in case of PET/PVC/PE as
demonstrated in fig.2

Tensile strength of recycled polymer blends
35
30
Tensile Strength (M Pa)
25
20
PE/PET/PVC
15
PET/PE/PVC
10 PET/PVC/PE
0
0 10 20 30 40 50 60
composition of recycled blends (%)

Fig-1
60

Mechanical Properties of recycled blends Ch-7 Recycling of mixed plastics waste

Modulus of recycled polymer blends
1400
1200
1000
Modulus (M Pa)
800
PE/PET/PVC
600
PET/PE/PVC
400
PET/PVC/PE
200
0
0 10 20 30 40 50 60
comosition of recycled blends (%)

Fig-2
Elongation at break of recycled blends
25
20
elongation at break (%)
15
PE/PET/PVC
10 PET/PE/PVC
PET/PVC/PE
5
0
0 10 20 30 40 50 60
composition of recycled polymer blends (%)

Fig-3
61

Conclusion & Recommendations Ch-8 Recycling of mixed plastics waste

Chapter-8
CONCLUSION & RECOMMENDATIONS
8.1 Conclusion
As recycling of plastics becomes inevitable for sustainable development, the challenges of using
these recycled materials to make useful products will increase. The challenges are significant
with recycled plastics because as their properties are usually not as good as their virgin
counterparts. In order to characterize the properties of a given batch of recycled plastic extensive
testing of each blend needs to be done. Once the testing establishes the properties, the next step
is to establish the suitability of a given blend for use in a commercial application. Suitability of
recycled plastics can be established either by building a prototype similar to the targeted product
and then testing it.
The results in this analysis indicate that MFI increases with increase of PET concentration in
PE/PET/PVC recycled blends. But MFI decreases with increase of PVC and PE in PET/PVC/PE
and PET/PE/PVC recycled blends respectively. Viscosity increases with decreasing shear rate
and shear rate thinning behavior is to be observed. It is also observed that melt flow rate for all
these recycled blends increases with increasing load. This is due to the fact that as load increases,
force that is being applied on the melt present in the heated barrel increases that pushes the melt
rapidly through the barrel and hence the melt flow rate is increased. Melt flow rate shows similar
dependence (direct relationship) upon the temperature. Results demonstrate that apparent
viscosity as a function of apparent shear rate over range of temperature for various compositions
of blends. Rise in temperature causes shear rate to increase due to higher melt flow rate. As both
samples exhibit pseudo plastic behavior (shear thinning), increase in shear rate causes the
viscosity to decrease. At constant temperature, increase in shear rate is due to increase in applied
load that pushes the melt through the capillary. Elongation viscosities maintained the similar
temperature dependence to that of shear viscosities i.e., decreasing by increasing the temperature.
The power law index increases with increasing temperature for all blends samples. It is clear
from the results that power law index for blend having varying composition of polyethylene
increases with increasing composition. As composition of polyethylene increases, the
composition of PVC and PET is decreased in the blend, and the material approaches to the
Newtonian fluids behavior due to increase in power law index values.
The mechanical properties of recycled blends are improved by adding EPDM and clay. Results
indicate that enhanced tensile strength and elongation at break is achieved for all these blends.

62

Conclusion & Recommendations Ch-8 Recycling of mixed plastics waste

Micrographical studies revealed that the dispersed phase is easy to be pulled from the blend and
leaves uneven surface, indicating low immiscibility among three polymers. Because of the high
interfacial tension, the morphology of recycled blend is not stable. Coalescence readily occurs in
the molten state.
FTIR studies divulged that when blend formation takes place at higher temperature, there will be
a formation of different types of copolymers and complex products owing to side reactions.
8.2 Recommendations
Further study would strengthen the understanding of the recycling of plastics,
• Development of techniques to increase the recyclability of polymers
• Modification of recycled material (addition of additives during processing)
• Study of the effect of binary, tertiary and higher order blends on crystallization, melting,
rheology, mechanical properties and morphology
• Conversion of non-upgradeable waste materials into composites and low cost fillers and
insulating material
• Understand the mechanism by which stabilizers can stop the reduction of mechanical
properties of polymers in polymer waste recycling process

63

References Recycling of mixed plastics waste

REFERENCES
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5. Fang Z., Xu C., Bao, S. and Zhao Y., In situ cross-linking and its synergism with
compatibilization in PVC/PE blends, Polymer, 38, 1, 131-133 (1997).
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wastes, J. Appl. Polym. Sci., 76, 1048-1053 (2000).
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Polym. Eng. Sci., 35, 64-71 (1995).
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dispersants synthesized by a mechano-chemical procedure, Eur. Polym. J., 20, 135-138
(1984)
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compatibilization of blends of postconsumer resin with virgin PP and HDPE, J. Appl.
Polym. Sci., 70, 2081-2095 (1998).
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polypropylene on PP/HDPE blends; J. Appl. Polym. Sci., 80,1305-1311 (2001).
11. Vivier, T. and Xantos, M., Peroxide modification of multicomponent polymer blend with
potential applications, J. Appl. Polym. Sci., 54, 569-575 (1994).
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contaminated with paper, Resources, Conservation and Recycling, 2, 57-67 (1988).
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Recycling, 10, 169-175 (1987).
14. F.N. Cogswell, Polymer Melt Rheology:, A Guide for Industrial Practice, Woodhead
Publishing, Cambridge, UK, 1994.
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Bittner, G. Menges and W. Michaeli, Carl Hanser Verlag, Munich, Germany, 1996,
p.350.
16. Waste and Resources Action Programme (WRAP), www.wrap.org.uk, accessed
September 2007
17. F.P. La Mantia, in 38th IUPAC Proceedings of Microsymposium on Recycling of
Polymers, Prague,Czechoslovakia, 1997, p.157.
18. Luo M, Curtis CW. Effect of reaction parameters and catalyst type on waste plastics
liquefaction and coprocessing with coal. Fuel Process Technol 1996;49:177–96.
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19. Brophy BJH. In: Menges G, editor. Recycling and recovery of plastics. Munich: Hanser;
1996. p. 422–33.
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22. DEFRA, Department for Environment, Food and Rural Affairs. Waste Strategy 2000 for
England and Wales: part II chapter 5,
www.defra.gov.uk/environment/waste/strategy/cm4693/index. htm
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1996. p. 393–412.
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potential applications, J. Appl. Polym. Sci., 54, 569-575 (1994).
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65

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Introduction Ch-1 Recycling of mixed plastics waste

Any strategy for waste management is based around three guidelines.

• Elimination, the disposal of non-recyclable materials, for example by landfill.

1.2 Effects of Processing on Thermoplastics

• Deformation processes, which enable the product to be formed.

• Changes to structure and properties as a result of processing.

1. Squeezing toothpaste through a tube,

1.3 Reprocessing of Thermoplastic Recyclates

• How many times it has been reprocessed previously?

1.4 Recycling Techniques

1. Physical/mechanical treatment to prepare and homogenise the waste, and

Figure 1.1 A process stream for recycled plastic material

1.4 .1 Size Reduction

1.4.3 Identification and Sorting of Plastics

Figure 1.2 Society of Plastics Industry (SPI) packaging codes

Figure 1.3 Film waste before and after agglomeration

1.5 Additives for Recyclates

1.5.1 The Degradation of Plastics

1.5.2 Restabilization of Recyclates

II. Light Stabilization

The mechanical properties of blends of isotactic polypropylene and high-density polyethylene

• The degradation it has already undergone

• Nature of the waste i.e. Single or a combination of plastics

• Effect due to environmental exposure

3.1 Objectives of research

• To study the thermal and rheological behavior of recycled polymer blends

• To study the morphological structure of recycled polymer blends

• To find the optimum concentration of each component of waste in recycled polymer

• Size reduction crusher

• Universal testing machine

• Compression molding machine

• Melt flow indexer

• Scanning electron microscope (SEM)

• Polymer 70% and additives 30%

Sr. No Additives Function

3 Amines To enhance thermal properties of recycled blends

When PET is variable

Sr .No PET% & gm PVC PE EPDM Clay AMINES

Sr .No PE% & gm PVC PET (EPDM) Clay AMINES

Sr .No PVC% & PET PE (EPDM) Clay AMINES

4.1 Infrared spectroscopy

4.2 Fourier transform

Fig- 4.1 Optical System

Fig-4.2 Signal flow

4.4 Common Applications

• Identification of functional groups in unknown substances

• Identification of reaction components and kinetic studies of reactions

• Identification of molecular orientation in polymer films

• Detection of molecular impurities or additives present in amounts of 1% and in some

• Identification of polymers, plastics, and resins

• Analysis of formulations such as insecticides and copolymers

4.5 (a) FTIR spectrum of PET

Bond Range Mode

Poly (ethylene terephthalate), PET, is manufactured as a polycondensation between ethylene

Bond Range Mode

Bond Range Mode

• Poly (n-butyl acrylate)

4.6 (a) Aliphatic Polyester-Polymer IR (Group: Poly (n-butyl acrylate)

Bond Range Mode

Bond Range Mode

Bond Range Mode

Bond Range Mode

Bond Range Mode