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"Effect of stabilizers on properties of PVC.

INTRODUCTION
Poly (vinyl chloride) (PVC) is one of the most fascinating, interesting,
universal and oldest thermoplastics of all. On one hand it is the polymer
which comes into contact with a baby’s skin only a few minutes after its
birth, in many countries the bracelet on which the name and the birthday of
the newborn are noted is made of PVC. A lot of other medical items such as
oxygen tents and blood bags are also based on PVC because of the chemical
and physical properties of PVC not offered by other materials. On the other
hand many PVC products, for example toys as children or more durable
items as u-PVC windows, cladding, electrical insulation on wires and cables,
resilient flooring, pipes for land drainage, sewage and drinking water are
with us throughout our lives. Even the coffins that we are finally buried in
are probably covered in PVC foil or veneer and lined with flexible PVC
film.

Polyvinyl chloride, known as PVC, is one of the world’s leading


synthetic polymers. It has many uses, ranging from long-term construction
applications, such as pipes used in the transportation of potable water, to
short-term uses, such as food packaging. Because of the presence of
chlorine, it is a highly polar polymer, which allows a wide range of additives
to be incorporated within it. This variety of additives permits a broad range
of physical property characteristics; hence there is not one PVC composition
but many. This also explains the great diversity of applications in which
PVC has been used from the time of its original commercial development in
the early 1930s, when a few hundred tonnes were produced, to its annual
global consumption rate of nearly 25 million tones in the year 2000.

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Worldwide demand for plastic pipe is forecast to increase more than


four percent per year through 2007, continuing to outpace gains for overall
pipe demand. China- which is already one of the largest national markets -
will register some of the strongest increases, with plastic pipe demand
growing over eight percent annually through 2007. A number of other
countries? Including India, Russia, and Turkey? Will also exhibit strong
sales gains, fueled by acceleration in infrastructure construction activity and
industrialization.

In this project an attempt has been made to improve the thermal and
physical property of the PVC pipe by optimizing the additives such as
stabilizer for reducing the cost of PVC pipe.

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MARKET DATA

Polyvinyl chloride is the leading plastic pipe resin in global use,


accounting for over two-thirds of plastic pipe demand by weight. PVC pipe
is popular because of its low cost, durability, strength and ease of extrusion,
allowing it to make inroads against non-plastic pipe materials. Demand for
high density polyethylene pipe will benefit from use as small-diameter pipe
in natural gas transmission, as conduit for electrical and telecommunications

applications, and as corrugated pipe for drains and sewers.

Table:

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Table:

Table:

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Literature Survey

Polyvinyl chloride, better known as PVC or vinyl, is an in expensive plastic


so versatile it has become completely pervasive in modern society. The list
of products made from polyvinyl chloride is exhaustive, ranging from
phonograph records to drainage and potable piping, water bottles, cling film,
credit cards and toys. More uses include window frames, rain gutters, wall
paneling, doors, wallpapers, flooring, garden furniture, binders and even
pens. Even imitation leather is a product of polyvinyl chloride. In fact, it's
hard to turn anywhere without seeing some form of this plastic.

During the fifty years following the end of World War II, PVC has
become the second most widely used plastic in the world. Today more than
20 million tonnes are Manufactured each year. In Europe the total
consumption of PVC products was estimated at approximately 7.4 million
tonnes in 1998, which corresponds to ca. 5.5 million tonnes of PVC polymer
(ECVM). About one third of the total production of PVC polymer is used for
the production of flexible PVC products, the remaining two thirds fall into
the category of rigid PVC products.
Virgin PVC is thermally and photochemically unstable and depending on
requirements and desired characteristics of the application, a number of
additives are applied to reduce these problems prior to manufacture of PVC
products. The quantitatively important classes of additives are heat
stabilizers, plasticisers, and inert fillers, the latter generally added to reduce
cost and get more volume for a given amount of polymer Other classes of
additives for specific applications include pigments, impact modifiers,

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lubricants, fillers, UV stabilizers, biocides (to prevent fungal growth on


flexible PVC) and antistatic agents.
In the following sections an overview is provided of the main application
areas of PVC and the most important classes of additives. The average
quantities of these components used in PVC products are given wherever
possible. It has to be borne in mind that a wide range of applications and
substances are added to different PVC products, accordingly, a more detailed
and quantified inventory of components applied to PVC is hardly possible
within the scope of this study.
PVC products with long and extra long service life are predominately used
in the building and automotive sector, while PVC products for packaging
purposes have a short service life. Except for cables, flexible PVC has a
rather short to medium-term service life and the majority of rigid PVC
products is in use for a long time period. PVC products with very long life-
span are presently still retained in the use phase. Thus, the present PVC
waste stream is not directly correlated with the current production, in
particular PVC products with a comparatively long life-span used in large
quantities in the building sector are just beginning to appear in the waste
stream and will certainly effect future PVC waste stream composition.
All PVC products contain at the minimum a PVC polymer, a stabiliser and
a lubricant. Various other components are incorporated in PVC, sometimes
in large quantities with regard to the polymer. Generally, the percentage of
additives varies between 10 and 25 % in weight of the resin, in the case of
rigid products. Flexible PVC can contain plasticisers up to 60 % of the
weight, the average content is about 30%. Although the composition of PVC
products is broadly known, the actual formulation of a product differs
depending on the year of production and on compounding specifics of

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different PVC converters, thus even in the same application (e.g. window
profiles, pipes, films) the composition of the PVC material varies. In the
following sections the most commonly used additives are described in brief.
The effect of additives on the properties and characteristics of the product is
summarised in the following overview:
Table:

• Stabilizers are ingredients that are generally added to the PVC


polymer in order to prevent thermal degradation and hydrogen
chloride evolution during processing and to give the finished article
optimum properties (heat and UV stability). Approximately 1-8 %
may be added to PVC formulation depending on other components

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and the final application. The most important group of stabilisers are
metal salts (i.e. calcium and zinc stearates, basic lead sulphate and
lead phosphite)
• organo metals (i.e. mono- and diorganotin, tin thioglycolate)
• organo phosphites (i.e. trialkyl-phosphites)
• epoxy compounds (i.e. epoxidised soya bean oil, sunflower oil and
linseed oil)
• antioxidants, polyols (i.e. BHT, pentaerythritol)

• Lubricants are used in amounts of 1 – 4 weight %, they are added


to prevent the plastic from adhering to the metal walls of the moulding
machines, and to modify the properties of mixtures. Examples of such
lubricants are waxes, fatty acids (stearic acid etc), fatty alcohols, etc.
• Fillers are added to improve certain properties, i.e. mechanical and
electrical resistance, and may comprise 50% of a PVC formulation. In
rigid PVC for building applications, no more than 5 % fillers are
added. The main fillers are of mineral origin: calcium carbonate
(limestone), talc, chalks etc.
• These are mainly organic pigments and colouring agents and mineral

pigments (titanium oxide, iron oxide, chromium oxide, cadmium


oxide, etc). Typical amounts are 0,1 weight%, but up to 15% may be
used in extraordinary cases. (see para. 11 for the use of cadmium as
pigment).
In many applications, the presence of chlorine in PVC provides
satisfactory fire performance, but the addition of flame retardants is used
in particular in some flexible PVC building materials in relatively high
concentrations – up to 10 – 20 weight %. Flexible PVC has a lower

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chlorine-content than rigid PVC and is therefore more flammable.


Chlorinated paraffins are commonly used as
• flame-retardants:- the chlorinated paraffins used are almost
exclusively of medium chain length or longer Chlorinated paraffins
also have plasticising properties and therefore are also used as
secondary plasticiser for PVC products such as floorings, cable
insulation, garden hoses, coatings, and shoes.
• Other additives:- are added for specific purposes, such as
biocides or fungicides. Impact modifiers are used in concentrations of
up to 15 weight % to improve the impact resistance of rigid PVC.

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The Economic and Technical Importance of PVC :-


Stabilizers Polyvinyl chloride (PVC) was one of the first thermoplastics
developed. It has become worldwide a very important bulk plastic over its
almost 70 year history. PVC consumption in different geographic areas and
expecteddemand through 2000 are shown in Fig. 3.1.PVC consumption
(Mio.t).

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PVC – including the various copolymers of vinyl chloride and chlorinated


PVC – is expected to remain important among thermoplastics because of its
compatibility with a large number of other products (e. g., plasticizers,
impact modifiers), in contrast to other plastics. Because PVC’s mechanical
properties can be adjusted over a wide range, yielding everything from rigid
to flexible end products, there are many different processing methods and
applications for PVC. The toxicological problems which at one time were
major obstacles in the manufacture and processing of PVC were solved
satisfactorily many years ago.
When PVC was first developed, flexible PVC was dominant, but rigid
PVC production has increased continually and is now approximately two-
thirds of total consumption in many countries. The low thermal stability of
PVC is well known. Despite this fact, processing at elevated temperatures is
possible by adding specific heat stabilizers that stop the damage. This is one
of the main reasons PVC has become a major bulk plastic. The development
and production of suitable heat stabilizers followed the production of PVC
from the beginning, and remains a precondition for processing and
application in the future. Consumption of heat stabilizers in Western Europe
was approximately 150,000 tons in 1995 and is estimated to be 170,000 tons
by the year 2000. The consumption of thermal stabilizers for PVC
worldwide is estimated to be 450,000 tons.

Thermal Degradation and Stabilization of PVC:-


Mechanism of PVC Degradation:-
When PVC is processed at high temperatures, it is degraded by
dehydrochlorination, chain scission, and crosslinking of macromolecules.

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Free hydrogen chloride (HCl) evolves and discoloration of the resin occurs
along with important changes in physical and chemical properties. The
evolution of HCl takes place by elimination from the polymer backbone;
discoloration results from the formation of conjugated polyene sequences of
5 to 30 double bonds (primary reactions). Subsequent reactions of highly
reactive conjugated polyenes crosslink or cleave the polymer chain, and
form benzene and condensed and/or alkylated benzenes in trace amounts
depending on temperature and available oxygen (secondary reactions).
Dehydrochlorination of PVC in the Absence of Air (Primary Degradation)
Any mechanism of degradation has to explain a series of experimental facts.
Structural irregularities, such as tertiary or allylic chlorine atoms, increase
the degradation rates measurably at the beginning of the process by a rapid
dehydrochlorination that starts the degradation process (Scheme 3.1). Initial
rates of degradation are proportional to the content of these irregularities.
However, PVC degrades even if these irregularities are eliminated by special
polymerization conditions or treatments because of the dehydrochlorination
of normal monomer units (random elimination) (Scheme 3.1). It is estimated
that after allowing for the differences in concentrations and reaction rates,
the rate of random degradation in commercial PVC because of normal chain
secondary chlorine atoms has the same order of magnitude as does
degradation that results from structural irregularities. Cis-ketoallylic
structures, although very reactive in dehydrochlorination (Scheme 3.1), are
not present in commercial PVC but can be generated by thermal oxidative
processes. After the reactive irregularities initially present are exhausted,
degradation continues because of the elimination initiated from normal
monomer units. These findings indicate that thermal degradation in PVC is
an intrinsic property of this polymer and that changes in synthesis conditions

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or specialtreatments that eliminate structural irregularities improve the


stability of PVC, but can not completely eliminate its degradation.
Stabilizers must be used.

Not all allylic chlorine atoms preexisting and/or formed in the degradation
process accelerate degradation. Single double bonds can be identified in
degraded PVC by NMR spectroscopy. Double bond sequences, once formed,
do not increase by continuation of degradation. There are allylic chlorides
with some forms of alkenic double bonds that are stable under degradation
conditions . The conjugated polyene sequences are generated in apparently
parallel processes from the first moment of degradation. For relatively low

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conversions, their concentrations increase linearly with time. Zero order rate
constants calculated as slopes of these lines decrease exponentially with the
increase of the number of double bonds in the sequence. In the thermal
degradation of solid PVC, an induction period is observed, and then for
higher conversions, the degradation rate increases with time, indicating an
autocatalytic process. Hydrogen chloride formed in the degradation
increases both the degradation rate and the mean number of double bonds in
the polyene sequence, and consequently plays an essential catalytic role in
PVC degradation . Some local configurations and conformations of the
polymer chain of PVC, such as the conformation GTTG (G for Gauche T for
Trans) at the end of certain isotactic sequences, favor degradation. These
conformations exhibit a high local mobility relative to the remaining
structures in PVC and possess some chlorine atoms with very high degrees
of freedom. Both features make possible the adoption of the conformation
enabling the elimination reaction. It follows that dehydrochlorination is
possible only for specific local conformations. Along the same line, PVC
molecules at the surface of primary particles in the solid state have a much
higher conformational mobility than molecules in the interior. PVC
degradation consequently is expected to take place predominantly at the
surface of primary particles. It is well known that dehydrochlorination of
PVC proceeds violently in the presence of Lewis acids such as FeCl3,
ZnCl2, ,AlCl3, SiCl4, GeCl4, SnCl4, BCl3, and GaCl3. This process is
responsible for the very fast discoloration of PVC in the presence of Zn or
Sn carboxylates that act as stabilizers till the corresponding halides are
formed and fast dehydrochlorination starts. The reaction mechanism of a
complex chemical process such as PVC degradation defines the sequence of
elementary reactions leading from reactants to products and describes each

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of these reactions. The mechanism of PVC degradation should explain the


above fundamental observations and should also agree with the observations
related to PVC stabilization that are discussed later in this chapter. The
dehydrochlorination of PVC is a very specific chemical process because of
the existence of a long series of alternating CHCl and CH2 groups in the
polymer backbone that makes possible a chain of multiple consecutive
eliminations. However, the parallel formation of conjugated polyene
sequences containing 1 to 30 double bonds cannot be explained by a simple
consecutive elimination. The chain reaction model from Scheme 3.2 can
explain this apparent contradiction .

The first elimination from a monomer residue from the chain (-CH2-
CHCl-) or a structural irregularity such as a tertiary chlorine atom (-CH2-
CCl<) forms an active intermediate or a stable monoalkene. This active

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intermediate partitions between a stable sequence of two double bonds and a


new intermediate . The fate of the second intermediate is analogous to that
of the first one and the process continues in this way, generating all the
double bond sequences. The concentration of each intermediate is lower
than the concentration of the previous one. A simple steady state
approximation shows that all polyene sequences in the distribution are
formed simultaneously and the apparent rate constants decrease
exponentially in agreement with experiment . There is a general consensus
that the intermediates in the degradation process are allylic sequences with
progressively increased numbers of conjugated double bonds However, the
mechanism of initiation, propagation, and termination steps is controversial.
An early mechanism hypothesized that the intermediates were allylic
radicals (Scheme 3.3).

The major problem with this mechanism is that the chlorine atom is known
to be so reactive as to be non-selective. Data on model compounds showed
that the allylic hydrogen atom, (>C=CH-CH2-CCl<), has only slightly

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higher reactivity toward abstraction by a chlorine atom that is free to diffuse


throughout the polymer matrix than does a hydrogen atom from a secondary
carbon (-CH2-CCl<). The above mechanism consequently generates
primarily isolated double bonds and not the observed sequences of
conjugated polyenes, owing to the much higher concentration of hydrogen
on secondary carbon atoms . This radical mechanism also fails to explain the
very important catalytic role of HCl. In addition, there are no reliable proofs
that radicals are intermediates in PVC degradation in the absence of
initiators and/or oxygen .
An ion pair mechanism (Scheme 3.4) was considered for the initiation step
by ionization of chlorine followed by rapid elimination of a proton. A much
faster ionization of the activated allylic chlorine formed was considered
responsible for the chain reactions . However, this mechanism does not
explain the previously presented experimental facts. Moreover, it does not
postulate any interruption reactions of the degradation chain. The only
product of degradation should be a polyene resulting from elimination of all
chlorine atoms from the PVC molecule. Consequently, the ion pair
mechanism cannot explain the real distribution of polyene sequences as a
function of the number of double bonds. This mechanism also does not
explain the catalytic role of HCl. Formation enthalpy of Cl2Hcomplexes of 3
to 4 kcal/mol as an intermediate for the catalyzed process in this mechanism
does not compensate for the high activation enthalpy of C-Cl ionization
(140–180 kcal/ mol). A concerted elimination mechanism postulated by A.
R. Amer and J. S. Shapiro, modified by M. Fisch and R. Bacaloglu , and
based on experimental data and molecular orbital calculations and
additional experimental data from W. H. Starnes and coworkers best
explains the experimental facts (Scheme 3.5). The first step is slow

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formation of a double bond randomly along the polymer chain via a 1,2-
unimolecular elimination of HCl through a four-center transition state
(Scheme 3.5) or a

six-center transition state in the catalytic presence of HCl or metal chloride


dike ZnCl2 (Scheme 3.6). Structural irregularities such as allylic or tertiary
chlorine atoms eliminate much faster than do normal secondary chlorines in
the chain.

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The second and third steps of the processes constitute the chain
elimination, regardless of the initiation site. In the second step, an HCl
molecule is eliminated from a cis _-alkyl-allyl chlorine through a six-center
transition state, generating a conjugated diene or polyene.

Next is an HCl-catalyzed, 1,3 chlorine rearrangement, generating a new


cis _-alkyl-allyl chlorine from the conjugated polyene. The second and third
processes may continue as long as HCl is still present in the system.
Elimination of HCl stops the 1,3-rearrangement of chlorine and
consequently, the reaction chain. This explains the very important role of
HCl in PVC degradation. All the metallic chlorides that are Lewis acids and
can form complexes with chloroalkanes may have a similar role. (Scheme
3.7). The analogy with chloroalkanes and chloroalkenes provides important
support for the above mechanism, as it was shown that activation parameters
for the initiation of PVC degradation correlate with the activation parameters
of gas phase elimination from secondary chloroalkanes and fall on the same

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straight line. This suggests that both processes may have the same
mechanism: a 1,2-elimination of hydrogen chloride from a synperiplanar
conformation involving backbone chlorine through a transition state of four
centers. In the same way, it was shown that the chain reactions may have the
same mechanism as the elimination from cis _-alkyl-allylic chlorides
(chloroalkenes): a 1,4-elimination of hydrogen chloride through a transition
state of six atoms from a cis allylic structure. Only the cis-allylic system
with one double bond that has a relatively low activation enthalpy of
dehydrochlorination is reactive in chain propagation in the degradation
process. Trans conjugated polyenes are much more stable in the absence of
HCl. To dehydrochlorinate, they require a 1,2-elimination at the one end that
has a much higher activation enthalpy. This process is similar to a random
initiation and is much more likely statistically to occur at a different place in
the polymer molecule or on a different polymer molecule entirely. In this
way, a chain reaction, once interrupted, does not continue, and the sequences
of conjugated polyenes remain as such in the system. Trans conjugated
polyenic systems are known to be very stable relative to their cis isomers
because of their favorable conformation that allows polymer packing to
occur.

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Thermal Oxidative Degradation of PVC:-


During processing, in addition to thermal dehydrochlorination, the
polymer is exposed to thermo-oxidative degradation resulting from oxygen;
in addition, mechanical stress may cause chain scission. The main feature in
thermo-oxidative degradation is dehydrochlorination as in thermal
degradation. The presence of oxygen causes the dehydrochlorination process
to accelerate, but the discoloration is not as severe as during thermal
degradation. The polyene sequences are shorter as a result of the reaction
between them and oxygen.
The overall activation energy of dehydrochlorination is practically the
same for thermal and thermo-oxidative processes . The initial
dehydrochlorination proceeds by the same mechanism. The most significant
damage during the commercial processing of PVC occurs as a result of
mechano-chemical reactions in the presence of entrapped oxygen. The shear
forces cause chain scission, generating radicals. Thermally-initiated HCl loss
is followed by radical oxidation of polyenes to form peroxy radicals and
hydroperoxides. Hydroperoxides decompose to generate alkoxy and hydroxy
radicals that accelerate the oxidation process and form ketones and acid
chlorides . Ketoallylic chlorides initiate the thermal dehydrochlorination
process, as described earlier.

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Although the radical process is much more complex than shown in


Scheme 3.8, it is clear that thermo-oxidative degradation does not differ in
any essential way from thermal degradation. Dehydrochlorination, the most
important process, has the same mechanism in both types of degradations.

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Secondary Processes in PVC Degradation:-


In PVC degradation at low dehydrochlorination levels, polyene
concentrations increase linearly and in parallel with HCl evolution. At
higher dehydrochlorination levels, the increase in polyene concentration
levels off. The plateau value is lower when degradation temperatures and
oxygen pressures are higher. When the plateau is reached,
dehydrochlorination level for all double bond sequences show that no
consecutive reactions to longer polyenes take place . In the absence of
oxygen during the thermal degradation of solid samples, a measurable
increase in molecular weight occurs and the molecular weight distribution
becomes wider and shifts toward higher values. At some point during
degradation, the melt viscosity increases considerably, as can be observed by
increasing torque in a Brabender Plasticorder experiments [33]. The
crosslinking process is catalyzed by HCl . The most important crosslinking
reaction is the Diels-Alder condensation of cisoid trans-trans dienes with
other polyenes (Scheme 3.9).

Benzene is formed in very small amounts even at temperatures as low as


160 to 170 °C by an intramolecular process (Scheme 3.9). At higher
temperatures, substituted benzenes and condensed aromatic hydrocarbons
are formed by radical scission of Diels- Alder condensation products and
radical cyclization of polyenes. In the presence of oxygen, the same
reactions take place, but they are more complex because of the processes
described earlier. Oxidative scission of the chain predominates and, in
general, the molecular weight of the polymer decreases .

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Heat Stabilization of PVC:-


The degradation of PVC at elevated temperatures required in
thermoplastic processing is an intrinsic characteristic of the polymer and
consists of dehydrochlorination, auto-oxidation, mechano-chemical chain
scission, crosslinking, and condensation reactions. This degradation must be
controlled by the addition of stabilizers. The heat stabilizer must prevent the
dehydrochlorination reaction that is the primary process in degradation.
There are two ways the stabilizer can act:
• By reacting with allylic chlorides, the intermediates in the zipper
degradation chain. This process should be faster than the chain propagation
itself, requiring a very active nucleophile. However. the reactivity of the
nucleophile should not be so high as to react with the secondary chlorine of
the PVC chain, a process that rapidly exhausts the stabilizer. To be effective,
the stabilizer must be associated by complex formation with polymer
chlorine atoms, which means it should have a Lewis acid character. This
association should take place in regions where the polymer molecules have
maximum mobility; in other words, where the conformation of the polymer
can favor the degradation processes.
• Once the degradation starts, it is very fast and can be stopped only if the
stabilizer is already associated with the chlorine atom that becomes allylic.
These regions are the surfaces of the primary particles of PVC, where the
stabilizer molecules are associated with the chlorine atoms. The exceptional
effectiveness of such stabilizers at very low concentrations is explained by
their entropically favorable position for stopping degradation. In general,
these stabilizers, because of their effectiveness, prevent the formation of

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polyenes longer than four to five double bonds and maintain very good early
color in the polymer. These stabilizers are called primary stabilizers.
• Scavenging the hydrogen chloride generated by degradation is another way
to stop the process as the HCl is a catalyst for the chain propagation reaction
and the initiation step. However, the diffusion of HCl is quite slow because
HCl is associated with the double bond where it was generated. When HCl
diffuses away from the reaction center, the zipper degradation reaction stops.
The stabilizer should scavenge HCl with high effectiveness to avoid its
catalytic effect in chain initiation that starts another zipper
dehydrochlorination chain. Because this type of stabilizer cannot prevent the
dehydrochlorination in its early stages, polyenes longer than four to five
double bonds are formed. PVC discolors and the initial color is not
maintained. However, by scavenging HCl, this type of stabilizer avoids the
autocatalytic degradation and consequently, overall degradation is much
slower. These stabilizers provide very good long term stability and are
usually referred to secondary stabilizers.
To have good stabilization of PVC with good early color and long term
stability, the two types of stabilizer should be combined appropriately for
each particular PVC formulation. Stabilization is complicated by the fact
that primary stabilizers become strong Lewis acids by reacting with the HCl
that catalyzes the initiation and propagation of PVC degradation. To avoid
this, secondary stabilizers should react efficiently with HCl to protect the
primary stabilizers. Another possibility is to include compounds called
costabilizers in the system. Costabilizers form relatively stable complexes
with the chloro derivatives of primary stabilizers (the Lewis acids) and
suppress their degradative effect.

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The most important classes of stabilizers and how they act in PVC
stabilization is briefly discussed below.

Alkyltin Stabilizers:-
The most commercially important alkyltin derivatives are the mono and
dimethyl-, butyland octyltin alkyl thioglycolates, mercaptopropionates and
alkyl maleates. All these compounds react with HCl to form the
corresponding tin chlorides (Scheme 3.10). However, their stabilization
effect does not correlate with the amount of HCl reacted nor with the rate of
this reaction. It has been established that in the stabilization of PVC with
alkyltin alkyl thioglycolates, alkyl thioglycolates are released by reaction
with HCl . These alkyltin compounds consequently function as secondary
stabilizers, but this is not the main mechanism of their action.

During PVC stabilization with alkyltin alkyl thioglycolates, thioglycolate


groups are incorporated into the polymer chain as was determined by 113Sn
and 14C tagging, Alkyltin thioglycolates exchange thioglycolate groups
with chlorine atoms in reactions with model allylic chlorides and the
reactivity in this process parallels the PVC stabilization effect . The main

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stabilization mechanism of these compounds is consequently substitution of


allylic chlorine and they are primary stabilizers (Scheme 3.11). In alkyltin
thioglycolates, one thioglycolate group bonds to tin to form a complex and is
not active in stabilization. Alkyltin mercaptopropionate groups do not form
such complex structures; all mercaptopropionate groups are active in
stabilization and their activity is higher compared to the corresponding
thioglycolates on a molar basis. In general, monoalkyltins are more reactive
than dialkyltin derivatives; however, as a result of the very fast exchange of

thioglycolate groups, compositions comprised of at least 40 to 50% mono


content exhibit activity equal to that of the monoalkyltin derivatives
themselves. Consequently, pure monalkyltin derivatives are not required to
obtain maximum stabilization. Based on their high compatibility with PVC
and difficulty of extracting them from PVC blends, it has been postulated
that tin stabilizers associate with chlorine atoms at the surface of PVC
primary particles which explains their high efficiency in PVC stabilization
(Scheme 3.12).

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Mercapto compounds generated by the reaction of alkyltin mercapto


derivative with HCl add to double bond sequences and by this process,
retard PVC’s discoloration . Dialkyltin di(alkyl maleates) are able to add in a
Diels Alder reaction to polyene sequences and reduce the discoloration of
degraded PVC . In both cases, the average polyene sequence length is
shortened, thereby shifting the absorption maximum toward the ultraviolet
and away from the visible wavelengths. 3.2.2.2 Mixed Metal Stabilizers
Metal carboxylates stabilize PVC by either mechanism, depending on the
metal. Strongly basic carboxylates derived from metals such as K, Ca, or Ba,
which have little or no Lewis acidity are mostly HCl scavengers. Metals
such as Zn and Cd, which are stronger Lewis acids and form covalent
carboxylates, not only scavenge HCl, but also substitute carboxylate for the
allylic chlorine atoms (Scheme 3.13). It has been shown that when the
concentration of the metal carboxylates is decreased, the ester group
introduced into the backbone by direct substitution can be eliminated by

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"Effect of stabilizers on properties of PVC.”

reaction with HCl or by thermal degradation at higher temperatures


(reversible blocking mechanism) (Scheme 3.13). IR spectroscopy has shown
that Zn carboxylates associate with PVC molecules at the surface of primary
particles and are, consequently, very effective in the substitution of allylic
chlorine. The synergism between Zn or Cd carboxylates and Ba or Ca
carboxylates is attributed to fast exchange reactions between zinc or
cadmium chlorides and barium or calcium carboxylates. These reactions
regenerate the active zinc or cadmium carboxylates and also avoid the
catalytic effect of zinc or cadmium chlorides in PVC degradation (Scheme
However, it has been shown that the synergistic effect is increased by
preheating zinc and calcium stearates together. In this way, a complex zinc
stearate is formed that is more active in allylic chlorine substitution (Scheme
3.14).

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The damaging effect of Zn or Cd chlorides in PVC degradation can be


considerably reduced by using costabilizers that form metal complexes with
them. The most common costabilizers used with solid Cd and Zn
carboxylates are polyols .

Alkyl Phosphites Stabilizers:-


Dialkyl phosphites have no effect on PVC degradation. Trialkyl phosphites
scavenge HCl by an Arbuzov reaction and form dialkyl phosphites. They
react also with allylic chlorides, but this process plays a secondary role
(Scheme 3.15). When used alone, phosphites are secondary stabilizers,
giving good long term stability but poor early color. However, in the
presence of zinc di(dialkyl phosphites) (formed from zinc salts and trialkyl
phosphites as stabilization proceeds), allylic substitution is considerably

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"Effect of stabilizers on properties of PVC.”

increased and becomes the dominant process in PVC stabilization. The early
color is very considerably improved.

Diketones Stabilizers:-
Diketones and similar compounds with active methylenes react in the
presence of Zn carboxylates as catalysts with allylic chlorides generated by
PVC degradation by a Calkylation process . The stabilization effect
increases with the CH acidity of these compounds .

Epoxidized Fatty Acid Esters Stabilizers:-


Epoxides are HCl scavengers and are also reported to be effective in allylic
chlorine replacement in the catalytic presence of Zn and Cd salts (Scheme
3.16) .

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Hydrotalcites Stabilizers:-

Hydrotalcite, a natural mineral, is the hydroxycarbonate of Mg and Al with


the exact formula: Mg6Al2 (OH)16CO3.4H2O. It is constituted from
infinite sheets of octahedra of Mg2+ six-fold coordinated to OH-, sharing
edges (brucite-like sheets), where Al3+ substitutes for some of the Mg2+
ions. A positive charge is generated in the hydroxyl sheet that is
compensated for by CO3 2- anions, which lie in the interlayer regions
between two sheets. In the free space of these interlayers, there is water of
crystallization, associated by hydrogen bonds with both OH- and CO3 2-
anions. Hydrotalcite-like clays with anions of weak acids react with strong
acids such as HCl and exchange the anions with Cl-. This reaction allows
hydrotalcite-like clays to be used as HCl scavengers in PVC stabilization .
Product Groups and Their Specific Chemical and Application
Characteristics
Despite the great variety of thermostabilizers known, only a few have gained
industrial importance. According to their chemical composition, they are
usually divided into four groups: tin stabilizers, mixed metal carboxylates,

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lead stabilizers, and metal free stabilizers. Besides the thermostabilizers,


there is the important group of costabilizers, which are products with no
significant efficiency alone, but which are used together with stabilizers to
provide strongly enhanced effects.
Tin Stabilizers:-
As early as 1936, Yngve recommended not only tetraalkyltin but also
alkyltin carboxylates as PVC stabilizers . In 1950, Firestone filed patent
applications for organotin mercaptides, which became extremely important
in further developments in PVC technology .
Organotin compounds with at least one tin-sulfur bond are generally called
organotin mercaptides, sulfur-containing tin stabilizers, or thiotins.
Organotin salts of carboxylic acids – mainly maleic acid or half esters of
maleic acid – are usually known as organotin carboxylates, and the
corresponding stabilizers are sometimes called sulfur-free tin stabilizers.

Organotin Mercaptides and Organotin Sulfides:-


Sulfur-containing organotin compounds are among the most efficient and
most widely used heat stabilizers. They can be described by the following
structures (Scheme 3.17):

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Among these, the liquid thioglycolates are the predominant group on the
market. Mono- and diorganotin mercaptides are often used in combination,
because these mixtures improve initial color as well as the long-term heat
stability of PVC (synergistically) . This is shown in Fig. 3.2.

Fig 3.2 Synergism of mono- and dioctyltin isooctyl thioglycolates


exemplified by yellowness Index (YI) as a function of milling time (t) in the

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"Effect of stabilizers on properties of PVC.”

dynamic heat stability test on a two-roll mill at 200 °C a: dioctyltin-


bis(isooctylthioglycolate),b:monooctyltintris(isooctylthioglycolate),c: 80%
dioctyltin-bis (isooctylthioglycolate) and 20% monooctyltin-tris
(isooctylthioglycolate) The term “dialkyltin” is also used for mixtures of
dialkyltin with smaller amounts ofmonoalkyltin compounds in order to
exploit the synergistic effect of the combination of mono- and dialkyltin.
Very efficient, solid stabilizers of a type not mentioned above are derived
from ß-mercaptopropionic acid (Scheme 3.18): Sulfides of mono- and
diorganotin are used in liquid mixtures with certain tin stabilizers, mainly
together with thioglycolates and reverse esters.
The heat stabilizing effect of these organotin stabilizers depends on the
type of mercapto group they contain. These groups are directly involved in
the stabilizing reaction; they can either replace the labile chlorine directly
according to Scheme 3.11, or add onto polyene sequences after intermediate
formation of the mercaptide HSR .
Organotin mercaptides are able to react with HCl, to annihilate initiating
sites by substitutionand also help impede auto-oxidation. The combination
of these functions gives the organotin mercaptides exceptional
thermostabilizing properties not found in any other class of stabilizer.Details
about the mechanism of organotin stabilization can be found in Section 3.2 .
The organotin-sulfur stabilizers, especially as mixtures of mono- and
dialkyl-tin i-octyl thioglycolates, can be used in all PVC applications where
high thermostability is required.
They can stabilize all homopolymers, emulsion, suspension, and bulk
PVC (E-, S-, MPVC), as well as copolymers of vinyl chloride, graft
polymers, polyblends, and postchlorinated PVC (CPVC). One of the most
appreciated properties of the whole organotin stabilizer group is the absolute

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crystal clarity of finished articles, an advantage in the manufacture of rigid


PVC packaging and transparent film, bottles, and containers. Organotin
thioglycolates are used also in the manufacture of plasticized PVC hoses,
profiles, sheet, and transparent top coats or layers. Sulfur-containing
organotin stabilizers are not, in general, self-lubricating.
Therefore, the high processing temperatures necessary for optimum
transparency may cause the hot melt to adhere to the metal surfaces of
processing equipment, unless suitable lubricants are added. Adding high-
polymeric processing aids based on PMMA to organotin-stabilized PVC
imparts better flow properties and improves the surface quality of finished
articles, e.g., in calendering films, extruded profiles and sheet, blown bottles,
and injection molded fittings.

Organotin mercaptides should not be used with cadmium- or lead-


containing stabilizers or pigments because the resulting formation of
cadmium or lead sulfide can discolor the PVC (“sulfur staining”). Organotin
stabilizers migrate from rigid PVC only very slightly. This fact, together
with favorable toxicological properties, is the basis for the worldwide
approval of certain types of methyl- and octyltin isooctylthioglycolates for
use in food packaging and potable water pipe .
As described in the previous Section (3.2.2.), organotin stabilizers are
transformed during processing into the corresponding organotin chlorides.
Methyltin chlorides have considerably higher vapor pressure than the
analogous butyl- or octyltin compounds. Because of their volatility during
processing, the maximum allowed concentration (MAC) for tin (0.1 mg/m3)
must be monitored and enforced strictly, especially in open systems such as
calendering. Butyltin mercaptides are widely used as stabilizers in the

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production of films, sheet, injection moldings, floor tiles, and wall


coverings. In the US, they are also used for pipe extrusion, and siding with
high titanium dioxide content is manufactured almost exclusively with
organotin mercaptides. Transparent and translucent articles for outdoor use
can be stabilized with sulfur-containing organotin stabilizers only if suitable
UV absorbers are also present.
A special application for sulfur-containing organotin stabilizers is the
production of foamed, rigid PVC profiles and sheet. Reverse esters are
mercaptides of mono- or di-methyl or butyltin, based on mercaptoethanol
esters of long chain fatty acids. They are especially effective in the
manufacture of PVC pipe and siding. Approvals for water pipe exist for
certain organotin reverse esters. The liquid estertin iso-octyl thioglycolates
(alkyl-O-CO-CH2CH2)2Sn(SCH2COO-i-octyl)2 are also efficient non-
toxic stabilizers, but they have not developed significant market share.

Organotin Carboxylates:-
Only carboxylates carboxylate with the following structures are of practical
interest (Scheme 3.19):

As already mentioned, organotin derivatives of maleic acid may have an


additional stabilizer function, i.e., the Diels-Alder reaction . Their
performance is good in all types of suspension, emulsion, and bulk PVC.

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Optimum results are obtained when they are combined with small amounts
of phenolic antioxidants, particularly in plasticized PVC, impact-modified
PVC, and PVC copolymers. Because stabilizers containing maleic acid
occasionally lead to eye and mucous membrane irritations, there have been
many attempts to replace them with other systems. For many years,
organotin stabilizers free of maleic acid have been on the market. These
consist of a combination of organotin carboxylates, e.g., laurates, and a
small amount of an organotin mercaptide. Just as with sulfur-free organotin
stabilizers, when used in a suitable formulations, this combination gives
rigid PVC high transparency and excellent weathering stability. In the melt,
PVC stabilized with alkyltin maleates tends to stick to hot contact areas of
the processing equipment. However, this problem can be prevented by
suitable lubricants. Organotin carboxylates work especially well in the
manufacture of rigid or plasticized PVC articles for outdoor use, as for
example, transparent and translucent double-walled panels for greenhouses,
siding, and window profiles, particularly when pigmented.

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Recommended Formulations

Sr.no Ingridient %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 1.6
7 Dibasic lead sterate 0.8
8 Calcium sterate 0.8
9 Lead sterate 0.4

Experimental Work
In this project we have processed the PVC pressure pipe of different
compounding minimizing the percentage of stabilizer and we have taken the

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thermal stability test as well as other standard test for determining the
properties of PVC pipes.
We have made various batches of different composition which is
given below.

BATCH –A
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Steraic Acid 0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 0.7
7 Dibasic lead sterate 0.5
8 Calcium sterate 0.5
9 Lead sterate 0.2

BATCH –B
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 0.8
7 Dibasic lead sterate 0.55
8 Calcium stearte 0.55

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9 Lead stearte 0.25

BATCH –C
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 0.9
7 Dibasic lead sterate 0.6
8 Calcium sterate 0.6
9 Lead sterate 0.3

BATCH –D
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 1.
7 Dibasic lead sterate 0.65
8 Calcium sterate 0.65

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9 Lead sterate 0.35

BATCH –E
Sr.no Ingredients %
1 PVC 100
2 Calcium Carbonate 16-12
3 Stearic Acid .0.6
4 Tio2 0.4.
5 Paraffin wax 0.6
6 Tribasic Lead Sulfate 1.1
7 Dibasic lead sterate 0.7
8 Calcium sterate 0.7
9 Lead sterate 0.4

The processing parameters are as below.


Processing Parameters
Single screw exruderwiht belt drive
barrel temperature:
zone 1 125 °C
zone 2 150 °C
zone 3 160 °C
Die temperature 165°C
m/c RPM 12
vacuum pressure 250mmof Hg
output 2m/min
sizing unit length 3feet
cooling tube length 5feet
Traction unit RPM 12
Traction unit length 3feet

Compounding
Compounding temperature 110 -120°C
Compounding time 15 min

Pipe Dimension
diameter of pipe 25mm

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length of pipe 3m
thickness of pipe 1.5mm
weight of pipe 450 gm
Test for compounds.

Static Thermal stability of PVC:-

Theory:-
Resin sample is heated and emitted vapour are passed through a tube
containing canes red paper . The liberation of HCL is indicated by the colour
change.
Principle :-
During the degradation of PVC ,HCL is liberated which changes the
colour of canes red paper to blue.
Apparatus:-
i. Red indicator paper : 6 mm X50 mm.
ii. Stop-watch with accuracy of 0.2 sec.
iii. Oill bath : Capable of maintaining the temperature to the accuracy of
1°C in the range of 120 to 210°C ( Chetan Electrical Worksmake ).
iv. Stirrer with variable speed (Remi make).
v. Test tube : 18 + 1 mm diameter ,150 + 2 mm length.
vi. Rubber stopper : With a hole to accommodate 2+3 mm diameter tube.
vii. Silicon oil : Viscosity of 50 + 5cp

Safety:-
Carry out the experiment in the fuming chamber with glass door shut.
Wear safety glasses during test.

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Procedure :-
1) Heat the oil bath to test temperature (180°C) and maintain in it

0+2°C.
2) Fill the test tube with sample PVC resin up to 50+2 mm depth ( do

not top the tube to form a compact mass) .


3) Place small glass tube in hole of stopper .Roll one end of moist cargo

red paper / blue litmus and insert it in tube so that 30 + 2 mm of


paper strip extends from the glass tube.
4) Stopper the test tube with the stopper and position the glass tube in

the stopper so that end of paper is 25 + 2 mm above sample surface.


5) Immerse the in oil bath to the level of upper surface of sample and
simultaneously start stop watch.
6) Measure the time till the indicator paper shown first signs of colour
change.
Observation:-
Sample Temp °C Time for degradation(min)
Batch A compound 180 102
Batch B compound 180 114
Batch C compound 180 110
Batch D compound 180 117
Batch E compound 180 115

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Test for PVC pipes:


Following test are generally performed for assessing suitability of PVC
pipes
Dimensions of the pipes:
Pipes are checked for outside diameter and thickness with the help of ball
ended micrometer tolerance on outside diameter is +0.3 mm for 16-90 mm
O.D pipes + 0.4 mm for 110 mm pipes and 0.5 mm for 140 X160 mm O.D.
pipes. Wall thickness for a working pressure of 4kg/cm2/90mm O.D. pipes is
min .2.1 and max.2.6mm for 110 mm OD / 4kg/cm2 other size and working
pressure ratings, dimensions are available in.
Visual appearance:
The pipes shall be reasonably round. The internal and external surface of
pipe shall be smooth and clean, reasonably free from grooving and other
defects. The end shall be clean cut and square with axis of the pipe.
Short Term Hydraulic Test:
A sample of pipe equal to 10 times the nominal size of the pipe(not less than
25 cms or more than 75 cms) shall withstand a circumferential stresses of
360kg/Cm2 for at least 1 hour. At 27±1°C without any sign of leaking or
weeping.
Internal Presser to be applied is P= 2δ S/D-S.
Where P = Pressure to be applied in Kgf/cm2
δ = Circumferential stress in Kgf/cm2
S = Minimum wall thickness in mm.
D = Mean OD in mm

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Batch 4kgf/cm2 pressure is applied for 1hr


A Pass
B Pass
C Pass
D Pass
E Pass

Reversion Test:
A 20 cm peace of pipe on which two marks are made 100 mm apart,
and is placed in oven at 150 °C for 1 hour After the stipulated time is over
the reduction in length of 100 mm mark is measured. The Shrinkage is less
than 5% than the sample was passed the reversion test was accepted for the
ISI test.

Batch Shrinkage
A 2%
B 3%
C 4%
D 3%
E 3%

Water absorption:-
The 4.5 cm length of pipe is cut and weight. The beaker of 500 ml is
taken then the distilled water of 250ml is taken into this beaker. And the
piece of pipe is immersed for 24 hr. and this pipe is weighted after

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immersion the difference in the weight of pipe gives us the percentage of


water absorption.

Batch % of water absorption for 24 hr


A 1.38%
B 0.81%
C 1.72%
D 1.46%
E 0.98%

Sulphuric Acid Test for PVC pipe:


In this test the pipe sample of measured length and weight was
immersed in H2SO4 bath for 14 days. After the period of pipe was dried with
the cloth and then its weight was measured the weight is increased or
decreased by 0.010-0.013 Grams the sample was accepted other wise not.

Batch Difference in weight in gm


A 0.06
B 0.01
C 0.08
D 0.10
E 0.017
Impact strength test:
30cm pipe pieces are cut and conditioned at 0°± 1° for 1hr specimen
shall be tested on following the weight machine within 10 sec of removal
from the bath. Mass of striker and height of free fall shall be under:
O.D.(mm) Total mass of kg Height (meter)
20 0.25 0.5
25-40 0.25 1.0
50-63 0.25 2.0
80-100 0.50 2.0

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125 1.0 2.0

Each specimen shall be drawn with longitudinal parallel line not less
then 50 mm. the weighted striker shall be allowed to fall freely on the mark
line. If the specimen does not fail by cracking or splitting, the specimen shall
be rotated to the next longitudinal line and so on. The process shall be
repeated until all the marked lines have been tested or until a failure is
recorded. If 14 strikes are made without failure pipes shall be deemed to
have passed the test.

Batch striker of 0.25kg weight is fall at height of 1 meter


A Pass
B Pass
C Pass
D Pass
E Pass

Result & Discussion


Comparison table:-

Test
A B C D E
Batch
Thermal 102 114 110 117 115
stability
(in min)

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Water 1.38% 0.81% 1.72% 1.46% 0.98%


absop.
Reversion 2% 3% 4% 3% 3%
Test
I. H. S. P PASS PASS PASS PASS PASS
Impact PASS PASS PASS PASS FAIL
Strength
H2SO4
0.06 0.01 0.08 0.10 0.017
Test (in
gm)

It is clear from the above table of various batches of different


proportion of stabilizer. The batch B is satisfying criteria of ASTM. For
thermal stability, Batch B obtain good thermal stability with optimum
percentage of stabilizers and from this it considered as the formulation of
making low cost PVC pipe with good properties.

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"Effect of stabilizers on properties of PVC.”

Conclusion
Worldwide demand for plastic pipe is forecast to increase more than
four percent per year through 2007, continuing to outpace gains for overall
pipe demand. This continues increase in production would not been possible
without the improvement in processing of PVC pipe with changes in
additives proportion during compounding.
This makes us to thing that why not we make the pipe which gives
good individual properties in PVC pipe system with economical aspect.
After thermal stability test and other test for various properties we have
concluded that % of stabilizer used in batch B improved the properties such
as thermal stability which reduces the percentage of stabilizer to about 30
percent.
Thus the batch B is giving similar properties like standard formulation
so it reduces the cost of processing to two percent.

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References
BOOKS:
1) PVC Technology by A.S.ATHALYE & Dr.PRAKASH TRIVEDI first
edition 1994 page no: (197-199), (168-169),(92-120).
2) PVC Stabilization by JERRY WYE PITCH 4th edition page no (12-

30),(198- 220),
3) PVC Technology by W.Y.Titow Elsevier applied science publication,
London and new York page no 4-23,37-49,59-65
4) Plastic material 5th edition (1995), J.A. Brydson butter worth

London page no. 293-345.


5) Polymer science V.R. Gowerikar new age international Pvt Ltd Pub
new Delhi, page no. 236-238

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WEBSITES:
1) www.cmie.com

2) www.specialchem4.com

3) www.plasticnews.com

4) www.ril.com

5) www.finolex.com

College Of Engg.& Tech. Akola 52

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