LIBRARY REFERRENCE PROJECT ON Additive for Plastics
Submitted By: Shaikh Md. Izhar PG/K/2010/03
Topic Introduction Why do additives add to plastics How additive effects in polymer Types of additives Role of additives in packaging Report highlight
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How will additive shape the future 25
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.
How additives are essential?
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., highdensity 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. 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 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 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, 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 crossblending 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, 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: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%.
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.
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.
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.
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
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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
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. 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 (³soft´) 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. 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 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 lightassisted oxidation when plastics are exposed to UV light. Antioxidant
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 ³primary´: - 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.
b) Hydro peroxide Deactiving Antioxidant or ³secondary´:- 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 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. 2Hydroxybenzophenones 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 & 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.
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, 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 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.
y Plastic in Packaging ± Dr Otto.G.Piringer & Dr Albbert.L.Baner y PLASTICS IN PACKAGING by I.I.P y Plastics and the Environment ± Anthony L. Andrady y PACKAGING TECHNOLOGY VOL 2 by I.I.P y Encylopedia.