Polypropylene Practical Guide

Practical Guide to Polypropylene
4 Properties
The mechanical and thermal properties of PP are dependent on the isotacticity, the molecular weight and its distribution, crystallinity, and the type and the amount of comonomer. Additionally, PP is, like other thermoplastics, a viscoelastic material. Consequently its mechanical properties are strongly dependent on time, temperature and stress. The properties of 7 commercial materials (all made by the same manufacturer and subjected to the same test methods) are compared in Table 12. These grades are of approximately the same isotactic content but differ in molecular weight (indicated by the change in melt flow rate) and in being either homopolymers, random, block copolymer or controlled rheology grades. 4.1 Density The typical density of PP is 0.9 g/cm3 and it is the lightest among the widely used thermoplastics (see Table 1). Therefore, it offers the advantage of being able to manufacture more items for a given weight of the polymer. Polymethylpentene (TPX), a commercially available semi-crystalline transparent thermoplastic, has a lower density (0.83 g/cm3) than PP. Unlike PE, where changes in the degree of crystallinity result in quite large variations in density, the density of PP changes little over the whole range of homopolymer and copolymers. The density of the random polymers is marginally lower than the homopolymer grades (Table 12). On the other hand, elastomer-modified, filled or reinforced grades might have significantly higher density depending on their formulation. For example, a 40% talc-filled grade has a density of 1.2 g/cm3. 4.2 Thermal Properties Unlike metals, plastics are extremely sensitive to changes in temperature. The mechanical, electrical or chemical properties of plastics cannot be considered without knowing the temperature at which the values are derived. The thermal properties of a polymer typically determine its low- and high-temperature applications, impact properties and processing characteristics. Typical low-temperature applications for PP are in refrigerator parts and food packaging for refrigerated shelves. The applications where high-temperature properties of PP are of particular interest include sterilisation, particularly steam sterilisation, microwave oven proof containers and parts for dishwashers and washing machine which are subjected to hot water in the presence of detergents. 4.2.1 Glass Transition Temperature and Melting Point The mechanical properties of PP at a particular temperature are dependent on the glass transition temperature. At very low temperature, the macromolecules are largely immobile. As the polymer is heated, the restricted macromolecular zones become progressively more mobile. At the transition temperatures, the material changes from a glassy hard state to a soft tough state because certain molecular segments become more
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mobile. A polymer above its glass transition temperature acts a tough ductile material while below it, the material is hard and glassy. On cooling, the glass transition temperature is sometimes known as the freeze temperature. Glass transition temperature is measured using a dynamic mechanical thermal analyser (DMTA) or differential scanning calorimeter (DSC). PP has the following transition temperatures: Second-order glass transition temperature at 10 C (predicted). The actual value may be observed between 0 to 20C depending on the frequency/heating rate. Crystalline melting point between 160170 C depending on the grade and the frequency/heating rate. Recrystallisation temperature on slow cooling of the melt between 115 C and 135 C.
A typical temperature curve for shear modulus and mechanical loss factor, measured using torsion pendulum, for different grades of PP is shown in Figure 8. It can be seen from the figure that a copolymerised grades of PP has two peaks in the mechanical loss factor curve while PP homopolymer has only one peak. The first peak, above 0 C, denotes the glass transition temperature, similar to that of homopolymer PP. The secondary transition peak at 45 C is due to the presence of comonomer which provides some mobility to polymer chains above 45 C, thereby, giving enhanced impact properties.
Figure 8 A typical DMTA trace of PP showing different transition temperatures
PP copolymers, due to lower crystallinity, and metallocene-catalysed PP have lower melting points in comparison to homopolymerised PP. Recrystallisation temperature is quite important for injection moulding. Since the recrystallisation temperature of PP is between 115135 C, most of the crystallisation occurs during the cooling of the artefact in the mould. Since the recommended mould
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temperature is in the region of 2060 C, this allows the possibility to restrict warpage and improve dimensional stability during processing (Section 5.1.3). In addition, PP continues to crystallise after processing at a rate varying with moulding conditions and storage or treatment temperature. Brittle temperature is very closely related to the glass transition temperature and determines the minimum temperature at which a semi-crystalline polymer could be used without significant loss of its impact properties. 4.2.2 Maximum Continuous Use Temperature Maximum continuous use temperatures are based upon the Underwriters Laboratories (UL) rating for long-term (100,000 hours) continuous use, and specifically on the elevated temperature which causes the ambient temperature tensile strength of the material to fall to half its unexposed initial value following exposure to that elevated temperature for 100,000 hours. The tests provide a continuous use temperature for a plastic in the absence of stresses. The maximum use temperature of PP is compared with other thermoplastics in Table 13. It can be seen that other commodity plastics and some other engineering plastics have a significantly lower maximum continuous use temperature than PP. However, polycarbonate has a higher maximum continuous use temperature in comparison to PP.
Table 13 Maximum continuous use temperature of different plastics [1] Polymer C PP 100 HDPE 55 LDPE 50 PVC 50 ABS 70 HIPS 50 PA 6 80 PA 66 80 PC 115
Occasionally it is required that the service life of the component is predicted at a temperature above its maximum continuous use temperature or vice-versa. As a rule of thumb, a 10 C increase in temperature is equivalent to a decade increase in time. Since the maximum continuous use temperature of PP is 100,000 hours at 100 C, this would be equivalent to 10,000 hours at 110 C or 1,000,000 hours at 90 C. Hence, certain grades of PP may be theoretically suitable for a very short-term use at 140 C. However, the maximum use temperature of a polymer depends on the specific grade and its heat stabilisation system and should be carefully noted from the relevant trade literature. However, the functionality of the polymer for high temperature application might be quite limited in the presence of stresses.
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4.2.3 Heat Deflection Temperatures and Softening Points Heat deflection temperature is defined as the temperature at which a standard test bar deflects by a standard amount under a standard load. Generally loads of 0.45 and 1.80 MPa are used. The values of heat deflection temperature of various plastics are compared at different loads in Table 14. It can be seen from the table that the heat deflection temperature of PP is higher than the PE but, it is outranked by more expensive engineering thermoplastics. The Vicat softening temperature is the temperature at which a flat-ended needle of 1 mm2 circular cross-section area will penetrate a thermoplastic specimen to a depth of 1 mm under a specified load using a selected uniform rate of temperature rise. The Vicat softening point of PP lies between 9095 C and is considerably higher than the PEs. Above the Vicat softening point, the material becomes progressively softer and the crystalline melting point of PP homopolymer is about 165 C, depending on the grade. The practical application of the Vicat softening point data is limited to quality control and material characterisation. However, it is taken as a rough estimate of the maximum temperature for ejection of the artefact from the injection moulding machine.
Table 14 Thermal behaviour of other thermoplastics in comparison to PP [1] Heat deflection Heat deflection temperature at 1.8 MPa Polymer temperature at 0.45 MPa (C) (C) PP 8895 5060 HDPE 75 46 LDPE 50 35 PVC 70 67 ABS 98 85 HIPS 85 75 PA 6 200 80 PA 66 200 100 PC 143 137
Heat deflection temperature is a single point measurement and does not indicate longterm heat resistance of plastic material. However, it may be used to distinguish between those materials that are able to sustain light loads at high temperatures. The heat deflection temperature of a specimen is affected by the presence of residual stresses. Warpage of the specimen due to stress relaxation may lead to erroneous results. In addition, injection-moulded specimens tend to give a lower heat deflection temperature than compression-moulded specimens. This is because compression-moulded specimens are relatively stress free. The data obtained by these tests cannot be used to predict the behaviour of plastic materials at elevated temperature nor can it be used in designing a part or selecting and specifying material. If an article is subjected to high temperature in the absence of stresses, maximum continuous use temperature (Section 4.2.2) can provide a suitable
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criterion for the selection of material. In addition, if load bearing properties are required from the component at high temperatures, the modulus of the plastic as a function of temperature (Section 4.3.1.2) could provide data for the design calculations. The flexural modulus of different plastics as a function of temperature have been plotted in Figure 9. The remarkable difference between different polymers can be explained on the basis of amorphous and semi-crystalline polymers. It can be seen from the figure that the amorphous polymers, such as PVC and ABS, maintain their strength quite well up to their maximum use temperature. However, their strength falls sharply when they reach their glass transition temperature. On the other hand, semi-crystalline polymers, such as PE and PP, slowly lose their strength above the glass transition temperature. However, the residual strength of a semi-crystalline material may be higher than the amorphous material at a higher temperature, and an amorphous polymer may be stronger at the lower temperature.
Figure 9 Flexural modulus of different plastics as a function of temperature [2]
4.2.4 Brittle Temperature At low temperatures, all plastics tend to become rigid and brittle. This happens mainly because the mobility of polymer chains is greatly reduced. Brittle temperature is closely related to the second-order glass transition temperature (Section 4.2.1). Brittle temperature is defined as the temperature at which 50% of the specimens tested exhibit brittle failure under specified impact conditions. The brittle temperature of different grades of PP are given in Table 15.
Table 15 Brittle temperature of different types of PP PP grade Brittle Temperature Homopolymer 5 to 15 C Random copolymer 10 to 15 C Block copolymer 40 to 10 C 29
Due to the comparatively higher brittle temperature of PP, its use in low-temperature environments should be carefully considered and compared with other available thermoplastics. Low-temperature brittleness of some common thermoplastics is compared in Table 4. It can be seen that LDPE, HDPE, ABS and PVC offer lower brittle temperature. Impact strength at lower temperatures, e.g., 40 C, should also be considered as a useful criterion for material selection for use under arctic conditions. 4.2.5 Specific Heat Many features of the processing behaviour of PP may be predicted by consideration of thermal properties. The specific heat of PP is lower than that of PE but higher than that of PS. Therefore, the plasticising capacity of an injection moulding machine using PP is lower than when PS is used but generally higher than with HDPE. The plasticising capacity is defined as the amount of the material which can be melted and plasticised in the barrel in a given time in a given injection moulding machine. Specific heat is a function of temperature below melting temperature. However, a significant rise in specific heat is observed near the melting point due to the partial crystalline nature of the polymer. However, the specific heat of the polymer melt is virtually independent of temperature. The specific heat, or more precisely the enthalpy, of the material controls the cooling of the artefact in the mould and predominantly the design of the cooling channels in the mould. The heat requirement for cooling of a PP artefact can be calculated from a graph such as that illustrated in Figure 10. To achieve faster cycles, mould cooling requirements should be considered from the beginning. The cooling system should balance the heat flow from the part to ensure uniform part cooling and minimise residual stresses, differential shrinkage and warpage. Other thermal properties of PP are given in Table 16.
Table 16 Thermal properties of PP Property Specific heat (J/g C) at 23 C Specific heat (J/g C) at 100 C Thermal conductivity at 20 C (W/m K) Linear coefficient of thermal expansion (/C) 2060 C 60100 C 100140 C
Value 1.68 2.10 0.22 -5 10 x 10 -5 15 x 10 -5 21 x 10
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Figure 10 Specific heat of PP as a function of temperature
4.2.6 Thermal Conductivity The lower thermal conductivity of PP and other plastics compared to metals, gives protection against external temperature changes and so PP could be used for insulation applications. However, the use of PP, unless foamed, as a primary insulating material is rather limited (owing to cost factors). PP has been used for food packaging of refrigerated foodstuffs due to its suitability for food applications rather than its suitability as an insulating material. Lower thermal conductivity limits the production cycles and can result in cooling strains in thick sections, which may lead to warpage of the article. Similar to other plastic materials, the conductivity of the PP is a function of density and foamed PP has lower conductivity than the unfoamed PP. 4.2.7 Thermal Expansion The coefficient of thermal expansion is defined as the fractional change in length or volume of a material for a unit change in temperature. The coefficient of thermal expansion of plastics is considerably higher than metals, up to 6 to 10 times as high. This difference in the coefficient of thermal expansion can lead to internal stresses and stress concentrations. Consequently, premature failure may occur. Thermal expansion in PP gives significant volume changes on melting. It thus shrinks by 12% in moulding, this must be allowed for when designing the tool. Mould shrinkage and thermal expansion values for PP are compared with other thermoplastics in Table 2. The use of filler lowers the coefficient of thermal expansion considerably and brings the value closer to that of metals and ceramics (Section 4.3.6). The effect of thermal expansion on shrinkage, warpage and dimensional tolerances is discussed in Section 5.1.3.
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4.3 Mechanical Properties The mechanical properties of PP depend on several factors and are strongly influenced by the molecular weight. General observations suggest that an increase in molecular weight, keeping all other structural parameters similar, leads to a reduction in tensile strength, stiffness, hardness, brittle point but an increase in impact strength. This effect of molecular weight on the properties of PP is contrary to most other well-known plastics. The properties of some PP grades with different melt flow indices and structure are compared in Table 12. It can be observed that an increase in mechanical properties is not necessarily reflected in a trend predicted only on the basis of molecular weight, and other structural parameters, particularly crystallinity, play a very important role. Hence, the prediction of the mechanical properties on the basis of molecular weight or melt flow rate should be treated with caution. Appropriate data for the properties of the material should always be consulted. 4.3.1 Short-term Mechanical Properties A tensile test reveals that tensile force increases with increasing elongation, up to the yield point (Figure 11). After this, force initially decreases, i.e., the material can be further stretched with a smaller force. This is accompanied by a marked necking of the cross section of the test specimen. When this necking down has progressed along the entire length of the specimen, force increases again until elongation at break is reached. The second increase in deformation resistance is due to partial orientation of the macromolecules which strengthens the material. This typical behaviour of PP is similar to other ductile plastics. It can be seen from Table 12 that the mechanical properties of random and block copolymer grades are lower than the homopolymers for the same value of melt flow rate or molecular weight. The difference in their tensile stress/strain curves is highlighted in Figure 12.
Figure 11 A schematic tensile stress/strain curve for PP 32
Figure 12 Tensile stress/strain curves for different types of PP
It can be seen from Table 1 that the flexural modulus and tensile strength of PP is lower than most of the plastic materials except LDPE and HDPE. However, PP offers an advantageously high flexural modulus to cost ratio which makes it an ideal candidate for replacement material to many engineering plastics on the cost reduction basis. The short-term stress/strain data of different grades of PP (and for other plastics) is of limited use and should only be used for pre-selection of material. In reality, plastic components are seldom designed and subjected to such high levels of strain as applied in short-term tensile tests. In addition, most of the cases of product failure are brittle in nature. Consequently, the long-term creep and fatigue properties of PP, discussed in Sections 4.3.3 to 4.3.5, are more important for structural applications. 4.3.1.1 The Effect of Test Speed Like other viscoelastic thermoplastics, the mechanical properties of PP depend on the speed of the test. For instance, raising the speed of the test decreases the observed flexibility and increases the observed brittleness. 4.3.1.2 The Effect of Temperature The stiffness of PP is a function of temperature. The variation of flexural modulus of different grades of PP as a function of temperature is shown in Figure 13. PP homopolymers are slightly stiffer than copolymers at room temperature. However, the difference between the two types is diminished as the temperature rises. The flexural modulus of elastomer-modified PP is significantly lower than the homopolymer or copolymer PP, and its service temperature is around 90 C, much lower than that of homopolymer PP. PP becomes more ductile as the usage temperature increases, shown by an increase in elongation at break and decrease in ultimate tensile strength and yield stress.
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Figure 13 Flexural modulus of different grades of PP as a function of temperature [2]
4.3.1.3 Time-temperature Superposition PP is a viscoelastic material, and, consequently, its mechanical properties are strongly dependent on time, temperature, the level and type of applied stress and the testing speed. The apparent stiffness or elastic modulus of all plastics reduces with time under load due to the processes of stress relaxation and creep. Similarly, the modulus reduces with increasing temperature. In other words, the effect of time and temperature on the mechanical properties is interchangeable. The theory behind this behaviour of polymeric materials was given by Williams, Landel and Ferry. The detailed description of this theory can be found in standard textbooks [e.g., 14]. However, at this point, it will suffice to say that the effect of time during service could be simulated in the shortterm using high temperature. This superposition of time and temperature could be used in practice to predict the durability of the products. 4.3.2 Impact Strength The second-order transition temperature of PP homopolymer is 10 C. This explains the drop in its impact strength at temperatures around 0 C. The impact strengths of different grades of PP at different temperatures are given in Table 12. Several methods are used for measuring the impact strength of PP. However, none of the methods satisfactorily predict performance under conditions of end use. In the Izod or Charpy test, a notch is incorporated in the sample to concentrate stress; this normally leads to brittle failure. Impact strength is reduced as the notch gets sharper. Consequently, sharp corners in load-bearing sections must be avoided in the design of the article, as a general rule for all the plastics. The impact strength of an article depends on the inherent molecular structure of the grade used and the morphology arising from the processing conditions. Changes in the
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geometry of an item can have a major effect on its toughness rating. Impact strength increases with the molecular weight but more markedly with comonomer content. The most important way of improving the impact strength of PP is by incorporating a rubbery phase, as in heterophasic copolymers. Toughness increases rapidly with higher rubber content, and its transition from ductile to brittle failure occurs at lower temperatures. One of the major reasons for the failure of PP artefacts is the brittle failure. This is mainly caused by the incorrect selection the PP grade, particularly the use of PP homopolymer in place of copolymer or use of wrong material at the moulding floor. Infrared microscopy and gel permeation chromatography can quickly identify the source of the problem. 4.3.2.1 Falling Dart Impact Test The falling weight or dart drop test method simulates actual day-to-day abuse and can be carried out either on standard laboratory specimens or on the articles themselves. Failure may occur in various ways ranging from brittle to ductile failure (Figure 14). Particular care must be taken to avoid the brittle failure by proper selection of grade. At temperatures below 20 C, elastomer-modified PP is more impact resistant than PP copolymer and homopolymer.
Ductile Bructile Brittle
Figure 14 Example of ductile, bructile or brittle material failure Reproduced with permission from Shell, Shell, website: www.basell.com
4.3.2.2 Notched Impact Strength PP copolymer has higher impact strength than homopolymers even at low temperature (Figure 15). Higher molar mass provides better impact and notched impact strength
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above 0 C. Elastomer-modified PP shows high notched impact strength even at temperatures below 0 C.
Figure 15 Typical notched impact strength of PP as a function of temperature
4.3.2.3 Tensile-impact Strength Impact strength tests permit no differentiation between specimens undergoing the test without failure. In this respect, the tensile-impact strength test is superior. Other test variables such as notch sensitivity, loss factor and specimen thickness are eliminated in the tensile-impact strength test. In addition, tensile-impact strength tests can be used for very thin specimens. The tensile-impact strength test consists of a specimen-in-head type of set up. In this case, the specimen is mounted in the pendulum and attains full kinetic energy at the point of impact. One end of the specimen is mounted in the pendulum and the other end be gripped by a crashing member, which travels with the pendulum until the instant of impact. The energy to break by impact in tension is determined by kinetic energy extracted from the pendulum in the process of breaking the specimen. The superior impact properties of elastomer-modified PP are, once again, observed. 4.3.3 Creep PP is a viscoelastic material and, like all other thermoplastics, it exhibits creep (or cold flow). Creep is the deformation or total strain which occurs after a stress has been applied. Its extent depends on the magnitude and nature of stress, the temperature and time for which the stress is applied. Over a period of time, PP undergoes deformation, even at room temperature and under relatively low stress. After removal of stress, a moulding more or less regains its original shape, depending on the time under stress and
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magnitude of stress. Recoverable deformation is known as elastic deformation and permanent deformation as plastic deformation. Typical creep curves plot deformation or creep against time on logarithmic scale for a range of loads or stresses. This basic creep data could be used to plot isochronous stress/strain curves, isometric stress curves or creep modulus as a function of time. In an isochronous graph, stress is plotted against strain at a constant series of time intervals (Figure 16). In isometric curves, stress or strain is plotted as a function of time for a series of constant strains or stresses. Creep modulus curves are the time-dependent value of modulus (Figure 17). As the properties of polymers are a function of temperature, these curves can be produced at different temperatures. This type of data is available from the raw material suppliers in most of the cases. However, sometime the creep data for the conditions which the component might observe in service are not available, hence the data is extrapolated to the required conditions. Care should be exercised in extrapolating the data to higher temperatures or longer durations outside the experimental creep data range. Copolymer type and melt flow rate also influence the creep behaviour. Copolymer grades of PP have substantially lower creep modulus than the homopolymer grades. PP has a similar modulus to high density PE, but its resistance to creep is much better and, at a equivalent time under similar load, the creep modulus of PP is more than that of high density PE. However, the creep resistance of amorphous plastics is much better than the semi-crystalline plastics such as PP and PE. Creep resistance of PP could be further improved by addition of fillers or reinforcements. The creep behaviour of moulded artefacts is affected by the residual stress or orientation effect in the moulded article.
Figure 16a Isochronous stress/strain curves of PP at 23 C
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Figure 16b Isochronous stress/strain curves of PP at 80 C
Figure 17 Tensile creep modulus of PP as a function of time under stress (T1 = 23 C, T2 = 65 C and T3 = 110 C)
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PP shows different responses to different stresses or combination of stresses. For PP, it is reported that, up to strains of 0.8%, stress is proportional to strain measured during the creep tests. Up to this level of deformation, stress/strain behaviour under both compressive and flexural stress can be approximately calculated from the tensile creep tests. 4.3.4 Fatigue An alternative case to creep, where the deformation of the material is measured as a function of time at a constant stress, is fatigue (or stress relaxation). In this case, the material is subjected to constant strain, the relaxation in the stress in the component is measured as a function of time. This scenario occurs in press fits, springs, interference fits, screws and washers, etc., which during service undergo stress relaxation. A typical stress relaxation curve for PP is shown in Figure 18. A significant relaxation in the tensile modulus occurs over the 10 year period depicted in this graph (logarithmic scale), the value dropping from around 1,000 N/mm2 to around 350 N/mm2.
Figure 18 Tensile stress relaxation modulus for PP homopolymer at 23 C
4.3.5 Dynamic Fatigue Materials subjected to cyclic loads or stresses fail at a point far below the ultimate strength measured in short-term mechanical tests. The cyclic loads may be caused by periodic or intermittent loading in on-off situations. It is well known that the amorphous plastics are more susceptible to fatigue than semi-crystalline plastics such as PP. But it should be noted that the semi-crystalline materials also suffer from dynamic fatigue and the stress level decreases significantly as the number of cycles increases, though semicrystalline materials do not undergo the ductile to brittle transition of amorphous materials. The stress levels for cycles to failure for different plastics are compared in Figure 19. This figure clearly demonstrates that the amorphous plastics (PC and ABS)
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are seriously prone to fatigue related problems. However, most semi-crystalline plastics show a similar slope in the fatigue strength curve. A notable exception is acetal resin which shows a transition. However, it should be noted that PP is not a very stiff plastic, hence the safe stress level for PP under fatigue conditions is very low.
Figure 19 Stress levels for cycles to failure for different plastics
Fatigue data is usually published in the form of Wohler curves where stress or strain amplitude is plotted against the number of cycles to failure on a logarithmic scale. Dynamic fatigue is a complex issue. However, the following common observations can be made: Fatigue strength decreases with increasing temperature. Fatigue strength is sensitive to stress concentration such as notches or sharp corners. Fatigue strength depends on the stress frequency. The effect of fatigue at low frequencies is much more severe. In other words, at low frequencies the failure could occur earlier than that predicted using high frequency tests.
4.3.6 Mechanical Properties of Filled Grades The properties of filled or reinforced grades of PP are heavily influenced by the type and amount of the filler. For example, the density of a heavily filled grade can be up to 50% higher than the unfilled material. In the next paragraphs, the effect of fillers or reinforcing agents on the properties of PP is explained. The typical properties of filled grades of PP are given in Table 17.
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It can be seen from the table that the mechanical properties of filled grades of PP are substantially modified by the presence of filler. Depending on the type and content of filler or reinforcement, PP may even show a brittle failure at low applied strains at low testing rates. The improvement/reduction in the tensile strength of the filled grades is marginal (with the exception of 30% glass fibre reinforced PP with coupling agent) due to stress concentration effects. However, the modulus is significantly improved on addition of fillers and reinforcements, particularly for glass fibre reinforced grades with a suitable coupling agent. The impact properties of the glass fibre reinforced grades are reduced. However, reinforced copolymer grades provide good low-temperature impact properties but at the expense of rigidity. The notched impact strength of the glass fibre reinforced grades is better due to blunting of the crack propagation mechanism. Reinforced grades of PP have a distinctly higher surface hardness than the nonreinforced grades; hardness varies according to the type of reinforcing material and its proportion by weight. The reinforced materials can be used for sliding elements but the wear of other materials in contact may be very high. The crystalline melting temperature and glass transition temperature of reinforced PP is not substantially different to those of the unreinforced grades. However, substantial changes in HDT values are observed. Reinforced PP grades have reduced specific heat values since the reinforcing materials have considerably lower values than the base polymer. The coefficient of linear expansion, to a large degree, is dependent on the orientation and distribution of the reinforcing material. In general, it is lower for a reinforced material than for an unreinforced material. Shrinkage of the filled or reinforced grades of PP is dependent on the aspect ratio of the filler. Differential shrinkage, the difference between longitudinal and transverse shrinkage, is relatively low for talc or calcium carbonate filled grades in comparison to glass fibre or mica reinforced grades due to the higher aspect ratio of glass fibre and mica reinforcements. The effect of shrinkage due to molecular orientation in the partially crystalline matrix is encountered when reinforcing material is incorporated. As a result, with an increase in the proportion of spherical filler (e.g., talc or calcium carbonate), increasingly isotropic shrinkage occurs. Consequently, injection-moulded articles made from reinforced PP containing such a filler have less tendency to distort than the parts moulded from non-reinforced PP and can be manufactured with closer tolerances. On the other hand, during injection moulding, glass fibres are generally oriented in the flow direction. The glass fibres oriented in the melt bring about a very large reduction in shrinkage in the direction of orientation while a smaller reduction takes place at right angles to the direction of orientation. This difference between the shrinkage in two directions can give rise to distortion problems. Filled and reinforced grades of PP have a substantially higher creep modulus than unfilled grades. This is due to the higher initial modulus of the filled or reinforced
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grades and the reduced amount of the polymer in the material which is able to creep. The glass fibre reinforced grades offer higher creep modulus, particularly when used with proper coupling agents. The general discussion about the fatigue and creep of unmodified PP discussed in Sections 4.3.24.3.5 is also valid here. Choice of compounding method is very important to limit the effect of fibre length distribution on the mechanical properties of glass fibre reinforced PP. Since glass fibres are damaged under high shear compounding conditions and during injection moulding, knowledge of screw design and moulding conditions is essential to control the fibre attrition and reproducibility of product performance. The weld lines in the glass fibre reinforced components are particularly weak in comparison to the rest of the moulded articles since the reinforcing fibres are oriented perpendicular to the direction of flow. Thus the weld strength in reinforced artefact is similar to the unreinforced material. This is one of the major causes of weakness in reinforced articles and proper care is required in designing the gate. 4.3.7 Biaxial Orientation The second increase in deformation resistance of PP is exploited by uniaxially stretching of monofilament and polymer tapes, and uniaxial or biaxial stretching of film. The various microstructural changes occurring during stretching of PP are shown in Figure 20. The difference between the original length (or width) of a monofilament, tape or film and its length after stretching is known as the stretch ratio. After stretching, the material has considerably higher tensile strength and lower elongation at break in the stretch direction. By using suitable stretching rates and temperatures below the crystalline melting temperature, optimum stretch ratios and hence very high degrees of orientation can be obtained. Depending on the stretch ratio, tensile strength values several times higher than that of the unstretched material can be attained. Elongation at break is greatly reduced. Typical figures illustrating these effects are given in Table 18.
Table 18 Comparison of cast, monoaxially oriented and biaxially oriented PP films [16] Monoaxiall Biaxially Property Cast film y oriented oriented Tensile strengthmachine direction (MPa) 39 55 180 Tensile strengthtransverse direction (MPa) 22 280 152 Elongation at breakmachine direction (%) 425 300 80 Elongation at breaktransverse direction (%) 300 40 65 Gloss (ASTM D523) 7580 >80 >80
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Figure 20 Schematic representation of structural changes during stretching of PP
4.4 Electrical Properties PP is an excellent electrical insulator, as can be expected from a non-polar hydrocarbon. The electrical properties of PP are very similar to those of PE and are compared in Table 19.
Table 19 Electrical properties of PP and PE [1] Property PP LDPE 17 16 Volume resistivity ( cm) 10 10 Dielectric strength (MV/m) 28 27 Dielectric constant at 1 kHz 2.28 2.3 Dissipation factor at 1 kHz 0.0001 0.0003 HDPE 17 10 22 2.3 0.0005
The following terms are commonly used to describe the electrical properties of a material: Dielectric strength is a measure of dielectric breakdown resistance of a material under an applied voltage. The dielectric voltage just before breakdown is divided by the specimen thickness to give the value in kV/mm or MV/m. However, thickness should be specified since the results depend on the thickness. Volume resistivity is the electrical resistance when an electrical potential is applied between the opposite faces of a unit cube of material. It is usually measured in cm.
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Surface resistivity is a measure of the ability to resist the surface current. It is the resistance when a direct voltage is applied between two surfaces mounted electrodes of unit width and unit spacing. The value is expressed in ohms. Arc resistance is the measure of the time (in seconds) required to make an insulating surface conductive under a high voltage, low current arc. When an electric current is allowed to travel across the surface of an insulator the surface will become damaged over time and become more conductive. Dielectric constant, or relative permittivity, is defined as the ratio of the electric flux density produced in a material to the value in free space produced by the same electric field. It is a ratio, and thus dimensionless. Power and dissipation factors are the measures of the fraction of energy absorbed per cycle by the dielectric from the field. These terms arise by considering the delay between the changes in the field and the change in polarisation which in turn leads to a current in a dielectric material leading the voltage across it. The angle of the lead is known as the phase angle (). The power factor is defined as Cos and dissipation factor is Tan(90-). The loss factor is the product of dielectric constant and dissipation factor.
Typical electrical properties of a few grades of PP are given in Table 12 and are a function of temperature and frequency. In general, PP shows outstandingly high resistivity, low dielectric constant and negligible power factor, all substantially unaffected by temperature, frequency and humidity over the usual range of service conditions. The electrical properties of PP are independent of melt flow rate. However, certain additives and fillers can have an adverse effect on the electrical properties. The electrical properties of the PP are unaffected by prolonged immersion in water. Further, low values of dielectric constant can also be achieved using PP in the form of structural foam. The power factor is critically dependent on the amount of catalyst residues in the polymer. Typical electrical application of PP is in insulating power cable, particularly for telephone wires. The other functional requirements for this application are high impact strengths at low temperature and heat stabilisation for use in contact with copper. However, with the increasing use of optical fibres, the use of PP in this application is limited. The dissipation factor of PP is low and is hardly affected by temperature and frequency. The low dissipation factor rules out the use of high frequency heating and welding of PP. Hence, special techniques are required for welding of PP, discussed in Section 7.1.
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4.5 Optical Properties PP granules are naturally white and translucent. However, the final appearance of the material can be very different and ranges from hard, fairly rigid, brightly coloured, glossy, flexible or transparent film to high tenacity fibre. Mouldings made from the natural coloured homopolymer are semi-transparent, depending on the thickness and other processing and material parameters. The optical properties of a material are defined in terms of refractive index, clarity or transparency, haze and gloss. The refractive index of PP is 1.49. The remaining catalyst residue in the resin may affect the opacity of the PP resin and produce yellowness. Different catalyst systems may have different effects on the transparency and yellowness of the resin. Hence, the optical properties of equivalent grades of PP may be different. 4.5.1 Transparency Transparency may be defined as the state permitting perception of objects through or beyond the specimen. It is often assessed as that fraction of the normally incident light transmitted with a deviation of less than 0.1 degree from the primary beam direction. A material with good transparency will have high transmittance and low haze. Transmittance is the ratio of transmitted light to incident light and is complementary to reflectance. Uncoloured PP is translucent in thick sections. In thin sections or films, it can be transparent or opaque depending on the grade and the processing conditions. Homopolymers can be converted into transparent film with good optical properties. The light scattering due to formation of crystal structure should be minimised. Because of their phase structure, copolymers which have high impact strength do not in general yield transparent films. However, single phase random copolymers which suppress the formation of the crystal due to their irregular structure usually have better clarity than the homopolymers. Furthermore, it is important that the refractive index is constant throughout the sample in the line of direction between the object in view and the eye. The presence of interfaces between regions of different refractive index will cause scattering of the light rays. A high melt flow rate material should be used. Biorientation of PP film improves transparency since layering of the crystalline structures reduces the variations in refractive index across the thickness of the film, and this in turn reduces the amount of light scattering. Transparency of PP articles can be improved by using moulds or dies that provide a very good surface finish. Further improvements can be made by choosing the processing conditions which restrict the formation of spherulites, e.g., rapid cooling, low melt and mould temperature. However, low mould temperature will reduce the surface gloss of the moulding. Nucleating agents and clarifying agents which suppress the formation of spherulites can further improve the transparency of PP artefacts.
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Transparency is improved by contact with liquids to the point where the liquid level inside a container can be seen from outside (contact transparency). 4.5.2 Gloss Gloss is defined as the relative luminous reflectance factor of a specimen at the specular angle. This method has been developed to correlate the visual observations of surface shininess made at different angles. A highly polished black glass is assigned a specular gloss value of 100. Three basic angles of incidence are used for measuring gloss: 20, 60 and 85. The gloss increases as the angle of incidence increases. The gloss is a function of the reflectance and the surface finish of the material which, in turn, depends on the finish of the mould. Gloss is an extremely important factor where replacement of ABS with PP articles is considered on cost grounds. 4.5.3 Haze Sometimes a polymer may have a cloudy or milky appearance, generally known as haze. It is often measured quantitatively as the amount of light deviating by more than 2.5 degrees from the transmitted beam direction. Haze is often the result of surface imperfections. Recent developments in sheet manufacturing machinery with two cooling lines, which polish both sides of PP sheet, have resulted in low haze and high gloss sheets. 4.6 Surface Properties 4.6.1 Hardness and Scratch Resistance Although PP can be scratched with a metal point, its hardness is sufficient to resist the rule of thumb which often distinguishes between the polyolefins. LDPE is easily marred by a thumbnail, HDPE is scratched in this way with difficulty but PP is marked little, if at all. Hardness is defined as the resistance of a material to deformation, particularly permanent deformation, indentation or scratching. Hardness is purely a relative term and should not be confused with wear and abrasion resistance of plastics. For example, polystyrene has a high hardness but a poor abrasion resistance. Many tests have been devised to measure hardness. However, Rockwell and Durometer hardness tests are commonly used. The Rockwell hardness test measures the net increase in depth impression as the load on an indentor is increased from a fixed minor load to a major load and then returned to a minor load. The hardness numbers derived are just numbers without units. Rockwell hardness numbers in increasing order of hardness are R, L, M, E and K scales. The higher the number in each scale, the harder is the material. The Durometer hardness test is based on the penetration of a specified indentor forced into
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the material under specified conditions. Two types of durometers are commonly used: Type A for softer materials and Type D for relatively harder materials. The hardness values of different PP grades are compared in Table 12. Furthermore, the indentation hardness of PP decreases with the temperature (Figure 21). The hardness of PP depends on its crystallinity. With decreasing molar mass, crystallinity decreases and so does the hardness.
Figure 21 Ball indentation hardness of PP as a function of temperature (C)
4.6.2 Abrasion Resistance Resistance to abrasion is defined as the ability of a material to withstand mechanical action that tends to progressively remove material from its surface. Abrasion resistance of polymeric materials is a complex subject. The resistance to abrasion is closely related to other factors such as hardness, resiliency and the type and amount of added fillers and additives. Resistance to abrasion depends on factors such as test conditions, type of abradant and development and dissipation of heat during the test cycle. This all makes abrasion a difficult mechanical property to define as well as to measure adequately. A materials ability to resist abrasion is most often measured by its loss in weight when abraded with an abrader. The Taber abrader is widely used to measure abrasion resistance. In the Taber abrasion test, the test specimen is placed on a revolving turntable with a suitable abrading wheel under a set certain dead weight. The weight loss after a large number of revolutions (at least 5000 revolutions) is measured. For softer materials, less abrasive wheels with a smaller load on the wheels may be used.
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Wear may be high when reinforced parts are in contact with unreinforced parts. This situation could lead to excessive wear of unreinforced parts. Use of lubricated reinforced grades may reduce wear when in contact with the unreinforced component. China clay additives may be used to improve scratch and mar resistance of PP. Scratch resistance is quite important for car body panels. Recently, development of highcrystallinity copolymer grades has occurred in response to the automotive sector requirement for low-cost, low-weight materials for interior trim that do not show evidence of scratching [17]. These grades are around 15% lighter than ABS, with higher stress crack resistance and the same toughness. Highly crystalline PP copolymers have similar scratch resistance to talc filled PP but, because they do not contain white filler, they do not show the evidence of scratch. However, disadvantages of the high-crystallinity copolymers are 30% less stiffness in comparison to talc filled counterpart and higher gloss, which is not preferred by the automotive manufacturers, greater shrinkage and less acoustic damping. 4.6.3 Friction PP has a friction coefficient between 0.25 to 0.45, higher than the friction coefficient for typical bearing materials (from 0.10 to 0.25). However, the friction performance of PP can be improved by addition of silicone oil and/or polytetrafluoroethylene (PTFE) additives. PTFE-modified grades of PP with very low dynamic and static friction coefficients are available from resin compounders. The poor mechanical properties of PP, particularly low shear yield strength, also contribute to its near zero use in sliding applications. One reported sliding application of PP is in a conveyor belt guide bar for the beverage industry. Friction characteristics are very important for fibre to fibre interaction in spin technology. Internal lubricants can be used to reduce the friction which can be quite important in slide applications such as medical syringes. 4.7 Acoustic Properties PP offers excellent acoustic damping properties with considerable rigidity at normal service temperatures. Articles made from PS, ABS or HDPE have their own resonance and tend to rattle. On the other hand, components made from PP are more or less acoustically dead because acoustic vibrations are heavily damped in this plastic. The DMTA or torsional pendulum curves (Figure 8) provide primary data about the acoustic properties of the material. A good loss factor with sufficient rigidity is required to achieve damping of vibrations. It is primarily the components own vibrations which are heavily damped, e.g., eigen tones or natural vibration frequencies of the housing. However, PP does not have good air-borne sound absorption because of its rigidity. To achieve effective sound insulation, additional measures are required such as suitable cladding or spring mounting of the noise source.
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4.8 Biological Behaviour 4.8.1 Assessment Under Food and Water Legislation PP is generally accepted as a non-toxic and non-carcinogenic material. PP homopolymers and copolymers are used in many food contact applications ranging from simple beverage closures to retortable pouch applications. The main requirements for contact with food are that the article must not impart odour or taste to the food and should be suitable for the intended application. The main reason for assessment of PP for contact with food or potable water comes from the use of additives in material formulation. Additives, monomers, catalyst residues, polymer degradation products, etc., can migrate to any food in contact if the concentration of these substances is lower in the food than in the plastic. The migration of these species is a function of time and temperature. The rate of migration of chemicals or additives is inversely proportional to the molecular weight of the PP. The migration of these species could produce toxicity or the formation of undesirable flavours or odours, commonly known as organoleptic problems. The application of PP in contact with food and water is covered by the relevant standards/regulations by different authorities in different countries. Health assessment of plastics under food legislation varies from one country to another. In USA, clearance from the Food and Drug Authority (FDA) is required while relevant European directives form the basis of suitability of resin for food contact applications. Normally, the migration/extraction of resins and additives is measured for contact with different food simulants, e.g., distilled water, vegetable oil or acetic acid. Although similar principles apply, it is advisable to check in each case with the raw material manufacturers. Many grades are available which have the material composition meeting the requirements of the various regulatory authorities. Provided the approved grades are used and compliance with relevant regulations is checked, there should not be any problem in using PP for food and water contact applications. However, the finished part must also meet the requirements of the relevant regulations. The degradation of material during processing, use of mould release agents, etc., can make the final product non compliant. 4.8.2 Resistance to Microorganisms PP is not a nutrient medium for microorganisms and is therefore not attacked by them. It cannot be penetrated by microorganisms provided the wall or film thickness is at least 0.1 m. In thinner walls, small pores may be introduced during manufacture. Low molecular weight additives, such as plasticisers, lubricants, stablisers and antioxidants, may migrate to the surface of plastic components and encourage the growth of microorganisms. The detrimental effects can be readily seen through the loss of properties, change in aesthetic quality, loss of optical transmission and increase in brittleness. Preservatives, also known as fungicides or biocides, are added to plastic materials to prevent the growth of microorganisms.
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4.8.3 Physiological Compatibility Toxicology tests in acute and chronic animal feed trials have shown no damage attributable to the PP that could be detected in the organs of animals, even after a two year trial. Skin and mucous membrane compatibility tests have shown no signs of irritation. New medical devices must undergo thorough biocompatibility testing by the manufacturer in order to meet regulatory requirements. Biocompatibility tests are designed to determine the risk of adverse health affects from the use/abuse of the component. Toxicity of a material device depends on the toxicity of the added ingredients and their migration into the body. Potential toxic substances include plastic additives (e.g., antioxidants, stabilisers, plasticisers), substances added during manufacturing (e.g., lubricants, mould release agents, cleaning agents) and products from polymer degradation during storage or implantation. ISO 10993Biological Evaluation of Medical Devices outlines the methods for evaluating the safety of medical devices, directly or indirectly in contact with the body or with bodily fluids. The extent of the testing depends on the duration of contact, the nature of contact with the body (externally or internally) and the body part in contact (e.g., skin, mucous membrane, breached or compromised surfaces, blood, tissue or bone, etc.). Most of the grades of PP approved for food contact applications are normally suitable to produce articles for pharmaceuticals and medicines. However, relevant manufacturers standards should always be checked. Parts correctly manufactured from PP can meet the requirements specified by the relevant controlling bodies for pharmaceutical packing and medical articles. Once again, the suitability of the article for the intended application should be checked rather than the starting raw material. 4.9 Additives 4.9.1 Antistatic Agents Owing to its high electrical resistance, PP tends to accumulate electrostatic charge, in common with other polymers. This is a disadvantage because dust can form on articles in a rather unattractive pattern. Furthermore, the possibility of sparks presents a hazard in application where explosive fumes may be present. Antistatic agents are added, either directly or in masterbatch form, to PP to overcome this problem. During processing, traces of antistatic agent migrate to the surface of the moulding and form a moisture absorbent, weakly conductive layer. This reduces the surface resistance, thus allowing the faster dissipation of accumulated electrostatic charges. For useful antistatic properties, the surface resistivity need to be in the range of 109 to 1014 /m2. The optimum antistatic effect is generally obtained after a storage period of about two or three weeks. In many cases, the optimum effect is attained only after a few days, but under arid conditions it is reached very much later and is diminished. The antistatic
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effect persists for a considerable time and articles made from this plastic can be washed in water without any marked decrease in antistatic activity. Grades with low crystallinity (e.g., random copolymers) allow faster migration of antistatic agents to surface, thereby, achieving the optimum performance quickly. The incorporation of an antistatic agent has little or no effect on the mechanical, chemical or thermal properties of PP and no effect at all on the processing conditions. However, the presence of antistatic agents may affect the transparency and printability and may make PP non compliant to FDA regulations, although FDA approved antistatic agents are available. With the inherent hygroscopic nature of antistatic agents, it is advisable to pre-dry the granules before processing. Antistatic agents can be ionic or non ionic in nature. Glyceryl monostearate, a non ionic antistatic agent, is commonly used in injection moulding of PP up to a loading of 1% or more. The exact amount of the antistatic agent added depends on other property requirements such as transparency, FDA approval, printability and its compatibility to the polymer. Artefacts can be coated with suitable antistatic agents also. To a lesser degree, lubricants can also act as an antistatic agent and vice versa by reducing the friction. Typical applications where antistatic properties are required are household items, housings for electrical and electronic appliances, parts which undergo friction or sliding, etc. 4.9.2 Electromagnetic Interference/Radio Frequency Interference Shielding There might be few occasions when a reduction in the dielectric properties of PP might be desirable, e.g., antistatic properties. However, for certain applications, the reduction in surface resistivity achieved by addition of antistatic agents may not be sufficient. The two cases where greater reduction might be required are to achieve electrostatic dissipation (ESD) where a PP component is in contact with semi-conductor devices or is used in a hazardous environment, or to shield the component against electromagnetic interference (EMI) or radio frequency interference (RFI). Many electronic and electrical devices such as computers, mobile phones, etc., emit signals which may interfere with communications. Regulations now require that the plastic enclosures used to house these devices should eliminate or attenuate these signals.
The high dielectric strength, low dielectric constant and dissipation factor of PP make it a bad choice of material for EMI/RFI shielding. In these cases, carbon black can be added to provide increased electrical conductivity. This might be sufficient in many cases. However, secondary shielding methods, such as metal deposition using metallising or electroplating, or adding metal fillers or nickel coated graphite fibres might be required to achieve sufficient protection from EMI/RFI.
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4.9.3 Slip and Antiblocking Agents During the use of PP films and laminates, the line speeds and reliability of the packaging machine are very important. To decrease the friction of the film on the processing and conversion equipment, a lubricating agent known as a slip agent is added. Slip agents migrate to the surface and reduce the coefficient of friction. Once on the surface, slip agents are able to lubricate the machine allowing for the faster line speeds. Primary amides, secondary amides and ethylenebisamides are commonly used as the slip agents. Reduction in the coefficient of friction and thermal stability of the slip agents are important issues. Slip agents should not interfere with corona treatment or printing and it should not have a deleterious effect on the clarity of clear films. Slip agents should meet FDA or equivalent approval for the recommended application. Another important property in the manufacture of films is blocking. Blocking is a term describing the polymer film sticking to itself as a result of storage in roll form. Antiblocking agents are added to overcome this problem. Typical antiblocking agents are silica, talc or diatomaceous earth. These materials are inorganic, are not miscible with the polymer and migrate to the surface. They create microscopic roughness on an otherwise smooth film surface. Addition of just the right amount and good dispersion are the critical factors. 4.9.4 Metal Deactivators and Acid Scavengers As with most polyolefins and polydiene, the presence of metals has a strong adverse effect on PP and most antioxidants are relatively ineffective. Copper and cuprous alloys produce the greatest effects, but other metals such as iron and nickel also accelerate degradation. Metal deactivators are widely used to deactivate metal residues present in the formulation due to catalyst residues, impurities in additives, direct contact with copper in wire and cable applications and metal inserts. Metal deactivators work by chelation of the metal. Metal deactivators are organic molecules containing heteroatoms or functional groups such as hydroxyl or carboxyl groups. Good results may be achieved by the use of 1% of a 50:50 blend of phenol alkane and dilauryl thiodiproprionate instead of the 0.10.2% of antioxidants commonly used in PP. Acid scavengers (or antacids) are used in PP to neutralise acidic catalyst residues. Calcium or zinc stearate are commonly used, and also function as internal lubricant. Inserts should, therefore, be made of light metal or be nickel or chromium plated. No adverse effect with brass screw fittings has been detected at temperatures below 100 C. 4.9.5 Blowing Agents Through the addition of suitable chemical blowing agents to PP, fine-celled foams with apparent density down to 0.6 g/cm3 can be produced by conventional extrusion or injection moulding. Injection-moulded foamed articles produce a very fine-celled
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structure creating a smooth surface finish. The blowing agent concentrates are generally added in amounts of 1% to 3%. High melt flow rate grades of PP are preferred. Extruded, foamed PP film and tape can be stretched and thermoformed for trays for meat applications, cups for drinks, tape yarns for carpet backing. Within the specified loading limits for blowing agent, the approval of PP for food applications is not compromised. 4.9.6 Nucleating Agents The use of nucleating agents can further modify the crystallinity and crystal structure of PP by providing numerous sites for growth of small spherulites during cooling of the melt. This results in less scattering of light. This technique is used in injection moulding to improve clarity and rigidity [18]. As seen in polarised light photomicrographs, PP containing nucleating agents has crystallites of much finer and more uniform size relative to unclarified PP. As the crystallites in the clarifier containing grades are generally smaller than the wavelength of visible light, scattering is reduced and clarity is greatly improved. As nucleating agents are generally organic in nature, they melt during normal processing and thus become completely and evenly distributed in the resin. Furthermore, many organic compounds and metal salts can act as nucleating agents, including pigments and residual monomer. The use of dimethyl benzylidene sorbitol, dibenzylidene sorbitol and sodium di 4-t-butylphenol phosphate has been reported. These additives are also used in resins to provide reduced manufacturing cost through increased productivity and reduced set up cost. 4.9.7 Antifogging Agents Fogging occurs when water droplets formed from exposure of the moisture in foods to low storage temperatures condense on the inside surfaces of packaging films. Use of polyglycerol ester or a sorbitan ester of a fatty acid has been reported for antifogging applications in refrigerator packaging. Slip agents can also, to a certain degree, act as antifogging agents. 4.9.8 Biocides Biocides in PP are not as common as in plasticised PVC. In traditional PP applications, the need for a biocide to control the growth of microorganisms is virtually non-existent. Some trash cans and other waste disposal containers make use of these components to inhibit bacterial growth. The improvement is both aesthetic and sanitary. The product is able to resist the formation of unpleasant and unsightly organisms.
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4.9.9 Flame Retardants PP is basically flammable and ignites at a temperature of about 600 C, although its burning rate is slow. PP ignites in contact with flame and burns with a faintly luminous flame. It continues to burn when the ignition source is removed and melts with burning drips. The spontaneous burning temperature of PP is 360 C and the temperature at which ignition is induced from an external source is 345 C. Combustion of unfilled PP produces no environmentally relevant pollutants. The burning produces very little soot, unlike PS or styrene-acrylonitrile copolymer (SAN), and no char, unlike oxygencontaining polymers such as polyphenylene ether (PPE) or PC. Polymers with superior fire resistance are thermosetting resins, fluorinated plastics and other plastics containing sulphur such as polyether sulphone and polyphenylene sulphide. The flammability of the polymers is commonly measured using Underwriters Laboratories, Inc., (UL) specifications. The UL 94 standard covers classification of a materials tendency to ignite in the presence of a flame and to continue to burn after the ignition source is removed. There are three distinct flame tests in UL 94 which are most often applied to a PP product: horizontal burn (94HB), vertical burn (94VB) and 125 mm vertical burn (94-5VA, 94-5VB). Recognition under 94HB does not imply any selfextinguishing character of the resin. However, the 94VB specification measures the self-extinguishing character of burning and V-0 is the most stringent specification. Flame retardants are added to reduce the flammability of PP. PP is one of the most difficult plastics to make flame retardant. A high level of flame retardant is required to achieve necessary protection against fire required by the application, a level which will impair the mechanical performance of the material. The unmodified PP grades generally have a 94HB rating up to 0.8 mm thickness. Suitably flame retarded grades with V-0 rating at 3.2 mm thickness are available from compounders. Flame retardants can reduce the processibility and interfere with the function of certain hindered amines as light stabilisers. Flame retardant grades of PP are generally not suitable for use in food contact applications. The integral hinge properties of flame retarded PP are greatly reduced. Flame retardants include halogens (bromine and chlorine), aluminium trihydrate, magnesium hydroxide, phosphates and antimony oxide. Each of these flame retardants has its own strengths and weaknesses when flame retarding PP products as well as on its effect on the stability of the resin. Brominated compounds commonly used for flame retardation of PP are decabromodiphenyl oxide and octabromodiphenyl oxide. Antimony oxide is generally added to halogenated flame retardants for a synergistic effect. The halogenated flame retardants act as free radical scavengers. Halogenated flame retardants have many problems. They are known to interfere with hindered amine light stabilisers due to the production of halogenated acids which could react with hindered amines, to cause the corrosion of the processing machinery, to produce toxic decomposition products such as brominated dioxins and furans. Magnesium and aluminium hydroxides dissociate in the presence of heat to form water and metal oxides. Water dilutes the combustion gases and takes away the heat from burning
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plastics. Aluminium oxide or magnesium oxide form an insulating char layer on the burning plastic. Use of magnesium hydroxide requires careful processing conditions since it dissociates at the processing temperature of PP. The limiting oxygen index (LOI) test is used to measure the minimum concentration of oxygen necessary for candle-like burning for 3 minutes or more. A higher LOI indicates that more oxygen is needed to support combustion. The presence of flame retardants increases the LOI. Unmodified PP has a LOI of 17. The key fire properties of some plastics are compared with PP in Table 20. Suitable flame retarded grades of PP can have a LOI of 28.
Polymer PE PP PS UPVC CPVC ABS PC PPO/PS PA Table 20 Fire performance of different plastics Flammability Limiting oxygen index HB 17 HB 17 HB 18 V-0 45 V-0 50 HB 19 V2 25 HB 20 HB 22
4.10 Performance in Service 4.10.1 Thermal or Heat Stability Owing to the high susceptibility to oxidation due to the pendant methyl group, unstabilised PP can begin to decompose at high temperatures. Unstabilised PP oxidises in the presence of air and the rate of oxidation increases with increased temperature. Oxidation leads to embrittlement, surface cracking, discolouration and loss of mechanical properties and clarity. High temperatures are encountered during melt processing or service. This degradation process is accelerated by contact with certain metals. All commercial grades of PP are incorporated with stabilisers which give protection against oxidation during processing. Stabilisers also provide protection during normal service conditions. It is, therefore, essential to determine the likely enduse conditions before the choice of the grade and stabilisation system is made. The mechanism of thermal oxidation in PP is through the formation of free radicals which react with environmental oxygen to produce peroxides. It could also occur due to radiation, light or the presence of metal residues. Primary antioxidants inhibit the oxidation reaction by combining with free radicals. Hindered phenolics (e.g., butylated hydroxytoluene (BHT)) are commonly used as primary antioxidants. BHT is FDA approved for many applications but suffers from high-temperature volatility. Furthermore, phenolics suffer from oxidation in the presence of metal residues left from catalysts and produce a yellow colour. Different residues or different amounts of
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residue can produce different extents of yellowness. High molecular weight phenolics are used for high-temperature processing or high-temperature service conditions. Secondary antioxidants, also called peroxide decomposers, inhibit oxidation of PP by decomposing hydroperoxides. Phosphites and thioesters are commonly used as secondary antioxidants. Secondary antioxidants are usually combined with primary antioxidants to produce a synergistic effect on oxidation. With proper selection of two antioxidants, it is possible to achieve protection against oxidation which is greater than the sum of protection given by the two antioxidants when working separately. Stabilisation with antioxidants may render PP unsuitable for food contact application as they may directly migrate into the food products, hydrolysing and imparting odour or taste to the food. Careful selection of a suitable stabiliser system is necessary for food contact applications. In addition, heat stabilisers could adversely affect the working of light stabilisers. In applications involving no undue mechanical stresses, PP articles will withstand 100 C for a long period of time, depending on the stabiliser systems. Consequently, the heat and thermal stability of PP is closely related to its maximum continuous use temperature (Section 4.2.2). Short-term exposure to 140 C is also possible. It has been observed that a properly heat stabilised and properly processed material can undergo up to five processing cycles without noticeable reduction in molecular weight or the level of antioxidant content. 4.10.2 Stability to Light and Ultraviolet Rays Most plastics are affected by ultraviolet (UV) light in the presence of air. PP is no exception and, when unstabilised, it very rapidly becomes brittle when exposed to sunlight. Degradation is accompanied by marked deterioration in mechanical properties. Mouldings generally lose gloss after short exposure; the surface and the material immediately beneath suffers the most. The appearance of chalky powder at the surface of the heavily degraded PP article has also been reported. The amount of the degradation depends on the duration of the exposure and whether the article is used behind glass. However, the screening effect of the glass may not be sufficient to prevent degradation if the stabilisation system is inadequate for the application. Like most plastics, PP exhibits little or no change under short-term exposure to radiation in the visible light range. Prolonged exposure to direct sunlight can, however, cause a deterioration in properties due mainly to UV radiation. UV absorbers are added to provide protection against harmful UV radiation. The UV absorbers absorb UV light and release the excess energy as heat. Commonly used UV absorbers for PP are derivatives of benzophenone, benzotriazoles and esters. The use of hindered amines has also been reported. The efficiency of the UV absorbers to protect the part depends on the part thickness. Stabilisation in thick parts is more effective than the thin parts, films or sheets.
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Carbon black in a suitable concentration can make the article sufficiently protected for 10 years continuous outdoor exposure in temperate climates. The use of carbon black is clearly restricted in fibres and films. In addition, the heat stability of the carbon black modified grades may be poor in comparison to unmodified grades. Hindered amine light stabilisers function as free radical scavengers and can double as thermal antioxidants. They are, though costly, effective at very low concentrations. Hindered amines can interact with other additives (e.g., phenolic antioxidants, titanium dioxide) in the PP to produce yellowishness. Halogenated flame retardants can react with hindered amine light stabilisers and render them ineffective. The protection of PP against UV radiation and heat is a very complex issue. The idea of this section is not to go in depth into formulation issues which are best left for resin manufacturers/formulator or stabiliser suppliers. However, from the above discussion, it can be appreciated that: The heat stabiliser and light stabiliser can interact with each other as well as other additives present in the PP formulation. The mechanical properties of the modified PP will depend on the amount of stabilisers. The addition of stabilisers may make material unsuitable for food applications by leaching and migration.
The reduction in the molecular weight of the PP on exposure to harmful UV radiation can be easily seen using gel permeation chromatography (Figure 22). It can be seen from the figure that the reduction in molecular weight is more severe at the part surface.
Molecular weight distribution
Figure 22 Gel permeation chromatogram showing the degradation of polymer caused by UV exposure
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Light stabilised grades have very good light, UV radiation and weathering resistance in both natural and colour formulations. These grades are supplied with different degrees of stabilisation to match the various application requirements. It should be noted that many additives and pigments can seriously impair the effectiveness of the stabiliser system. Hence a balance of stabilisation system, pigments and homogeneous distribution of additives is necessary to achieve optimum resistance to light, UV radiation and weathering. Light stabilised grades are generally unsuitable for food contact applications. However, formulations can be developed based on requirements. Compatibility of the light stabilisers is very important since they are added in significant quantities. Blooming and the migration of low molecular weight light stabilisers are important issues. The most accurate method to test the suitability of the material is the use of material in its intended environment for a long period of time. Due to the long-term nature of outdoor weathering, accelerated testing using weatherometers is common. Different light sources are used, such as xenon arc lamp, carbon arc lamp and fluorescent sun lamp. Filtered xenon most accurately reproduces the spectral energy distribution of sunlight. However, the results from accelerated testing may be different from the longterm outdoor testing. HDPE offers inherently better oxidation and UV resistance in comparison to PP. Whilst these properties may be greatly improved in PP by the use of additives, these may increase the cost of PP compounds to beyond that which is considered economically attractive. It is for this reason that HDPE has retained a substantial part of the crate market. Nevertheless, PP blow mouldings have been commercially used in horticultural sprayers and motor car parts. 4.10.3 Chemical Resistance As a non polar, high molecular weight paraffinic hydrocarbon, PP has outstanding chemical resistance, the best of all thermoplastics to organic chemicals. Indeed, there is no solvent for PP at room temperature, although it may swell in some cases. Since PP contains only hydrogen and carbon and does not contain polar atoms, non polar molecules (such as hydrocarbons and chlorinated solvents) are more easily absorbed by PP than polar molecules (such as soaps, wetting agents and alcohols), causing swelling, softening or surface crazing. PP is extremely resistant to inorganic environments. It is not affected by aqueous solutions of inorganic salts, nor by most mineral acids and bases, even when concentrated. It is, however, susceptible to attack by oxidising agents such as chlorosulphuric acid, pure fuming nitric and sulphuric acids, and the halogens. It must be remembered that stabilisers and other additives can be attacked by aggressive chemicals to which PP is resistant. This might affect the stability and properties of the material.
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Generally speaking, higher temperatures can considerably impair resistance depending on the chemical environment. Up to 60 C, PP is resistant to many solvents but aromatic and halogenated hydrocarbons, certain fats, oils and waxes cause swelling. At temperatures up to 30 C, the effect is only slight. The higher the degree of crystallinity in a PP material, the greater its chemical resistance. Consequently, homopolymers of PP have more chemical resistance than the random copolymer. Environmental stress cracking (ESC) is the surface initiated brittle fracture of a polymer under stress in contact with a medium in the absence of which fracture does not occur under the same conditions of stress. Combinations of external and/or internal stresses may be involved, and the sensitising medium may be gaseous, liquid or solid. A stress raiser or notch, an external and/or internal residual stress and a stress cracking medium must be present for ESC to occur. For example, PE products prematurely fail in the presence of detergents and other active environments. PP is widely used for packaging, fluid containment and transportation. However, PP is virtually free from environmental stress cracking observed in other polymers and attempts in the laboratory to identify a pure ESC agent for PP have failed. Many plastics are inclined to environmental stress cracking or embrittlement on prolonged contact with boiling detergent solutions. The PP components specially made for washing machines do not exhibit these disadvantages. A reflux test involving 1000 hours in boiling detergent solution is used to measure water absorption, embrittling and change of the dimensions. It has been reported that suitable grades show 0.5% higher water absorption than the normal grades when soaked in detergent solution. Furthermore, no embrittlement is observed and the yield stress, ultimate tensile strength, dimensions, surface hardness, rigidity and toughness of PP are not changed. 4.10.4 Permeability 4.10.4.1 Permeability of Water and Liquids PP is virtually impermeable to water and water-based products. It does not, therefore, swell when immersed in water. The water vapour permeability of PP film is compared with other plastics in Table 21. Changes in relative humidity have no effect on the properties of the material. The very slight water uptake can be determined when there is a change of temperature in a hot damp atmosphere. It is due entirely to surface adsorption. Fillers, reinforcements and additives may slightly increase the uptake of water. It is advisable to dry the material immediately before processing or to degas it during plasticisation. This particularly applies to carbon black pigmented PP. However, there is appreciable adsorption and permeation with certain organic solvents (especially if non-polar). The degree of permeation increases with temperature.
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Practical Guide to Polypropylene Table 21 Water vapour permeability of various plastics relative to the permeability of oriented PP 2 Polymer Water vapour (g/m 24 h) Oriented PP film 1.0 Cast PP film 2.0 HDPE 1.0 PVDC 0.10 LDPE 5.0 Rigid PVC 10.0 Plasticised PVC 3070 EVA 12.0 PA 11 20 PA 6 100 Oriented PS 40 Cellulose acetate 400 Cellophane P 1000
4.10.4.2 Permeability of Gases The permeation rate of PP with different gases is compared to other polymers in Table 22. It can be seen that the resistance to permeability of gases improves with orientation. In addition, PP offers good resistant to permeability of gases which is comparable to HDPE but significantly better than LDPE. In PP packaging for solvent containing substances or strong smelling products, migration of solvent must be expected and, as a result, loss of weight in the contents during prolonged storage. Most of the flexible packaging materials require stiffness, good printability, high gloss and good barrier properties. Oriented PP is coextruded with polyvinylidene fluoride (PVDF) to achieve suitable product requirements where excellent barrier properties are required. 4.10.5 Sterilisation 4.10.5.1 Autoclave and Ethylene Oxide Sterilisation Devices may be sterilised by one of three main techniques: autoclave, ethylene oxide or radiation treatment. Steam autoclaving is generally carried out at temperatures of 120 135 C. Being resistant to high temperatures and water, PP is one of the obvious choices. It is entirely unaffected by the autoclaving as long as the treatment temperature is kept below its softening temperature. Random polymers have lower softening temperature than the homopolymer and block copolymers and, hence, are not preferred for steam autoclaving. Use of ethylene oxide sterilisation is now on the decline due to the mutagenic nature of the material. PP is generally unaffected by ethylene oxide treatment.
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Practical Guide to Polypropylene Table 22 Permeability to gases of various plastics Polymer N2 O2 H2O CO2 Oriented PP film 7.0 35 140 175 Cast PP film 18 90 360 450 HDPE 15 75 300 375 Polyvinylidene 0.06 0.3 1.2 1.5 chloride (PVDC) LDPE 50 250 1000 1250 Rigid PVC 1 5 20 25 Plasticised PVC 5200 251000 1004000 1255000 Ethylene vinyl 80 400 1600 2000 acetate copolymer PA 11 3.0 15 60 75 PA 6 0.5 2.5 10 12.5 Oriented PS 20 100 400 500 Cellulose acetate 25 125 500 625 Cellophane P 10 50 200 250
SO2 280 720 600 2.4 2000 40 2008000 3200 120 20 800 1000 400
Medical sterilisation at temperatures above 100 C demands two opposing requirements from the polymer. The polymer should have high crystallinity to provide good tensile strength retention and heat resistance while low crystallinity is required to improve the transparency. PE plastomers based on metallocene technology have been blended with PP to achieve the optimum properties for syringe applications. The random copolymers have lower resistance to autoclave sterilisation due to their lower heat distortion temperature. Parts which are significantly stressed can deform during autoclave treatment. The stresses in a syringe may arise from pressure, vacuum, weight of the liquid or due to pressure exerted on syringe. 4.10.5.2 Radiation Sterilisation Radiation sterilisation is most damaging to PP. When PP is subjected to high energy ionising radiation, deterioration in its physical properties and changes in its molecular structure occur detectable by infrared (IR) spectroscopy. PP that will be radiation sterilised requires unique stabilisation packages. Since radiation sterilisation causes increased oxidation of the polymer, additive levels are also increased. Sterilisation of disposable articles is generally carried out with a radiation dose of about 25 kJ/kg or 2.5 Mrad. Although toughness suffers to some extent and shade changes are possible, articles properly made from PP still retain their serviceability. Suitable trials should be conducted to properly assess the effect of radiation. Thick-walled parts are less affected than thin-walled components. PP copolymers have markedly better resistance to high energy radiation than homopolymers, due to lower crystallinity and greater free volume. Flex to failure test is used for evaluating the radiation tolerance of PP. Main areas of application include syringes, needle shields, surgical trays and blow moulded containers. El Paso Products Co., Nested Chemicals International and Exxon Chemicals have reported development of suitable grades of gamma radiation sterilisable PP to
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satisfy the requirements for blow moulded containers and injection moulded articles [19, 20]. PE has considerable better radiation resistance than PP due to the absence of the tertiary carbon atom which initiates degradation of the material and loss of the mechanical properties. Irradiated PP has been used as a plant wrapping which gradually degrades in the soil. These wrappings are suitable for both manual and machine planting of forests and fields. PP can encounter radiation from various sources when used in the nuclear industry. Gamma radiation, used for medical sterilisation, is far more penetrating than beta, electron radiation or alpha radiation. The radiation dosage level harmful for PP is quite low. Hence, use of PP in the nuclear industry where high radiation occurs is not possible. Suitable resins for use in nuclear industry include phenolics, polystyrene, polyester, particular epoxies, silicone, etc.
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Polypropylene Practical Guide

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Polypropylene Practical Guide

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Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Figure 8 A typical DMTA trace of PP showing different transition temperatures

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Figure 9 Flexural modulus of different plastics as a function of temperature [2]

Practical Guide to Polypropylene

Value 1.68 2.10 0.22 -5 10 x 10 -5 15 x 10 -5 21 x 10

Practical Guide to Polypropylene

Figure 10 Specific heat of PP as a function of temperature

Practical Guide to Polypropylene

Figure 11 A schematic tensile stress/strain curve for PP 32

Practical Guide to Polypropylene

Figure 12 Tensile stress/strain curves for different types of PP

Practical Guide to Polypropylene

Figure 13 Flexural modulus of different grades of PP as a function of temperature [2]

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Figure 15 Typical notched impact strength of PP as a function of temperature

Practical Guide to Polypropylene

Figure 16a Isochronous stress/strain curves of PP at 23 C

Practical Guide to Polypropylene

Figure 16b Isochronous stress/strain curves of PP at 80 C

Practical Guide to Polypropylene

Figure 18 Tensile stress relaxation modulus for PP homopolymer at 23 C

Practical Guide to Polypropylene

Figure 19 Stress levels for cycles to failure for different plastics

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Figure 20 Schematic representation of structural changes during stretching of PP

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Figure 21 Ball indentation hardness of PP as a function of temperature (C)

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

Practical Guide to Polypropylene

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