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Introduction
Polypropylene (PP) sold for commercial consumption has some types of additive. We will define 'unmodified'PP as representing only those additives without which PP could not be viably processed in commercial extruders, moulding machines and the like. Accordingly, we will define'modified'PP as that which has additives designed to provide special environmental, processing or physical properties. Typical additives to unmodified PP include antacids such as calcium stearate., calcium pelargonate, zinc oxide or hydrocalcite. These compounds are required to neutralize catalyst residues that could otherwise form acids detrimental to the converter's equipment. The second basic additive to PP is antioxidant. This is required, as a minimum to protect the polymer from chain scission during processing and ageing. Typical process stabilizer antioxidants are hindered phenols. Most additional additives and modifiers such as clarifiers, flame retardants etc. are targeted to affect a certain class of properties. Further, fillers and reinforcements are incorporated to impart "Value Addition" to PP. High value added PP products can be made by "Modifying PP with elastomers such as EPM/EPDM. Compounding is defined as the process of incorporating additives, modifiers into PP for achieving uniformity on a scale appropriate to the quality of the articles subsequently made from the compound. It is also known as hot or melt blending. 2.0 Value added PP products 2.1 Low level additives 2.1-1 Environmental Property Enhancement In addition to process stabilizers, additional heat stabilizers are used to improve the long term heat ageing of PP. Several antioxidants will afford improvements, with the choice dependant on the environment requires. An important parameter is the continuous use temperature. Typical PP homopolymer with moderate stabilization has a continuous use temperature of 105 deg. c. Special stabilization can increase that temperature to 125 deg. C. Thioethers can act as long term heat stabilizers. The UV resistance of unmodified PP is poor. However, stabilization can improve its performance significantly. Typically, hindered amines-can be used in combination with other appropriate additives to deliver service life or more than 5 years outdoors in both pigmented and non-pigmented products. This can be done without affecting the appearance of a component. In addition, if a black appearance is acceptable, special grades of carbon black at levels above 2% can provide a service life of more than 20 years. In addition to the stabilized applications listed above, there are many specialized uses of PP that require low levels of stabilizers. Among the applications for these stabilizers are the protection of PP components in radiation sterilizing environments, the prevention of colour development in various environments and the stabilization of wire-coating resin against the effects of copper. Each of these unique applications requires specific additive packages. 2.1-2
In addition to the need for application heat stabilizers, some manufacturing processes require exceptional melt stability. For example, if products will be reprocessed repeatedly, if high levels of scrap are used or if extruded sheet subsequently will be exposed to high temperatures, as in a thermoforming application, the goal would be to minimize degradation in the extrusion process.. In these cases, additional melt stabilizers are required. Phosphite-based products are used for this purpose. In film resins, slip agents and antiblocks are added to improve the processing and performance characteristics of the film. Slip agents are typically amides, with the particular selection depending on the characteristics being sought. Typical antiblocks are utilized to prevent the film from sticking to itself, while
slip agents are utilized to prevent the film from sticking to other surfaces, such as the converting equipment. Also used in film for processing and application performance are antistats. These products act to minimize static build-up as the film passes over the downstream equipment, as well as to minimize the dust pick up inherent in packaged products. For the latter applications, antistats are sometimes incorporated into PP used in sheets, bottles and moulded articles. Monoglycerides and/or diglycerides are typical PP antistats. Injection moulding products may utilize additives to adjust processing performance in the form of lubricants and/or mould release additives. These additives may interfere with decorating.
2.2.-1 Selection criteria for fillers and reinforcements in PP when incorporating fillers and reinforcements into PP, a number of factors have to be considered. These are summarized below: Particle shape, mean particle size and particle size distribution of the fillers Dispersability and adhesion (linkage) with the PP matrix. Abrasive action of the filler on the processing machines. Properties of the filler/reinforcement such as specific gravity, intrinsic strength, inorganic impurities. Problems associated with dust when handling fine powders. Cost of the filler/reinforcement Reinforcement is justified only when a distinct improvement of properties/cost reduction compared to unreinforced PP is found or when a specific combination of properties is not achievable by other means. Some general rules for selecting fillers and reinforcements in PP are summarized below: Property Improvement Sought Improved surface finish Improved tensile strength and flexural modulus Increased conductivity Choice of Filler/Reinforcement Calcium carbonate, talc, glass beads Glass fibres, wollastonite, carbon fibres Carbon powder, A1 flakes, Ni-coated mica, stainless steel fibre
Reinforcing fillers produce the following improvements in thermoplastics: Increase in Tensile strength at break and compressive, shear and flexural strength Increase in modulus of elasticity and stiffness of the composite material Increase in HDT and decreasing temperature dependence of mechanical properties Lower shrinkage Two discrete phases are always present in reinforced plastics. The discontinuous filler phases should exhibit higher tensile strength and higher modulus of elasticity than the polymer matrix, whereas the continuous polymer phase should possess higher elongation at break than the fibre. For this reason, fibres are suitable as reinforcing agents. When the fibre reinforced material is subjected to a tensile load, local tensile stresses are transferred to the polymer/fibre interface by shear forces and distributed over the fibre surface. For this purpose, the fibre must adhere well to the polymer and possess a specific length, since otherwise it slips out of the matrix material. The higher the modulus of elasticity of the matrix polymer, the smaller can be the minimum length of the fibre. Adhesion can be considerably improved by coupling mechanism between the filler and the plastic. 2.2-2 Calcium Carbonate Filled PP Calcium Carbonate (CaCO3) can be classified as Mineral ground or natural Precipitated or synthetic Naturally occuring calcium carbonate is found as chalk, limestone, marble and is the preferred variety for filler incorporation into PP. A typical composition of filler grade calcium carbonate is shown below CaCo3 : MgCO3 : Fe2O3 : 98.5-99.5% Upto 0.5% Upto 0.2%
Other impurities include silica, alumina and aluminium silicate, depending on location, source of the ore. Typical mineral properties are Density : 2.70 g/cc Moh;s hardness : 3 Degree of whiteness 85-95% Oil absorption : 9-21g/100 g. powder Specific surface : 1-15 m2/gm area
Loadings of calcium carbonate in PP typically run from 10 to 50%, although concentrations as high a 80% have been produced. The filler is available in a variety of particle sizes and size distributions can be coated or uncoated. Generally speaking, large particle size, greater than 5 um CaCO3 are less expansive, but they reduce the impact strength of the PP compound. Smaller particle sizes (less than 1 um) cost more and are more difficult to compound, but provide superior impact strength and improved surface appearance. CaCO3 is usually selected as a filler when a moderate increase in stiffness is desired. minimal sacrifice in impact strength can be tolerated. Other effects of the mineral filler are to increase the density of the PP compound, reduce shrinkage, which can be helpful in terms of part distortion and the ability to mould in tools designed for other polymers. At typical levels 10-50%, the viscosity of the compound is not significantly affected by the CaCO3. The main secondary additive employed in CaCO3 formulations is a stearate. The stearate acts as a processing aid, helping to disperse the finer-particle size CaCO3. It also helps to prevent the absorption of stabilizers into the filler. Finally, as an added benefit, it acts to cushion the system, resulting in improved impact. (Figure 1.)
Table (1) illustrates several properties available based on CaCO3 formulations. Applications of this product range are in furniture, flush tanks, fan regulator covers, textile bobbins, refrigerator parts. It is an inexpensive substitute for polystyrene and ABS co-polymer. IN PP films, incorporation of CaCO3 improves drawing properties. In PP tapes, use of CaCO3, upto 5-6% greatly reduces tendency of PP to fibrillate. 2.2-3 Talc Filled PP
Talc, chemically is hydrated magnesium silicate and can be represented at 3 MgO.4SiO2-H2O. Naturally occuring talc can exist in various forms like fibrou,s lamellar, needle, modular etc. A typical composition of talc is as under: SiO2 Al2O3 Fe2O3 FeO CaO MgO H2O : : : : : : : 40-62% 0.2-11% 0.1-0.5% 0.1-6.0% 0.3-1.0% 30-33% 16-17%
Figure 1. (a) Effect of filler level on falling weight impact strength of PP at 23 deg. C. (b) Effect of filler level on notched izod impact strength PP at 23 deg. C.
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Property
Melt flow rate, condition L,g/10 min. Density, g/cc Tensile strength (yield) MPa. Flexural modulus(1% secant), MPa Rockwell R hardness Heat deflection temperature (deg. C) Notched izod (23C), J/m a No break, flex.
Melt flow rate, condition L,g/10 min. Density, g/cc Tensile strength (yield) MPa. Flexural modulus(1% secant), MPa Rockwell R hardness Heat deflection temperature (deg. C) Notched izod (23C), J/m
4 0.903 35 1656 99 88 42
Typical Mineral properties are Density : 2.90 g/cc Oil absorption 28-51 g/100 g. powder Moh's Hardness: 1 Talc is generally selected to achieve higher stiffness than is possible with CaCO3, although at the cost of reduced impact strength and greater sensitivity to moisture. It helps to decrease shrinkage and warpage and increases thermal conductivity of the PP compound. Additional effects are higher HDT's and higher tensile strength as compared to CaCO3 formulations. Table (2) summarizes typical physical properties of talc filled PP. In addition to structural and thermal property improvements, talc contributes to better dimensional stability, enhanced thermoforming opacity and depending on talc grade, white colour. The purity of talc is particularly important to the thermal properties. The presence of metal ions can catalyze the degradation of PP, which will decrease the long-term thermal stability of the composite. Small amounts of stabilizer packages are often used in combination with talc, as in under- the hood applications. Surface treated talc do not affect the thermal properties of PP adversely. Talc-filled masterbatches are availabale at loading upto 75%. Dark talc is often used for exterior and interior automotive engineering applications where colour is not so critical Although the reinforcement properties of dark talc are lower than those of white-talc grades, the dark talc provides acceptable performance and costs less.. Often compounds for such applications contain both talc and CaCO3. White talc are used in PP garden furniture and domestic appliances such as washers, dryers etc. PP is the largest volume plastic usage for talc. Talc provides the structural strength (stiffness) and high temperature resistance needed for automotive and appliances.
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Property Tensile strength, MPa Flexural modulus, MPa Izod impact, J/m Notched at 220 deg. C Unnotched at 22 deg. C heat deflection temperature deg. C at 264 psi Mould shrinkage, % lengthwise
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Following the trends that have been established, mica is the next step up in the stiffness/HDT ladder. Likewise, it results in further decreased impact. Mica is found in a platelet form rather than in the more particular form of CaCO3. As the fillers pass from the particulate form through the platelet form on their way to a fibrous-type form, the changes in physical properties correspond. From another view point, as the aspect ratio, or length-to-diameter (or thickness) ratio of the filler increases, strength tends to increase and impact to decrease. Mica offers outstanding stiffness as well as increased HDT. These properties are further enhanced by the addition of a coupling agent. Table (3a) summarizes data on some mica-filled PP. Mica-PP composites can be as stiff as steel sheet, but weight only 45% as such. Mica filled PP products are considered inexpensive substitute for glass fibre filled PP (Table 3b). An interesting use of mica is in PP-PE coopolymer foam for loud speakers and musical instruments due to excellent acoustic properties of mica mineral. The higher speed of sound in mica allows for a more compact speaker cone. 2.2-5 Glass -Fobre Reinforced PP
Glass fibre reinforced PP is a high growth segment of the market. These products have high tensile strength and HDT. Applications include those areas requiring the chemical resistance of PP with the strength of engineering resins. A drawback of these materials had been their tendency to distort in the final product. Recent advances have resulted in easy-flow grades that significantly reduce this tendency to warp. Other developments include the production of higher impact grades. These improvements have opened new applications in the appliance and industrial markets. Typical fibre lengths of glass are1/8 to 3/16 inch, although longer fibres are available for specialty applications. The standard glass diameter for PP applications is 13 microns. The factors influencing properties are the base resin, the starting glass-fibre geometry, the compounding and processing techniques, the presence or absence and type of a coupling agent. Table (4) lists typical properties of glass filled PP. Table (5) illustrates the effect of polymer type and melt flow rate of physical properties using standard 3/16 inch starting fibre length and a coupling agent. As can be seen the property balances available compare favourably with many other engineering materials. Table (6) demonstrates the effect of the type of coupling agent on PP. As can be seen, the coupling agent provides a considerable increase in tensile strength. In addition, other properties, such as creep resistance are also improved. The mechanism of the coupling agent is to form a bond between the sizing agent on the glass fibre and the specially treated PP resin.
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Density Tensile strength at yield Tensile strength at break Elongation at break Flexural strength HDT 66 psi
g/cc MPa
MPa
23
32.5
35.0
36.0
% MPa deg.C.
60 330 75
30 440 90
20 450 97
30 450 112
Homopolymer
40% 2 20% 18 40% 12
Copolymer
20% 1.8 40% 1.5
1.04 83
1.22 103
1.04 77
1.22 99
1.05 61
1.14 86
4209
6831
4071
7590
3450
4830
141
144
144
145
141
143
234
136
134
137
141
143
85
112
75
96
149
192
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Table- 6 Effect Coupling Agent on a 30% Glass-Reinforced PP Property Melt flow rate, condition L, g/10 min. tensile Strength (yield)MPa Yield Elongation (%) Flexural modulus(1% secant), MPa Heat deflection temperature (264 psi) deg. C. Notched Izod (23deg. C) J/m No. of Coupling Agent 15 71 1.8 6141 143 Coupling Agent A 12 88 2.1 6279 146 Coupling Agent B 12 100 2..9 6348 146
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85
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Applications of glass filled PP are in fan blades, head lamp housing, chemical process equipment, washing machine tanks etc. Table (7) shows a comparison of properties of filled PP homopolymer 2.2.6 Other fillers and Reinforcements
Many other fillers and reinforcements also can be used with PP, including wood flour, ground corn stalks and other cellulose containing substances. The cellulosic based products provide low-cost opportunities for achieving high stiffness, but their applications is limited owing to their tendency to char and generate water at processing temperatures. For the achievement of conductivity and/or static dissipation properties, metal powders, silver coated glass spheres, metal wires and conductive carbons have been used. TO reduce the coefficient of friction and to improve wear characteristics. TeflonR and Silicone are used. These systems are highly specialized and designed for particular applications. 2.2-6 Colour Systems
The production of precoloured PP can be accomplished through the use of previously selected pigment systems that have been distributed uniformly in the polymer. For successful colour matching, the viscosity of the resin, the ease of pigment dispersion, the compounding equipment used and the selection of dispersing aids must be considered. In order to ensure adequate dispersion, pigment systems are often predispersed in a masterbatch. When utilizing a masterbatch, the carrier must be compatible with PP matrix. In addition, the possible nucleating effect of certain pigments, heat stability of pigments which could affect processing and physical properties of PP respectively must also be considered.
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Property
Units
MFI Density Mould Shrinkage Tensile strength at break Elongation at break Flexural strength
% MPa deg.C
60 33 75
70 35 75
50 47 99
30 44 90
61 141
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60 V-0
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There are three broad categories of alme retardant polypropylene A) Chlorine based systems B) Bromine based systems C) Non-Halogenated systems There are a number of flame retardants available all over the world in each of the above system. The right choice among them depends on the end application and the cost. Another important inorganic filler is antimony trioxide which acts as a synergist with halogen i.e. mainly chlorine and bromine containing flame retardants. The halogen liberated from these during burning reacts with antimony trioxide to form volatile antimony halides and oxyhalides. These enter the gaseous part of the flame and help quench reaction occuring, thereby neutralizing free radicals. The antimony trioxide also reacts directly with the polymer to give water which cools and dilutes the flame.
UL Classification
Following is the basics of Underwriters Laboratory specifications: This is a flammability test devised by Underwriters Laboratories for plastic materials used in electrical devices and appliances. In this test, specimens are exposed for two successive 10 seconds ignitions from 3/4" burner flame. They are classified according to the time it takes the flame to extinguish and the length of time any"after glow" persists. Rating are as follows: 94 V-O Extinguishment time After glow time 0.5 seconds 0.30 seconds
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94 V-2 Extinguishment time After glow time Flaming drips permitted 0.25 seconds 0-62 seconds
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Table 9
UL 94
UL 94 V-1
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UL 94 V-0
Test Method
D 1505 D 638 D 638 D790 D256 D256 D2240
Units
gm/cc kg/cm2 % kg/cm2 % kg. cm/cm kg.cm/cm Shore
Blend I
0.9-1.0 45 500 1000
Blend II
0.9-1.0 100 500 7500
Blend III
0.9-1.0 150 500 7500 N.B N.B 70D
Blend IV
0.9-1.0 200 350 10000 60 NB 77D Bumpers
Blend
N.B N.B 85A O riungs, hoses, mats and mud flaps, bellows
N.B N.B 90A Automobile trims, toys, refrigerator liners, window profiles
II 60 40
III 70 30
IV 80 20
V 90 10
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In the recent past, the most important uses of PP-EPDM blends has been in the automobile industry. Comparative lightness, low cost and a wide range of mechanical properties are the main factors responsible for the continuous growth of these materials since 1975. Their main use in car bumpers using either PPEPDM flexible shapes mounted on a rigid steel framework or fabricated self-supporting finished articles such as complete car front masks. Suitable blends contain from 10 to 35% by weight of EPDM, according to flexibility and imapct requirements. EPDM-PP talc ternary blends find their biggest outlet as interment panel dash boards in many models of low to medium cost cars. For this application stiffness and shape stability, coupled with an impact resistance high enough to avoid splintering failures or dangerous sharp fragments in medium speed crashes provide these blends with an ideal application. According to an estimate 90% of the OO-EPDM blends used are for the automotive industry atpresent. A summary of filled and reinforced-PP products in the automobile industry is given in Table 13.
3.0Compounding Machinery
Compounding of PP with additiives, fillers and reinforcements can be achieved using various types of machines depending on cost and quality of mixing desired. A few of these are discussed in the section. 3.1 Compounding low add levels PP is generally an easily compounded material and the compounding of low-add-level products usually requires nothing more than a dry solids mixer for preblending and a single-screw extruder for pelletizing. Extrusion temperatures will depend primarily on the viscosity or melt flow rate of the PP homopolymer or copolymer component., with melt temperatures typically falling between 190 deg. c. and 2245 deg. c. Depending on the equipment, PP may give lower output rates on extruders than other polymers as a result of both its low density and its rheological properties. At high melt flow rates, pelletizing may present some problems owing to the low melt strength. With specialized equipment, melt flow rates as high as 1000 have been pelletized. Both hot-cut and cold-cut pellletizing systems are suitable for PP. The choice usually depends on the equipment available as well as downstream processing considerations. In some subsequent extrusion and injection moulding processes, the shape and size of the pellets will influence the products processing behaviour. For example, the flat, thin wafer configuration characteristic of the hot cut has been reported to cause slipping problem in the extrusion of thin film.
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Table 13 Plastic Components in Maruti Esteem Part Name Material Wt. in gms. No. of parts Wt. per car (grams.)
4000 350 200 420 650 180 236 160 800 300 1275 550 1000 780 2600 730 3200
Instrument Panel Glove box Glove box lid Garnish cowl ventilator Oil filer housing assembly Fan blade 80 W Fan Blade 120 W AC blower Air filter assembly Trim rear pillar Air ventilator assembly AC case and cover cooling Boot component Bumper (Front upper) Bumper (Front lower) Bumper (Rear upper) Bumper (Rear lower)
Filled PP Filled PP Filled PP Filled PP Filled PP Filled PP Filled PP Filled PP Filled PP Filled PP Filled PP Filled PP Filled PP PP modified PP modified PP modified PP modified
4000 350 200 210 650 180 236 160 800 150 1275 550 500 780 2600 730 3200
1 1 1 2 1 1 1 1 1 2 1 1 2 1 1 1 1
When particularly good dispersion is required, a better option for incorporating these additives is to produce an additive concentrate. To obtain the necessary dispersion in the final product, the concentrate is produced utilizing a fluxed melt mixer such as a Banbury prior to extrusion. The extruded concentrate may then be blended with the polymer matrix during a final compounding stage or may be added during the final moulding or extrusion step. Colour concentrates are a well known example, but lubricants. UV/light stabilizers may also be incorporated in this manner. 3.2 High Add Levels 3.3 3.2.1 Single screw extrusion The addition of higher-add-levels of fillers and reinforcements may be done on a single screw or a twinscrew extruder. The choice is determined by the type of filler/reinforcement. In general, the single screw use is limited to low-aspect-ratio additives such as Ca CO3 and talc. The production of CaCO3 filled and talc filled materials may be accomplished using only a dry-solid mixer and a two-stage vented extruder. An Auger-type hopper stuffer assists feeding. As the filler level increases, melt fluxing mixers, such as Farrel Continuous Mixer (Figures 2) may be used to optimize mixing and distribution. The Farrel Continuous Mixer is a counter rotating, non-intermeshing twin-rotor mixer. It can be divided into 3 zones: (a) Feed zone (b) Mixing zone (c) Discharge zone. The feed zone of the mixer is designed to opimize ingestion and delivery of feed m material (s) into the mixing zone. Upon entering the
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mixing zone, the feed material is melted and then continuously fluxed, pumped, backmixed and it exits through the discharge zone. The maximum achievable loading will depend, to some extent, on the melt viscosity of the polymer, but primarily on the type of filler. For example, specialized Ca CO3 concentrates have been produced with filler levels upto 80%, while it is difficult to reach a 50% loading with mica. At high filler loadings, intensive mixing may not be necessary, as long as the filler is uniformly distributed. Over-mixing can cause separation. In general, both batch (Banbury) and continuous(FCM type) mixers are suitable. metered feeding is necessary for all high filler-level systems. Fillers such as CaCO3 are liable to bridge in the hopper. In addition, there is a potential for separation and build-up of the filler on vertical metal surfaces. The critical design features of the feeders are the agitator and the feed screw and their relationship with each other. The agitator should sweep the hopper walls as closely as possible to prevent filler build-up. The hopper should be equipped with a level control feeder.
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The compoudning extruder should have relatively shallow flights. A compression ratio of 2.5:1 is preferred and no additional mixing devices are generally required. Mineral fillers tend to be hygroscopic. Therefore, a vacuum vent is utilized during the extrusion step. When a cold-cut pelletizing system is used, the emerging strands from the die face is taken into water bath and taken out quickly, taking care to ensure integrity of the strands. A blower assists water removal from the strands prior to chopping.
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3.2-3.2 Filled PP
Filled PP grades can be compounded with twin screw extruders. Dispersion requirements for talc and CaCO3 vary according to the final product application. The primary objectives are uniform incorporation and mixing. A schematic diagram of mixing elements which make up a configurations shown in Figure (5). Fillers are added downstream t a melt to isolate their abrasive effects. A melt seal is formed upsteam where large pitch screws are used. The downstream section is configured for low shear mixing for low performance applications. Applications requiring high degree of dispersion are compounded using a high shear intensive mixing section.
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