LIBRARY REFERRENCE
PROJECT
ON
Additive for Plastics
Submitted By:
Shaikh Md. Izhar
PG/K/2010/03
Topic
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Introduction
Why do additives add to plastics
How additive effects in polymer
Types of additives
Role of additives in packaging
Report highlight
How will additive shape the future
Additives
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Aim: The main aim of this report is to identify and highlight the importance of
additive in the field of Packaging, areas of application, market size, the
different properties that can be bring change into the plastic according to its
end use using additive and some of the important aspects of additives.
Introduction
How additives are essential?
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This Brief introductory section is designed to highlight the way in
which Plastics additives now constitute a highly successful and
essential Sector of the packaging industry. Additives are integral
components in plastics and contribute to the success of plastics not only in
process ability but also in property modification and performance. Plastics
would not have been able to deliver their performance without the addition of
these polymer additives. Although used at only 5-7% in terms of weight, or
about 10% by cost, they provide immense benefits and have contributed to the
success of plastics.
The polymers used in plastics are generally harmless. However, they
are rarely used in pure form. In almost all commercial plastics, they
are "compounded" with monomeric ingredients to improve their
processing and end-use performance. All these plastics products are
made from the essential polymer mixed with a complex blend of
materials known collectively as additives. Without additives, plastics
would not work, but with them they can be made safer, cleaner,
tougher and more colorful. Additives cost money, of course, but by
reducing production costs and making products last longer, they help
us to save money and conserve the world's precious raw material
reserves.
When considering mass transport phenomena in plasticsused as
packaging materials in contact with fresh or processed food , bottles
for drinks, cosmetics, pharmaceuticals, as greenhouse or mulching in
agriculture and various articles or implants in human and veterinary
medicine ( for example, bags for blood transfusion and dialysis,
surgical fibers etc.), special attention has to be paid to a possible
transfer of low molecular weight compounds. Commodity plastics
used for the development of above mentioned application, i.e., high-
density polyethylene (HDPE), low-density polyethylene, (LDPE), linear
low-density polyethylene (LLDPE), polypropylene (PP), polyvinyl
chloride (PVC), polyethylene terephthalate (PET), Polyamide (PA)
and Polystyrene (PS) are commercial failure without additives. The
later are organic or inorganic chemicals enabling processing of
plastics, shaping their use, and enhancing end-use performance.
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Additives influence the future development of plastics and make
them value added materials under increased environmental
regulations at regional differences
They are used at levels of 0.05wt% up to about 20.0wt%. Their
market is very cost competitive, standardized across the globe, and
correspond to the world growth of plastics production. Additives are
classified by functions not by chemistry and are used under stringent
legislation and environmental rules. The legal bans against particular
chemicals are global selective. Chemical legislation proposed by the
European Commission as Registration-Evaluation and Authorization
of Chemicals (REACH) (Bennemann, 2005) may effect additive
application rules.
About 75% of all additives have been consumed in PVC.
Additives modifying plastics properties constituents about 70% of
the totally consumed amount in comparison to 23% of property
extenders and 7% of processing aids (Pfandner. 2006).
Some additives or their residues remaining in trace amounts
in the plastics, such as processing aids, are not generally declared in
commercial articles. The presence of additives having properties of
plasticizers and stabilizers must be declared. Their suppliers must
provide every detail on the regulation status of each additive with
respect to industrial hygiene, the environment, and the indirect
contact with food.
Characteristics functions of plastics additives providing
marketable packaging materials and their representative structure are
outline below.
Why do Additives Add to Plastics?
1) Additives Make Plastics Easier To Process
Making things out of plastics is like playing a game with molecules.
The aim is to re-organize them into new shapes without their
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changing colour, sticking to the mould, or doing anything that could
spoil the finished article. Additives help with all these problems.
2) Additives Make Plastics Look good
Plastics are coloured using two main methods. The surface can be
painted or printed after moulding, or additives called PIGMENTS
can be incorporated before or during moulding. With this method,
colour pigments can create all sorts of decorative effects that go all
the way through the object and of course, will never wear off. This
property, coupled with the range of moulding techniques available,
gives designers today a tremendous freedom when working with
plastics.
3) Additives save Money
The additives that assist the moulding of plastics, such as lubricants,
process aids, and heat stabilizers, can cost many times more than the
raw Material, and although only small amounts are used, they are
nevertheless essential and greatly enhance the final performance.
Other additives such as mineral fillers like chalk, talc and clay, are
naturally occurring substances which tend to be cheaper than the raw
polymer. Its saves of one percent per moulding may not sound much,
but if it involves producing several injection mouldings every few
seconds, this small saving can become very significant.
4) Additives Make Plastics Safe And Sound
Good design in plastics includes the art of combining the inherent
safety properties of plastics, such as unbreakable materials, with
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appropriately designed product features. Rounded edges, child
resistant closures and tamper evident seals are examples. Even
greater safety factors can be built in through the use of additives.
5) Additives Make Plastics Clean and Healthy
PVC, for example, with its low toxicity, flexibility, clarity and
sealing properties, all achieved through additives, has become one of
the most important plastics in medicine. Additives have allowed the
development of a sealed system of PVC tubing and bags which
separates blood into its constituents without the need to open the
equipment. Plasticsed PVC medical bags help save lives.
To prevent plastics materials from becoming hard and brittle at low
temperatures, or soft and sticky at high temperatures, additives are
used to 'design' the plastics for its specific end use.
6) Additives Make Plastics Work Longer
In extending the life and service of plastics, the unseen protection
given by additives can result in materials which lead to new products
for even more demanding situations.
Non-fading pigments will help these Spectrum stadium seats to
hold their colour for many years (Hille).Children's toys, packaging
and flooring are just some of the products that form the backdrop to
our lives, and it is hard to overestimate the rough treatment they have
to endure. All of these are exposed to the weather, day and night,
summer and winter, but a combination of LIGHT STABILISERS,
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UV ABSORBERS and ANTIOXIDANTS ensure constant high
performance.
7) Additives Respect the Environment
Plastics waste disposal can cause problems, especially as plastics are
usually mixed up with other types of waste such as paper, metals and
food. For recycling them really need to be sorted into individual
polymer types such as polythene, polystyrene or polyvinyl chloride,
otherwise they have no strength if remoulded and may literally fall
apart. This is an area in which additives called COMPATIBILISERS
can help. They act like chemical adhesives, sticking the different
waste plastics material together so that a reasonable amount of cross-
blending can be accepted. Mixed plastics waste can be remoulded
into fencing, pallets and road markers, thus saving valuable timber.
All this comes from a waste product that would other wise have been
buried in a landfill site. Additives are vital for reprocessing waste
plastics into useful second generation products.
When certain plastics are moulded at around 220oC, particular additives
called BLOWING AGENTS break down to form gases such as nitrogen,
carbon dioxide and water. These gases, trapped in the plastics, turn the
material into foam, thus increasing the insulation and energy absorption
properties and reducing weight. These foams can be seen in everyday use
such as protective food packaging, cushioning in sports shoes and in
automobile parts where lower weight saves fuel.
How additive Effects in Polymers?
Plastic polymers have chemical reaction properties similar to those of
small molecules, though the polymers themselves are larger in size. This
means that a range of different factors, including thermal conditions,
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stress cracking, or the diffusion of chemical additives, can alter the
molecular structure, and thus the fundamental properties, of most plastic
polymer materials. Some changes, such as unintentional reduction in
molecular weight, can lead to plastic degradation and product failure,
while others can supplement or improve
a polymer’s characteristics.
Most plastic additives are introduced into a compound to produce a
specific result, whether to increase formability or merely change the
pigmentation. In the case of copolymers, which are composed of varied
and repeating molecular units, each substance included in the material
plays a part in its overall chemical makeup. This makes it important to
carefully control the amount and types of additives that are included
because they do not usually bond to a polymer molecule and thus increase
the chemical susceptibility of a plastic material. Different kinds of
additives display different vulnerabilities and strengths, but each of them
can influence the effectiveness of polymer production.
Types of additives
The following list provides a summary of the purposes of many of
the common additives:-
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1) Antifogging agents: - These improve packaging film clarity, by
preventing any water from the contents of the package from condensing as
droplets on the inside Surface of the film. Antifogging agents are
alkylphenol ethoxylates, complex polyol mono-esters, and polyoxyethylene
esters of oleic acid, polyoxyethylene sorbitan esters of oleic acid, and
sorbitan esters of fatty acids.
2) Antistatic agent: - Additive which reduces or eliminates surface
electrical charges and hence prevents dust pick-up etc. on
polymer surfaces. Plastics are generally insulating and so have the
capacity to build up static charges on the surface which greatly
disturb processing procedures and can be an issue for hygiene and
aesthetics. The agent may be incorporated in the material before
molding, or applied to the surface after molding and function
either by being inherently conductive or by absorbing moisture
from the air. Examples of antistatic additives are long-chain
aliphatic amines and amides, phosphate esters, quaternary
ammonium salts, polyethylene glycols, polyethylene glycol esters,
and ethoxylated long-chained aliphatic amines.
Concentration of antistatic in plastics is usually from 0.1% to
2wt%. Special grades of electro-conducting(EC) carbon black
are used in Polyolefins (PO) at levels higher than 10wt%.
Anti-static
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Color
Natural
Ingredients
Active: 5% proprietary mixture of non amide & non amine
Carrier: LLDPE
Dosage
Depending on end application and film thickness:
2% to 6% in LDPE/LLDPE/PP films
3% to 10% in HDPE/PP molded items.
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3) Blowing agents :- Substance added to a polymer, so as to
generate gas which will have the effect of expanding or foaming
the polymer. The gas can be produced chemically or by simple
evaporation.
An expanded materials has a cellular structure which,
depending on the material, can be produced physically introducing
bubbles (usually of air or an inert gas) , or by producing them
chemically by means of blowing agents which decompose during
the process (usually by heat) to release suitable gas. Chemical
blowing agents are used to produce polyurethane foam & PU
foam mouldings and to injection mould structural foam version of
thermoplastics.
To improve control of the formation of the foam during the
process, and to achieve cell structure, other additives ( called
nucleating agents) are often used.
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4) Colorants: - Color breathes life into plastic, whether in
packaging, consumer goods, or other applications. Adding
pigments and dyes to plastics calls for matching the right mix of
colorants to the shade and intensity of the desired colors. The base
polymer can dictate the colorant selected. Pigments are generally
used in polyolefin because most dyes have a tendency to migrate
in them. Dyes are often used with polycarbonate, polystyrene,
acrylic, and other polymers given the color strength and
transparency they offer.
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5) Fillers & Reinforcement Agents: - Fillers are particulate
additive, designed to change polymer physical properties (e.g. fire
resistance, modulus, shock resistance) or to lower cost. Usually
mineral-based, fillers literally increase the overall "bulk" of the
plastic. Used to reinforce or improve tensile strength, flexural
strength and stiffness of the material. Often fibre-based.
Fillers
Color
White
Ingredients
Active: 65% special filler
Carrier: LLDPE
Dosage
1 to 20% depending on the end application.
Recommended for LDPE & LLDPE colored films
Used for blown films & thermoformed plastic sheets
Suitable for HD, MD, LLDPE & LDPE
COM 651C filler additive acts as an anti-blocking additive for the LLDPE
& LDPE films.
Some filler additive is environmentally-friendly as it reduces polymer
consumption
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6) Lubricants: - Two main functions: they prevent a polymer from
sticking to the mould or the machinery, and reduce melt viscosity,
allowing the molten polymer to pass easily through intricate
channels. They also reduce friction between polymer particles
before they melt.
Lubricants are used in rigid PVC (PVC-U) in amounts of
0.3% to 0.8wt% (metallic soaps acting primarily as heat
stabilizers are used at levels up to 1.5wt %). In Polyolefins
(PO), calcium or zinc stearates used as antiacids provide the
lubricants effect at 0.1to 0.2wt% levels.
7) Nucleating agent: - Foaming Agents, also known as Blowing or Nucleating
Agents, can eliminate sink marks, reduce density, shorten cycle time and reduce
total production costs. In extrusion and injection molding, foaming agents can
save material weight and lower total cost. They also improve extrusion rates by
increasing the volume that can be processed per extruder in a given period of
time, and endothermic foaming agents absorb heat and improve injection
molding cycle time.
Nucleating Agents give a higher degree of crystallinity to polymers, resulting in
improved mechanical properties such as hardness and flexural modulus.
Clarifying agents have the additional benefit of also improving optical
properties, in particular transparency.
They are used in amounts of 0.1% to 0.3wt%.
8) Optical brighteners: - Fluorescent agents improve the whiteness or brilliant
white appearance of finished articles from thermoplastics & mask discoloration
accounting for polymer degradation. They absorb ultra-violet radiation and emit
it as visible light.
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The additives used up to 0.005wt%.
9) Plasticizers: - Additive designed to space out the polymer molecules,
facilitating their movements and leading to enhanced flexibility or stretchability,
improve processibility and ductility of plastics by decreasing their melt
viscosity, glass transition temperature , and modulus of elasticity of the final
product without alteration of the chemical character of the polymer. Internal
plasticizers are nonextractable copolymer of suitable monomers. They have
mostly substantially lower glass transition temperature due to the presence of
plasticizing (“soft”) segments (such as poly(ethylene-co-vinyl acetate) with
approximately 45 wt.% vinly acetate content, ethylene vinyl acetate-carbon
monoxide ter-polymer or chlorinared PE) and worse mechanical properties.
A combination with external plasticizers may provide an optimal balance of
effects. For example, for food contact products made from poly(vinylidene
chloride) a combination of 5wt.% of citrate or sebacate esters can be used with
cw 10 wt.% of polymeric plasticizers.
Widely used to convert PVC from the rigid to the flexible variety. Can
sometimes be polymeric. Polymeric plasticizers are known as PN-Series
plasticizers. Polymeric plasticizers provide excellent resistance to extraction of
oil and solvent, excellent low volatility and heat aging stability for flexible PVC.
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They are mainly used for heat resistant cable compounds, gaskets and
applications requiring resistance to oil extraction.
Anti-static plasticizers for PVC are known LV series. These plasticizers give
very good anti- static properties suitable for Flooring, Curtain, Hose, Footwear
and Others. Maximum anti- static property is achieved by combining different
types of LV series plasticizers.
10) Stabilizers: - All plastics used in packaging materials gradually degrade
during their lifetime by combined attacks of chemicals deteriogens, harmful
physical effects of the environment, high-energy radiation in sterilization
process, & micro-organism. They are used in polymer to protect them from
degradation during storage and processing and under performing conditions.
Different kinds of stabilizers are as follows.
10.1) Antacids: - Acid scavenger (antacids) are stabilizers contributing
significantly to the performance of PO,PVC, PA, or PET containing acid contained.
They are commonly use as base stabilization packages & contribute significantly to
the overall performance of the stabilizer in the polymer containing halogenated
flame retardants, prevent corrosion of metallic parts of the equipment, reduce
discoloration by chelating residual amounts of titanium & aluminum catalyst in
Poor from thermo degrading PVC.
10.2) Antimicrobials / Biostabilisers: - Help prevent deterioration of plastic
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materials where part of the material might be susceptible to microbiological attack.
Such attacks can cause staining, discolouration, odour and loss of aesthetics but
more importantly, loss of electrical insulating properties, hygiene and overall loss
of mechanical properties in the material.
It is used at a 0.6 wt. % to 5.0 wt.% level.
10.3) Antioxidant: - Substance which protects a polymer against oxidation,
whether during processing or in service life. Oxidation can cause loss of impact
strength, elongation, surface cracks and discolouration. It help prevent thermal
oxidation reactions when plastics are processed at high temperatures and light-
assisted oxidation when plastics are exposed to UV light.
Antioxidant
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Color
Natural
Ingredients
Active: 10% Phosphite & Phenolic blend
Carrier: LLDPE
Dosage
0.5 to 2 % depending on the end application.
a) Chain-breaking Antioxidant or “primary”: - Primary antioxidants are added
to the polymer to protect against degradation during the service life of the finished
product.
The common concentration of phenols in plastics ranges between 0.0025 and 0.3
wt.%. phenol may be used as single stabilizers. Di(octadencyl)hydroxylamine was
introduced for processing and LTHA stabilization of PP. It is used in
concentrations of 0004% to0.06 wt.% in combination with aromatic phosphites.
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b) Hydro peroxide Deactiving Antioxidant or “secondary”:- Secondary
antioxidants are added to the resin to reduce color formation and to provide
processing stability during the pelletization and extrusion/molding processes.
The application level of phosphites in this are between 0.05 % to 0.3% in PO,
PS, or PET. A higher concentration, up to 1 wt.% may be used in PVC.
10.4) Heat Stabilizers: - To prevent decomposition of the polymer even in absence of oxygen
during processing. Processing usually results in temperatures well above 180 deg celsius, which
without the addition of heat stabilizers would result in the plastic material literally falling apart.
Concentrations level of heat stabilizers in various PVC products are in the
range of 1.5-o.3 wt.% for metal soaps and of 0.3 to 2.5 wt.% for organotin
stabilizers.
10.5) Light stabilizers :- Chemical added to reduce or eliminate reactions
caused by visible or ultra-violet light radiation, which would otherwise cause
polymer degradation in outdoor use.
a) Ultra violet stabilizers:- As for light stabilizers, but active in the ultra-violet
part of the spectrum, and used especially in outdoor applications to preserve
polymers against harmful radiation which would otherwise cause degradation.
Color
Natural
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Ingredients
Active: 10% High Molecular Weight (HALS)
Antioxidant: Complex
Carrier: LDPE
Dosage
A ratio of 0.5 to 5 % depending on the final application
Suitable for cast film applications where UV stability in final film is needed with excellent
color conservation.
b) Photoantioxidant:- Plastics are indispensable for our comfortable life. But, they are
easily degraded by autoxidation, especially under the action of UV light, due to their
organic character. Therefore, additives preventing the photo-oxidation are needed. 2-
Hydroxybenzophenones are widely used as ultraviolet absorbers (UVA), and their effect
is discussed.
Color & Ingredients
Natural & Processing Aid: 3.0%.
Anti-Oxidant: 0.2%. Inert with other additives
Carrier: LLDPE/HDPE
Dosage
1 to 3% depending on the end application.
Role of Additive in packaging
The packaging industry use chiefly plastics, metal, glass, wood among all these
materials, thermoplastic doing well with almost 30% share by value, and this share
is increasing. In fact packaging now represents the biggest single use of
thermoplastic in world.
The packaging industry whole is growing, nevertheless growth in business is in
flexible plastic. Additive such as antiblocking, slip agents, antistatic agents &
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antimicrobials are in demand for packaging plastics as well as heat and light
stabilizers & of course color pigments. Oxygen scavengers are also be widely used
in food packaging.
PE is the dominant packaging polymer, used for supermarket bags, food packaging
and rubbish sacks. HDPE is most important resin for rigid pack but PS is widely
used in packaging sheet, as is PVC to lesser extent. PP is used for more specialized
packaging in industrial goods.
PVC usage in rigid packaging, including containers and bottles, has declined
sharply but it is used in flexible packaging by addition of additives in it which
results in properties change for flexible packaging.
Polyethelene nephthenate is being promoted in the form of thin, flexible film with
good barrier properties.
Food packaging is important for the plastics and for additives. Globalization
requires the preservation of packed food in lengthy journeys to supermarkets. The
technology to achieve this require special type of additives.
Completion for PET from cheaper, clear PP has been made possible by clarifying
additives. Clarity is greater advantage in packaging of substance where visual
inspection is required. Antifogging agents such as sorbitan ester and glycerol ester
is used in flexible PVC food wrapping. Additives for transparent bottles may
include UV absorbers to protect the contents as well as polymer, from the
fluorescent light and sunlight. The main additive automotive PP apart from mineral
fillers and associated coupling agents are nucleating agent, antioxidant, flame
retardants and light stabilizers. The need for effective stabilizers is accentuated by
changes in car design, using more glazing and allowing more sunlight into cars
interiors. Flame retardants are incorpareted into seats.
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REPORT HIGHLIGHTS
The global market for plastics additives is expected to increase from $36.2 billion in 2008
to an estimated $37.4 billion in 2009, and $45.8 billion in 2014, for a compound annual
growth rate (CAGR) of 4.1%.
Property modifiers have the largest share of the market, worth $18.2 billion in 2008 and
an estimated $18.7 billion in 2009. This is expected to increase at a CAGR of 4.1% to
reach $22.9 billion in 2014.
The property stabilizers segment is the second largest, generating $12.1 billion in 2008
and an estimated $12.6 billion in 2009. This segment should reach $15.4 billion in 2014,
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for a CAGR of 4.2%.
How will additives shape the future of plastics?
Additives are essential components of plastic formulations providing maintenance
and/or modification of polymer properties, performance and long-term use. The
extension of polymer properties by additives has played a substantial role in the
growth of plastics. At the beginning of the plastics age additives were used mainly
to maintain polymer properties and to help plastics to survive heat treatment during
transforming processes. The next generation of additives provided extension of
service life as well as modification of mechanical and physical properties. These
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well-established additives – antioxidants, heat stabilizers, light stabilizers and
others – cover the requirements of standard plastics and today's mass applications.
The more recent developments of high-performance additives address more
stringent or new requirements, more severe processing and use conditions and/or
environmental concerns, but still with the main target of maintaining plastic
properties. The future will introduce more and more new effects and functionalities
through additives in plastic applications tailoring the properties of polymers and
offering a vast potential of innovation in the plastics area. Recent examples of
emerging technologies show that additives will not only modify the polymer itself
and add new properties, but can also, when incorporated into the plastic,
beneficially impact properties, which are of high value for the user. The paper
shows the role of additives used in plastics from the past to the present with the
focus on stabilization and performance of additives incorporated during melt
processing, and outlines future trends.
REFERRENCE
Plastic in Packaging – Dr [Link] & Dr [Link]
PLASTICS IN PACKAGING by I.I.P
Plastics and the Environment – Anthony L. Andrady
PACKAGING TECHNOLOGY VOL 2 by I.I.P
Encylopedia.
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