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Practical Guide to
Polypropylene
Devesh Tripathi
Practical Guide to
Polypropylene
By
Devesh Tripathi
ISBN: 1-85957-282-0
All rights reserved. Except as permitted under current legislation no part of this
publication may be reproduced, stored in a retrieval system, or transmitted in any form
or by any means—electronic, mechanical, photocopying, recording or otherwise—
without prior permission from the copyright holder.
1 Introduction................................................................................................................. 1
1.1 Background ............................................................................................................ 1
1.2 Major Advantages .................................................................................................. 2
1.3 Major Disadvantages.............................................................................................. 3
1.4 Competitive Materials............................................................................................ 3
1.5 Applications ........................................................................................................... 5
1.6 Market Share and Consumption Trend .................................................................. 6
1.7 Major Suppliers...................................................................................................... 7
1.8 Material Price......................................................................................................... 8
2 Basic Types of PP ........................................................................................................ 9
2.1 Homopolymer ........................................................................................................ 9
2.2 Copolymer.............................................................................................................. 9
2.2.1 Random Copolymer ...................................................................................... 10
2.2.2 Block Copolymer .......................................................................................... 10
2.3 Elastomer-Modified Polypropylene..................................................................... 11
2.4 Controlled Rheology ............................................................................................ 11
2.5 Metallocene Polymers.......................................................................................... 12
2.6 Syndiotactic and Atactic PP................................................................................. 13
2.7 Filled Grades of PP .............................................................................................. 13
2.7.1 Talc Filled PP................................................................................................ 14
2.7.2 Calcium Carbonate Filled PP ........................................................................ 14
2.7.3 Glass Fibre Reinforced PP ............................................................................ 14
2.7.4 Mica Reinforced PP ...................................................................................... 15
2.8 Additives for PP................................................................................................... 15
2.9 Identification of PP Type ..................................................................................... 16
3 Structure .................................................................................................................... 19
3.1 Molecular Weight ................................................................................................ 19
3.2 Molecular Weight Distribution ............................................................................ 20
3.3 Crystallinity.......................................................................................................... 20
3.4 Orientation ........................................................................................................... 22
3.5 Isotacticity............................................................................................................ 22
4 Properties................................................................................................................... 24
4.1 Density ................................................................................................................. 24
4.2 Thermal Properties............................................................................................... 24
4.2.1 Glass Transition Temperature and Melting Point ......................................... 24
4.2.2 Maximum Continuous Use Temperature ...................................................... 27
4.2.3 Heat Deflection Temperatures and Softening Points .................................... 28
4.2.4 Brittle Temperature ....................................................................................... 29
4.2.5 Specific Heat ................................................................................................. 30
4.2.6 Thermal Conductivity ................................................................................... 31
4.2.7 Thermal Expansion ....................................................................................... 31
4.3 Mechanical Properties ..........................................................................................32
4.3.1 Short-term Mechanical Properties.................................................................32
4.3.1.1 The Effect of Test Speed .........................................................................33
4.3.1.2 The Effect of Temperature......................................................................33
4.3.1.3 Time-temperature Superposition............................................................34
4.3.2 Impact Strength .............................................................................................34
4.3.2.1 Falling Dart Impact Test........................................................................35
4.3.2.2 Notched Impact Strength........................................................................35
4.3.2.3 Tensile-impact Strength..........................................................................36
4.3.3 Creep .............................................................................................................36
4.3.4 Fatigue...........................................................................................................39
4.3.5 Dynamic Fatigue ...........................................................................................39
4.3.6 Mechanical Properties of Filled Grades ........................................................40
4.3.7 Biaxial Orientation ........................................................................................43
4.4 Electrical Properties .............................................................................................44
4.5 Optical Properties.................................................................................................46
4.5.1 Transparency .................................................................................................46
4.5.2 Gloss..............................................................................................................47
4.5.3 Haze...............................................................................................................47
4.6 Surface Properties ................................................................................................47
4.6.1 Hardness and Scratch Resistance ..................................................................47
4.6.2 Abrasion Resistance ......................................................................................48
4.6.3 Friction ..........................................................................................................49
4.7 Acoustic Properties ..............................................................................................49
4.8 Biological Behaviour............................................................................................50
4.8.1 Assessment Under Food and Water Legislation ...........................................50
4.8.2 Resistance to Microorganisms.......................................................................50
4.8.3 Physiological Compatibility..........................................................................51
4.9 Additives ..............................................................................................................51
4.9.1 Antistatic Agents ...........................................................................................51
4.9.2 Electromagnetic Interference/Radio Frequency Interference Shielding .......52
4.9.3 Slip and Antiblocking Agents .......................................................................53
4.9.4 Metal Deactivators and Acid Scavengers......................................................53
4.9.5 Blowing Agents.............................................................................................53
4.9.6 Nucleating Agents .........................................................................................54
4.9.7 Antifogging Agents .......................................................................................54
4.9.8 Biocides.........................................................................................................54
4.9.9 Flame Retardants...........................................................................................55
4.10 Performance in Service ......................................................................................56
4.10.1 Thermal or Heat Stability............................................................................56
4.10.2 Stability to Light and Ultraviolet Rays........................................................57
4.10.3 Chemical Resistance ...................................................................................59
4.10.4 Permeability ................................................................................................60
4.10.4.1 Permeability of Water and Liquids ...................................................... 60
4.10.4.2 Permeability of Gases .......................................................................... 61
4.10.5 Sterilisation ................................................................................................. 61
4.10.5.1 Autoclave and Ethylene Oxide Sterilisation......................................... 61
4.10.5.2 Radiation Sterilisation ......................................................................... 62
5 Design ......................................................................................................................... 65
5.1 Product Design..................................................................................................... 65
5.1.1 Design for Rigidity and Toughness............................................................... 65
5.1.2 Weld Lines .................................................................................................... 66
5.1.3 Shrinkage and Dimensional Stability............................................................ 66
5.1.4 Sinks and Voids ............................................................................................ 67
5.1.5 Design for Assembly..................................................................................... 68
5.1.6 Integral Hinges.............................................................................................. 68
5.1.7 Design to Avoid Failure and Durability........................................................ 69
5.1.8 Design Safety Factors ................................................................................... 69
5.2 Mould Design....................................................................................................... 70
5.2.1 Flow Length .................................................................................................. 70
5.2.2 Feed Systems................................................................................................. 71
5.2.3 Venting.......................................................................................................... 72
5.2.4 Mould Cooling .............................................................................................. 72
5.2.5 Taper and Ejection ........................................................................................ 73
5.2.6 Surface Finish ............................................................................................... 73
5.2.7 Filled Grades ................................................................................................. 74
6 Processing of PP ........................................................................................................ 75
6.1 Rheology .............................................................................................................. 76
6.1.1 Melt Flow Rate.............................................................................................. 76
6.1.2 Viscosity Versus Shear Rate ......................................................................... 76
6.2 Injection Moulding............................................................................................... 80
6.3 Extrusion .............................................................................................................. 82
6.3.1 Fibre and Filament ........................................................................................ 82
6.3.2 Film Extrusion............................................................................................... 82
6.3.2.1 Cast Film................................................................................................ 82
6.3.2.2 Blown Film............................................................................................. 83
6.3.2.3 Biaxially Oriented Film.......................................................................... 83
6.3.3 Coextrusion ................................................................................................... 83
6.3.4 Stretched Tapes ............................................................................................. 83
6.3.5 Sheet Extrusion ............................................................................................. 83
6.3.6 Pipes and Tubes ............................................................................................ 84
6.4 Blow and Stretch Blow Moulding ....................................................................... 85
6.5 Thermoforming and Vacuum Forming ................................................................ 86
6.6 Calendering .......................................................................................................... 87
6.7 Rotational Moulding ............................................................................................ 87
7 Post Processing and Assembly ................................................................................. 89
7.1 Joining..................................................................................................................89
7.1.1 Welding .........................................................................................................89
7.1.1.1 Heated Tool Welding..............................................................................90
7.1.1.2 Hot Gas Welding ....................................................................................90
7.1.1.3 Friction and Vibration Welding .............................................................90
7.1.1.4 Ultrasonic Welding ................................................................................91
7.1.1.5 Radio Frequency Welding......................................................................91
7.1.1.6 Other Welding Techniques .....................................................................91
7.1.2 Solvent Bonding............................................................................................91
7.1.3 Adhesive Gluing............................................................................................92
7.1.4 Sealability......................................................................................................92
7.2 Assembly and Fabrication....................................................................................92
7.2.1 Machining......................................................................................................92
7.2.2 Snap-fit Joints................................................................................................92
7.2.3 Mechanical Fastening....................................................................................93
7.3 Decorating ............................................................................................................93
7.3.1 Printability and Paintability...........................................................................93
7.3.2 Metallising and Electroplating ......................................................................94
7.3.3 Appliques ......................................................................................................94
8 Causes of Failure .......................................................................................................95
9 Product Development Issues ....................................................................................97
9.1 Material Selection ................................................................................................97
9.2 Design ..................................................................................................................97
9.3 Processing and Post Assembly.............................................................................98
9.4 Performance in Service ........................................................................................98
References ...................................................................................................................101
Abbreviations and Acronyms....................................................................................103
Practical Guide to Polypropylene
1 Introduction
1.1 Background
Polypropylene (PP) was first produced by G. Natta, following the work of K. Ziegler,
by the polymerisation of propylene monomer in 1954 (Figure 1). The macromolecule of
PP contains 10,000 to 20,000 monomer units. The steric arrangement of the methyl
groups attached to every second carbon atom in the chain may vary (see Figure 2). If all
the methyl groups are on the same side of the winding spiral chain molecule, the
product is referred to as isotactic PP. A PP structure where pendant methylene groups
are attached to the polymer backbone chain in an alternating manner is known as
syndiotactic PP. The structure where pendant groups are located in a random manner on
the polymer backbone is the atactic form.
CH2 = CH
CH3
CH3 CH3
syndiotactic polypropylene
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Practical Guide to Polypropylene
Only isotactic PP has the requisite properties required for a useful plastic material.
Stereospecific or Ziegler-Natta catalysts are used to polymerise PP in this form. All the
applications of PP described in this book are for isotactic PP, although brief mention is
made of the main applications and properties of syndiotactic and atactic PP.
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Practical Guide to Polypropylene
A typical material selection involves many properties which are not easily quantifiable
in numerical terms (such as weathering, warpage, surface finish, ease of machining,
etc.) or which may have very obscure units (such as transparency, fatigue, wear,
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Practical Guide to Polypropylene
bonding, detergent resistance, etc.). These properties for PP are compared with other
competitive materials on a judgemental value basis on a scale of zero to nine in Table 4.
1.5 Applications
The main applications of PP in different market sectors are given in Table 5. Some of
the critical requirements for these applications are explained in Table 6.
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Table 6 Critical requirements for applications where PP is one of the best choice
of material
Application Critical requirements
Good rigidity, good toughness, colourability, mouldability in
Chairs
complex shapes
High impact strength at low temperatures, excellent weathering,
Car bumper
high rigidity
Hair dryers, irons and Rigidity, brilliant surface gloss, good heat ageing resistance,
kitchen appliances antistatic properties, high HDT, mar resistance
Disposable food Rigidity, transparency (if required), heat sterilisable, no taste,
packaging good flow and fast cycling, low cost
Syringes, tubes, Transparency, sterilisable and unbreakability (toughness), good
cartridges flow length
Video cassette boxes Fatigue strength, high flexibility, warpage
Low frictional loss, good chemical resistance, high continuous
Pipes and fittings
use temperature, low noise
Luggage Impact strength, warpage
Over the last four decades, PP has established itself as one of the major commodity
plastics. PP is now the third largest consumed plastic material after PE and polyvinyl
chloride. The consumption of PP in comparison to other plastics is shown in Figure 3
[3]. Demand for PP has grown consistently, managing an impressive growth even
during recessions. Western European PP consumption in 1995 was estimated at about 5
million tonnes against a production capacity of about 6 million tonnes. Approximately
55% of PP is used in extrusion and the rest in injection moulding [3]. Sixty percent of
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Practical Guide to Polypropylene
the PP consumed is homopolymer, 20% block copolymer, with the rest either
compounded or random copolymer grades. It is estimated that the growth of PP in the
coming decade will be around 6%, the strongest growth pattern for the bulk polymers.
The major manufacturers of PP and their trade names are given in Table 7.
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2 Basic Types of PP
PP, a semi-crystalline thermoplastic, is made in its homopolymer form by polymerising
propylene monomer using stereospecific Ziegler-Natta catalysts. The catalyst system is
termed stereospecific because it controls the position of the side (methyl) group in each
propylene unit in the polymeric chain. A typical catalyst system may be prepared by
combining titanium trichloride with tributyl aluminium or its variants. Most commercial
PP is isotactic.
2.1 Homopolymer
2.2 Copolymer
The properties of PP depend on the type and amount of comonomer. There are two
basic types: random copolymer and heterophasic or block copolymer. The random
polymers contain 1.5% to 6% by weight of ethylene or higher alkenes (such as butene-
1) in random distribution and in a single chemical phase. The essential difference
between a random and a block copolymer is that the block copolymer contains
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Practical Guide to Polypropylene
comonomer in the form of a dispersed rubber phase [7]. The structure of random and
block copolymerised PP is shown schematically in Figure 4.
—P—P—P—P—E—P—P—P—E—P—P—P—P—P—E—P—P—P—P—P—P—E—P—P—
random copolymer
—P—P—E—E—P—P—P—P—E—E—E—P—P—P—P—P—E—E—E—E—E—P—P—P—
block copolymer
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The polymerisation techniques for PP lead to a wide range of molecular weight. The
molecular weight distribution can be controlled by splitting the PP chains using
hydrogen peroxide into smaller units in the post-reaction stage. This reduces molecular
weight and narrows its distribution and, consequently, increases melt flow rate. Most of
such controlled rheology (CR) grades have melt flow rate (MFR) values higher than 20
g/10 min at 230 °C at 2.16 kg load. It can be as high as 120–150 g/10 min or more.
Moulding cycles for the CR grades can be up to 15% faster, and warpage and shrinkage
is reduced because of reduced orientation of polymer chains in the flow direction and
the reduction in injection pressure due to easy flow of the material. Reactor grades of
PP have a broad molecular weight distribution (Mw to Mn ratio of 5–12), but CR grades
offer a substantially lower ratio (~3–5). However, the breakdown of polymeric chains
might lead to formation of low molecular weight polymers or oligomers that can cause
odour problems (organoleptic problems) in PP (Section 4.8.1). The other problem with
the CR grades is the reduction in impact strength due to the reduction in molecular
weight. The impact properties of the CR grades should be carefully monitored,
particularly at low temperatures.
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Syndiotactic PP is available from, e.g., Fina Oils and Chemicals, and Mitsui Toatsu
Chemicals, polymerised using metallocene catalysts. It is claimed that the syndiotactic
structure provides better impact strength, greater flexibility, lower haze, lower heat
deflection temperature and lower residual monomer content. However, the full
properties of these polymers are still to be evaluated and it remains to be seen whether
syndiotactic PP can offer properties which are unique enough to market it as superior to
isotactic PP and which can provide justification for the higher cost of material [8, 11,
12].
Atactic PP is an amorphous material and has little strength. The main application of
atactic PP is in coatings in conjunction with bitumen or asphalt.
While most of the PP produced is used without mineral filler, the use of such materials
is more common in PP than with PE. PE has very low modulus and stiffness.
Consequently, the improvement in mechanical properties achieved by addition of fillers
is not significant. By choosing the appropriate filler, PP type and compounding
technology, it is possible to design products with properties approaching those of some
engineering polymers. For these reasons, fillers are used not only to reduce the polymer
content and cost but also to enhance its performance. As a result, a significant number
of filled and reinforced PP grades has been developed and are successfully used in
different applications. The improved stiffness and heat deformation resistance has led to
the use of such compounds for the manufacture of heater housings, car mounting
components and several domestic appliances. The main fillers and reinforcements for
PP are discussed in this section. Their impact on its mechanical properties is discussed
in Section 4.3.6.
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It is reported that products made from PP have no effect on the biosphere after landfill
disposal. However, mineral fillers may remain on the disposal site for a very long time
or build up in incinerators.
Control of the average particle size, the particle size distribution, the purity and the
aspect ratio of the filler is necessary to achieve consistent product quality in talc filled
PP. In some grades of talc filled PP, water absorption may be an important factor. This
will affect the surface appearance of the moulded product and the adhesion of the resin
to the filler.
Grades filled with 10% to 40% talc by weight have been produced. Both homopolymer
and copolymer grades of PP are used. Talc filled grades offer higher stiffness, better
surface aesthetics, lower coefficient of thermal expansion, lower shrinkage, and
improved scratch and mar resistance than non-filled grades. Heat deflection temperature
and mould shrinkage are also improved by the addition of talc. Flexural modulus
increases dramatically with added talc at the expense of tensile strength. In some cases,
impact modifiers are added to maintain the impact strength, but at the expense of
stiffness. Filled copolymer grades offer higher yield elongation at the expense of tensile
yield strength.
The main applications for talc filled PP grades are in car heater casing, motor housing,
dryer drums, textile bobbins, industrial and agriculture plant components. Talc filled PP
sheet is used as an alternative to carton board.
Calcium carbonate is also commonly used as a filler for PP. In comparison to the talc
filled grades, the calcium carbonate filled grades are claimed to have higher impact
strength, brighter colour, higher thermal stability and improved fatigue strength, but
lower stiffness and tensile strength. Calcium carbonate is added to PP at the same
loading as talc, from 10–40% by weight. However, in a highly filled system, non-
uniformity of mechanical properties can result from poor dispersion during the
compounding process.
The main applications of calcium carbonate filled PP are in instrument panels, motor
vehicle grills, heater boxes and garden furniture.
Glass fibres are used to confer enhanced strength and rigidity. These fibres are usually
coated with silanes, lubricants, film formers and, sometimes, antioxidants and antistatic
agents. These coatings provide better fibre-matrix adhesion, consequently enhancing
the mechanical properties of the product. These coatings are also intended to reduce
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Practical Guide to Polypropylene
The higher aspect ratio of glass fibre imparts higher reinforcing efficiency than talc,
calcium carbonate or mica. Glass fibre reinforced PP has been successfully used to
replace engineering thermoplastics in various applications. It has replaced PC, ABS,
polyesters and PA in hand-held tools, automotive grill opening reinforcing panels and
pump housings. Glass fibre reinforced grades are used for car and truck fan shrouds, car
rear light housing, radiation expansion tank, grills, headlamp housing, furniture frames
and washing machine components.
The presence of additives in PP can significantly increase the toxicity of the resin.
These substances can migrate into food or water through plastic packaging or to the
body through medical devices. The handling of the additives might require special
handling instructions and they can produce toxic degradation products during
processing. Detailed information about the toxicity and hazard of special additive or
material may be obtained from the Material Safety Data Sheets from the manufacturer.
Some ingredients known to cause health and safety problems used in PP are blowing
agents, peroxides, fillers (such as glass fibre), pigments (particularly lead- and
cadmium-based pigments) and flame retardants.
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As a rule of thumb, if any additive is added to the formulation of the PP, it should be
tested for its likely impact on food and medical applications. Resin should conform to
the regulations for health and safety.
Identification of a plastic component may be required for various reasons, e.g., the
identification of the material of a competitive product or defective products returned
from the field. The simplest technique to identify PP is by burning a small specimen. PP
burns with a blue flame with a yellow tip and smells of burning candle when the flame
is extinguished. PP floats on water and can be easily cut providing smooth surfaces. PP
is soluble in hot toluene. Most of the above observations for identification of PP are
similar to those of PE. Hence, further tests are invariably required for confirmation of
polymer type. The results from flame testing are further complicated by the presence of
comonomers, fillers and additives such as flame retardants, blowing agents, lubricants
and stabilisers. Hence, chemical and thermal analysis is required for positive
identification of the polymer. Infrared (IR) spectroscopy is the most widely used
technique for the positive identification of PP. Typical IR spectra (transmittance (T)
plotted against wavenumber) for different types of PP are shown in Figure 5. IR
spectroscopy can provide limited information about the fillers as well. Differential
scanning calorimeter (DSC) thermograms may be required to confirm the presence of
ethylene comonomer in the case of copolymerised PP or to measure the degree of
crystallinity in the PP artefacts (Section 3.3).
Further information about the fillers can be obtained from thermogravimetric analysis
(TGA) and X-ray fluoroscence spectroscopy (XRF). In TGA, the weight loss and
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derivative weight loss of the polymer are measured as a function of temperature while
XRF provides the elemental analysis of the polymer compound.
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3 Structure
Similar to PE, PP is a linear hydrocarbon polymer containing little or no unsaturation. It
is, therefore, not surprising that PP and PE have many similarities in their properties,
particularly in their swelling and solution behaviour and in their electrical properties. In
spite of many similarities, the presence of a methyl group attached to alternate carbon
atoms in the chain backbone does alter the properties of the polymer in a number of
ways. For example, it causes slight stiffening of the polymer chain and interferes with
the molecular symmetry. The first effect leads to an increase in the crystalline melting
point whereas the interference with molecular symmetry would tend to depress it.
However, the increase in the melting point due to the presence of pendent group is
much higher than the corresponding reduction due to decrease in molecular symmetry.
The melting point of PP is approximately 50 °C higher than that of PE. The melting
point of HDPE ranges from 120–130 °C. The crystalline melting point of PP ranges
from 160–170 °C. Further, due to the presence of pendant methyl groups, PP generally
has higher tensile, flexural and compressive strength and higher modulii than PE. The
methyl side groups can also influence some aspects of chemical behaviour. For
example, the tertiary carbon atom provides a site for oxidation so that PP is less stable
than PE to the influence of oxygen. Thermal oxidation (Section 4.10.1) and high-energy
radiation (Section 4.10.5) lead to chain scission rather than crosslinking.
More sophisticated techniques such as gel permeation chromatography are used for
measuring the molecular weight (Section 3.2).
The influence of molecular weight on the bulk properties of PP is often opposite to that
experienced with most other well-known polymers. Although an increase in molecular
weight leads to an increase in melt viscosity and impact strength, in accord with most
other polymers, it also leads to a lower yield strength, lower hardness, lower stiffness
and softening point. This effect is generally believed to be due to the fact that a high
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molecular weight polymer does not crystallise as easily as lower molecular weight
material and it is the differences in the degree of crystallinity which affects the bulk
properties. It may also be mentioned that an increase in molecular weight leads to a
reduction in brittle point.
3.3 Crystallinity
The molecular chains in PP are linear so they are able to pack together in an ordered
crystal structure. Since chains may be entangled or otherwise imperfect (e.g.,
branching), the structure is not completely regular. Hence, PP is best described as a
semi-crystalline polymer.
The degree of crystallinity and crystal structure in a polymer depends on its thermal
history. A rapid quenching gives a tough clear product since it suppresses the formation
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Practical Guide to Polypropylene
of crystals, while annealing or slow cooling of the product leads to a rather brittle and
hazy product. Increased crystallinity increases hardness, modulus, strength, abrasion
and wear resistance, creep resistance, barrier properties, shrinkage and density. Low
crystallinity offers the advantages of good processibility, better transparency,
economical melt processing and good thermoforming capability. Depending on the
processing conditions, 60%–70% crystallinity in the finished product could be
achieved.
(a)
(b)
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Practical Guide to Polypropylene
Crystallinity in the final moulded artefact could be measured using differential scanning
calorimetry (Figure 7). In differential scanning calorimetry, the energy absorbed or
produced is measured by monitoring the difference in energy input into the substance
and into a reference material as a function of temperature. It can further provide
information about melting, crystallisation and glass transition temperature. It can be
seen from Figure 7 that the heat taken by the product to melt the crystals depends on the
cooling rate of the sample. Quenching suppresses the formation of cystallites, reflected
by the lower heat required for melting of crystals (19.87 cal/g compared to 21.87 cal/g).
The size of spherulites in PP may vary from 1 to 50 microns and can be seen using an
optical microscope under a cross polariser. 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 from the melt. This results in less scattering
of light. This technique is used in injection moulding to improve clarity and rigidity,
and to reduce set-up time. Further details are given in Section 4.9.6.
3.4 Orientation
PP may be oriented either in the melt phase or by stretching when it is solid. In both
processes, the polymer chains are aligned in the perfect direction usually along the line
of flow or stretch. Deliberately introduced orientation in fibres or oriented films can
lead to dramatic changes in molecular and crystalline arrangements. As a result, major
variation in the properties of the article can be expected. Orientation produced by
stretching increases tensile strength and reduces elongation in the direction of stretch.
Biaxial orientation of PP film improves clarity. Further effects of biaxial orientation on
the mechanical properties of PP are explained in Section 4.3.7.
3.5 Isotacticity
Isotacticity is the measure of the percentage of side methyl groups aligned on one
particular side of the polymer chain. The isotacticity of commercially produced grades
is measured in terms of isotactic index, the percentage of the polymer insoluble in n-
heptane. The isotacticity index for most commercially available grades of PP varies
from 85% to 95%. It is understood that within the range of commercial polymers, the
greater the amount of isotactic material, the greater the crystallinity, and hence the
greater the softening point, stiffness, tensile strength, modulus and hardness [14].
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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.
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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:
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.
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temperature is in the region of 20–60 °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.
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.
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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.
Heat deflection temperature is a single point measurement and does not indicate long-
term 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.
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.
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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.
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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.
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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.
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.
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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.
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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.
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.
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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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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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.
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4.3.4 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 semi-
crystalline 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.
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:
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 non-
reinforced 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.
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 4.3.2–4.3.5 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.
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The following terms are commonly used to describe the electrical properties of a
material:
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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.
• 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 (θ). The power factor is defined as Cos θ and
dissipation factor is Tan(90-θ). 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.
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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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
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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.
4.5.3 Haze
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.
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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.
A material’s 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 high-
crystallinity 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.
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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.
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 µm. 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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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.
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
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.
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.
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
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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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.
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 hetero-
atoms 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 0.1–0.2% 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.
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.
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.
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
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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 oxygen-
containing 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.
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.
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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.
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 end-
use conditions before the choice of the grade and stabilisation system is made.
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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.
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.
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.
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.
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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 long-
term 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.
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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.
4.10.4 Permeability
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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.
4.10.5 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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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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5 Design
5.1 Product Design
Rigidity and toughness are quite opposing material properties. It can be seen from
Table 12 and other manufacturers’ data sheets that the grades possessing higher impact
strength have lower stiffness or rigidity. Occasionally high impact strength and good
rigidity both might be required from the product. When both rigidity and toughness are
required, relatively thick sections are usually necessary. The other plastics which have
inherently high rigidity and toughness are PC, ABS, PPE and PA. The rigidity of PP
products may be improved by selecting the appropriate grade of the material with high
rigidity or opting for filled or reinforced grades which offer high rigidity at the expense
of impact strength. The other methods for improving rigidity are:
• By increasing the wall thickness. This is effective in increasing the rigidity as well
as impact strength. The disadvantages are an increase in the weight of the
component and slower cooling of the product in the mould.
• By incorporating ribs. Ribs are quite effective in increasing the rigidity with
minimum increase in the weight of the component. However, the disadvantages are
higher tool cost, risk of lower impact strength due to stress concentration and sink
marks.
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Weld or knit lines occur where flow fronts converge. They are inevitable in multi-gated
parts and in parts with moulded-in holes, metal inserts and bosses. They are generally
visible on close inspection and the more obvious they appear to be, the weaker they will
be. The strength of the material at a weld line can be less than 50% of the reported
strength of the material, and fibre reinforced plastics are more affected by the weld line
problem because the fibres will not bridge the weld. Although the weld strength can be
controlled by increasing the temperature and pressure at the flow fronts, the design of
the mould and the product plays a very crucial role. A pure butt weld where two flow
fronts meet at 180 degrees forms the weakest weld. The weld strength can be improved
if the weld forms by the merging of two flow fronts. Some techniques used to overcome
the problems of weld lines are knock-out holes and flow leaders.
PP has relatively high mould shrinkage (see Table 2) and it can range from 0.8% to
2.5%. The moulding shrinkage is influenced by the processing conditions.
Consequently, it is very difficult to achieve ultra-close dimensional tolerances in PP.
However, PP is a tough, resilient polymer with good resistance to stress cracking,
diminishing the need for very close tolerances.
It is usually good practice to maintain a constant wall thickness. This is necessary for
two reasons: to avoid the possibility of air entrapment while moulding and to avoid
warpage due to differential cooling and shrinkage. Thick sections cool more slowly
than thin sections and, consequently, shrinkage of thick sections is much higher than
that of thin sections. This can cause mouldings to bow, particularly if the difference in
wall thickness extends over a considerable distance. However, there are exceptions to
this general rule of maintaining constant wall thickness. Sometimes, the stresses created
by differential shrinkage due to different wall thickness may be used to offset
deformation induced by other causes. For example, the tendency of straight side walls
on a box-shaped moulding is to bow inwards. External ribs or tapered wall thickness
can stiffen the moulding, thus assisting in achieving undistorted wall thickness.
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To create the right dimensions in the moulded part, the dimensions of the mould cavity
must be increased by an amount known as the shrinkage allowance. The material
shrinks more in the direction of the flow than in the transverse direction. This is known
as differential shrinkage and is a consequence of the long chain molecular structure
which leads to partial orientation of chains and stretching of the chains during melt
flow. Differential shrinkage results in a distorted or warped moulding, and is more
marked in materials with a wide molecular weight distribution and is less in grades with
narrower molecular weight distribution. The differential shrinkage in controlled
rheology grades is remarkably less than the regular grades. The differential shrinkage is
not easy to design for since the differences are small and prediction of the flow
direction is required. Where close tolerances are required, the differential shrinkage
should be accounted for in design.
The injection pressure in the mould cavity decreases considerably with distance from
the gate. The location, shape and number of gates influence melt orientation. This
explains the very large variation in the shrinkage which sometimes occurs between
different parts of a moulding, particularly complex mouldings.
All injection-moulded thermoplastics are prone to sink marks and voids in areas where
sudden changes in section thickness occur, or over ribs and bosses. Semi-crystalline
polymers such as PP are more prone to sinks and voids. Voids occur when the external
skin of the moulding is rapidly cooled and becomes sufficiently rigid to support the
contraction of the underlying melt. Sinking or surface depression occurs in localised
thick sections where internal mass contains sufficient heat to keep the polymer in
molten stage and crystallises slowly producing sink marks.
Once again, the moulder can control these defects to a certain extent. However, a
product designer can play an important role in keeping the changes in wall thickness to
a minimum. Ribs and bosses which introduce locally increased section thicknesses are
the main items for consideration. The other methods for reducing the impact of sinking
in stepped sections are camouflaging the sink marks in design by placing them in a
section not visible directly, changing the wall thickness or putting beads or decorations
on the possible locations of sink marks.
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PP is a tough and resilient plastic and many types of mechanical fastening techniques,
(Section 7.2), can be easily used. However, PP is prone to creep and screws used under
high stress for assembly may slack due to creep. In these cases, metal inserts should be
preferred since they increase the load-bearing area in PP. Metal inserts may be moulded
in or pressed in after injection moulding. However, the stress concentration effect on
the impact strength due to sharp-edged inserts should be carefully considered.
Moulded-in internal or external threads can be used with PP. The design of threads is
important to avoid the possibility of thread jumping. Thread jumping may occur if high
torque is applied to the screw. If this happens, the moulded thread is still usually
unharmed and can still be used. Acme or buttress type threads can be used to decrease
the possibility of thread jumping.
Design of undercut sections for snap-fit assembly parts is another crucial point in the
design of PP artefacts. External undercuts can be easily demoulded using retracting
segments in the mould, provided part geometry allows for this. Internal undercuts can
be ‘jumped’ out of the mould and are limited in size and shape. In this case, the wall of
the moulding should be free to flex outwards during ejection.
PP is the best material for producing internal hinges. Thin sections of PP have shown
excellent resistance to continued flexing. This has led to the introduction of a number of
one-piece mouldings for boxes and cases in which the hinges are an integral part of the
moulding. In this special, very cost-effective production process, two parts plus hinge
are injection moulded in one moulding operation. After moulding, the integral hinge
must be initially flexed and hence stretched, if possible while still hot. Only in this way
are the polymer chains oriented along the hinge to give excellent flexural fatigue
resistance. The stretched hinges can be flexed several million times without failure even
when bent through large angles right back on themselves. This, of course, assumes
correct design, suitable injection moulding conditions and exposure to flexural stress
only. Where product design makes direct moulding impractical, the hinge may be
subsequently formed or machined. To a limited extent, hinges can be formed from filled
grades but the quality is unpredictable and they are not recommended.
To ensure straightforward mould filling and easy mobility of the hinge, the film
thickness should be between 0.25 mm and 0.8 mm. If transverse stresses and small
bending angles are expected, the film thickness might be up to 1.8 mm. There should be
fast, even flow through the hinge section when the melt is injected into the mould. With
multipoint gating, e.g., on lids and boxes, merging of melt fronts should never occur in
the hinge section. Moulded parts with hinges frequently require a higher melt flow rate
material to ensure a rapid mould fill and good hinge quality. However, material with
too high a flow reduces the strength of the hinge.
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Long-term creep and fatigue data should be used to ascertain long-term durability of PP
artefacts. Since PP offers a cost advantage as a replacement material for engineering
plastics, it is anticipated that, in the future, PP will be used to replace many engineering
components. Due to the lower modulus of PP in comparison to other engineering
plastics, ascertaining durability of the artefacts will be a crucial aspect of the design.
However, extrapolation of creep and fatigue data to longer durations of time or higher
service temperatures is fraught with problems owing to the unknown transitions in the
mechanical behaviour of material at longer durations/higher temperature. Tertiary creep
can eventually cause the ultimate failure of the product. Hence, when extrapolating the
long-term testing results, durability of the product should be checked using elevated
temperature testing to avoid catastrophic failure due to the tertiary creep.
The actual performance of the product may deviate from that predicted using short-term
tests. Consequently, the properties from the short-term standard tests should be taken as
guide only. Ideally, the properties of the finished product should be measured under
service conditions. Fatigue and creep data for individual trade-named grades are
normally available from the manufacturers.
In design calculations for moulded components, the property values determined from
the long-term tests must be divided by a safety factor. The safety factor recommended
in the designing of components for maximum permissible deformation is 1.2 while for
calculations to provide safety against fracture, factors of 1.3 to 5 are advised, depending
on the stress and the degree of risk to property and persons. It should be noted that these
safety factors are based on the long-term strength of the material, not on the short-term
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yield strength. The long-term recommended design stress might be 6–10 times lower
than the short-term yield strength.
The flow ratio is the flow length in the mould divided by the wall thickness of the
moulding. A number of factors can affect the flow ratio such as melt flow rate, the
processing conditions and the features of the mould. Thick sections enable higher flow
ratios to be achieved while very thin sections have the opposite effect. The flow length
of the material provides the mould designer with a guide to the minimum number or
position of feed points which will be advisable.
The effect of variations in thickness and melt temperature on the flow length of a
typical PP sample is shown in Figure 23. The relationship between the flow length and
MFR of CR grades is not simple. Generally, the flow length of CR grades is similar to
those of normal grades of about two-thirds of the MFR quoted for the CR type. This is
due to the narrow molecular weight distribution of CR grades.
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Another method for the practical assessment of the melt flow properties of PP is the
spiral flow test. The plasticised melt is injected into a spiral mould cavity. Before
reaching the end of this spiral channel, the melt freezes. The distance which the melt
flows along the channel before freezing (spiral flow length) depends on the flow
properties of the material and on the section thickness of the spiral. The flow properties,
obviously, vary with the particular grade of PP. The spiral flow data for different
materials is easily available from the raw material manufacturers. It is advisable to use
only 0.7 to 0.8 times the flow path length determined experimentally in the spiral flow
mould to leave adequate margin of safety to achieve complete filling of the mould.
The feed system to moulds has three principal components: sprue, runner and gate. The
sprue is a tapered bore in line with the axis of the injection unit that conducts the melt
to the parting line of the mould. The runner is a channel cut in the parting line of the
mould to conduct material flow from the sprue to a point very close to the melt cavity.
The gate is a relatively small and short channel which connects the runner to the mould
cavity. Runners may be cold or hot, indicating the temperature at which the runner is
maintained in comparison to the melt temperature.
Runner layouts should be designed for all plastic materials to deliver the plastics melt at
the same time and at the same temperature, pressure and velocity to each cavity of a
multi-cavity mould. A typical runner diameter for unfilled PP is 4.8–9.6 mm. A
balanced runner (all cavities fill at the same time at the same pressure) will usually
consume more material than an unbalanced type but this disadvantage is outweighed by
the improvement in the uniformity and quality of the mouldings. Unbalanced moulds
usually cause overpacking, warpage, differential shrinkage, brittleness, dimensional
inconsistency and parts that stick to the mould. If a naturally balanced runner is not
possible, the artificial balancing of runner via size and length changes should be carried
out to achieve good quality parts. Balancing by varying the gate size is not
recommended.
The position and type of gate(s) has a major bearing on the product quality. All possible
gate types are possible with PP and the usual recommendations for other plastics are
also valid for gates for PP artefacts. Some general recommendations for the design of
gates are:
• place the gate near the thick sections so that they will fill completely,
• place the gate in a cosmetically acceptable position,
• the gate should be easily removable,
• maintain the symmetry in flow,
• avoid gas traps and weld lines,
• avoid gating in parts which are subjected to high stresses, and
• minimise the differential shrinkage.
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5.2.3 Venting
Venting of the mould might be necessary to avoid a short shot or burning of the
material in certain cases. In other cases, venting will allow easy and quick mould
filling, possibly at lower injection pressure. When an injection mould fills, the incoming
high velocity melt stream is resisted by and must displace the air in the feed systems
and cavities. Often air gaps between the parting faces of the mould and between the
assembled part of the core and cavity provide a mechanism for escape of air. In some
cases, the location of vents will be quite obvious. In other complex cases, mould flow
simulation packages can predict the location of vents before machining the mould.
Vents are susceptible to corrosion and proper choice of the material, e.g., alloys or high
chromium steel containing a chromium fraction greater than 10%, are preferred.
However, if alloys containing copper are in contact with melt PP for an extended time
they can cause degradation of the material. The location of vents is quite important for
thin-walled mouldings where high injection speeds are necessary.
Good design of cooling channels is very important for moulds for PP due to the higher
heat capacity of the PP in comparison to most of the plastics, with the exception of
HDPE. It is very difficult to overdesign cooling channels in a PP mould. Mould cooling
is a very crucial requirement in the moulding of PP artefacts to achieve good quality
moulding in minimum time cycle.
Cooling time depends on the melt temperature, mould temperature, resin stiffness and
rate of crystallisation. If the wall thickness of the component is doubled, it is expected
that the cooling time is increased by 3 to 4 times. PP has a relatively high softening
point and therefore a wide range of mould temperatures between 20–90 °C can be used.
High mould temperatures are sometimes desirable to avoid distortion and to encourage
flow over long distances. Surface gloss is improved by the use of high mould
temperatures and voids may be eliminated by this means also; any sinking may be
accentuated. Within very small limits, the size of the mouldings is controlled by the
mould temperature; the amount of shrinkage increases as the rate of cooling decreases.
The aim of the design of the cooling circuits is not to cool a moulding as quickly as
possible. Very fast cooling may have undesirable effects on the physical properties or
surface appearance of the product. The design of the cooling circuit should attempt to
cool the whole moulding to the ejection temperature at the same time.
The temperature of the plastic melt decreases with outward flow from the feed point,
and the temperature of the water increases as it flows through the mould. This effect
could be utilised to counter the temperature drop in the material so that all the portions
of the moulding are cooled at the same rate, i.e., using a co-current system of cooling
where the cold water enters to a point close to the feed systems and travels outward in
the direction of melt flow. This would ensure, for all practical purposes, the
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simultaneous cooling of the whole moulding. Local cooling is required for thick
sections to avoid shrinkage variations and to reduce the possible increase in cycle time.
Narrow cores may prevent the incorporation of adequate cooling channels. In such
instances, the cores tend to overheat and, apart from increasing the cooling time, this
can cause the walls on each side of the core to shrink towards each other after the
moulding is ejected. Advantage may be taken of the superior heat transmission
characteristics of some alloys, such as beryllium-copper, to improve this situation. The
core is then provided with generous cooling at the base.
Turbulent flow in the cooling channels is more efficient than laminar flow. This can be
achieved by decreasing the size of the channels or by increasing the flow rate. This runs
counter to popular belief that large cooling channels are always better. It is difficult to
achieve turbulent flow with oils or antifreeze solutions due to their higher viscosities.
Normally, a generous draft taper should be provided for easy ejection of the artefact,
consistent with the design of the product. The ejection of PP artefacts is not very
difficult and sometimes a taper of 0.5° is sufficient. If enough taper is not possible,
mouldings can be produced with very low or even no taper, provided that ample load-
bearing area is provided for the ejection and that the thickness of the moulding is
sufficient to avoid buckling or permanent deformation.
PP is a resilient plastic which stretches rather than cracks if ejector pins of inadequate
area are employed. It is not a very hard or rigid material so the rule is to use ejectors
that are as large as possible. Ejectors inevitably leave witness marks on the mouldings.
Hence, it is preferred for ejectors to operate on side walls, ribs or bosses. When ejector
pins are to be positioned in flexible areas of moulding, they should be of ample
diameter.
Cylindrical ejector pins are most commonly used. However, rectangular pins or blade
ejectors could be used in constricted areas. A stripper plate acts on the entire wall of the
part and so distributes the ejection force. Air assisted ejection of thin walled articles
could be used.
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The design of the gating system for the component to be produced in the textured
surface is very important since the merging flow fronts can cause surface defects on the
moulded artefact. To avoid this fault, gates should be positioned to prevent converging
streams of material. If this is not possible any converging lines should be directed into
unseen areas of the moulding.
When designing mouldings in reinforced and filled PP, the general guidelines for
design of the product and the mould are the same as those for unreinforced PP.
However, filled and reinforced grades require some extra consideration:
• Avoid melt accumulation to avoid the degradation of material. Filled grades are
more temperature sensitive than the unreinforced grades and degradation
temperature is lower.
• Avoid notches such as transition, corner and edges. Use a rounding off radius of
greater than 0.5 mm.
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6 Processing of PP
A broad idea about the processibility of a plastic could be made from its crystalline
nature. In general, the following comments could be made about the processibility of
semi-crystalline and amorphous plastics.
• Semi-crystalline plastics have higher specific heat capacity than the amorphous
plastics. Hence, the energy required for melting of the resin will be more leading to
costly melt processing.
• The amount of heat to be removed from the mould during cooling is more in the
case of semi-crystalline material. Hence, the moulded artefacts will take longer to
cool. Cooling method and design of cooling channels are quite important.
• The shrinkage between the melt and solid state is more in semi-crystalline plastics.
The dimensions of the mouldings are thus more difficult to predict. In addition,
warping, sinking and voiding may occur. Higher die swell makes accurate
extrusion profiling difficult.
• The lower melt elasticity of semi-crystalline material means that forming by blow
moulding and thermoforming is quite difficult.
The economics of processing depend on the thermal characteristics of the material. The
thermal properties of PP are compared with some other plastics in Table 23. The heat
transfer requirement for cooling from the melt temperature to mould temperature in the
case of PP is much higher than those in the case of amorphous polymers such as ABS
and PS. Hence, the processing of PP is costly. In addition, thermal conductivity
determines the cooling time of the material in the mould. It can be seen that the thermal
conductivity of PP is less than HDPE. It would require more cooling time, and hence, a
slower production rate.
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The purpose of this text is not to go into the detail of the injection moulding process and
associated control but to highlight the complexities involved in injection moulding of
PP and how it is different from other plastics. For details on injection moulding, several
textbooks are available [e.g., 22].
6.1 Rheology
Melt flow rate is the traditional method of measuring the viscosity of PP. The melt flow
rate of PP is determined by measuring the flow of molten PP through a standard orifice
at 230 °C and 2.16 kg load. The processing technique basically decides the selection of
melt flow rate. The melt flow indices of PP may range from as low as 0.5 g/10 min to as
high as 1000 g/10 min. CR grades in general have higher MFRs. The current trend in
grade specification design is to increase MFR without loss of mechanical and thermal
properties.
A grade with a low index is preferred for techniques requiring a self-supporting melt,
like film blowing. High index grades give the easy flow needed for thin wall injection
moulding, film casting and fibre spinning. As a rough guide to selection of grades, a
MFR between 0.5–2 is chosen for pipes, sheets and blow moulding, 2–8 for films and
fibre applications, and greater than 8 for extrusion coating, injection moulding and fibre
spinning. Higher MFR grades are mainly used for thin-walled applications which
require rapid mould filling.
The MFR test as discussed above has certain limitations. Since it is a one-point test
only, it is quite possible for two materials with the same MFR to behave completely
differently at shear stresses that are different from the ones used during the MFR
measurements. Further, the low shear rates employed during the measurement cannot
give a reliable measure of mouldability, owing to the higher shear rates encountered in
injection moulding. The capillary rheometer measures apparent viscosity over an entire
range of shear stresses and shear rates encountered in compression moulding,
calendering, extrusion, injection moulding and other polymer melt processing
operations. The shear rates generated during compression moulding are quite low while
injection moulding operation generates very high shear rates. Shear rates during
extrusion fall between compression moulding and injection moulding. At least three
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different loads and speed settings are used to generate a shear stress versus shear strain
curve for a polymer in a capillary rheometer.
PP is sensitive to shear. When the shear stress or shear strain on the material is
increased, the viscosity of the melt decreases. The extent to which this occurs varies
with molecular weight distribution, particularly when molecular weight is high. The
viscosity versus shear rate curves for three homopolymers of PP with different MFRs
are compared in Figure 24. It can be seen from the figure that the viscosity of the resin
decreases non linearly as the shear rate increases and the extent of shear thinning
depends on the molecular weight and molecular weight distribution of the polymer.
Figure 24 Viscosity versus shear rate curve for three homopolymer grades of PP
with different melt flow rates
The viscosity versus shear strain curves for homopolymer and controlled rheology
grades of PP are shown in Figure 25. It can be seen from the figure that the viscosity of
the controlled rheology grades is lower than the conventional grades at low shear rates.
The extent of shear thinning at high shear rates is less than the conventional grades due
to the lower molecular weight distribution of controlled rheology grades. In other
words, controlled rheology grades are less shear sensitive.
PP grades with a wide molecular weight distribution respond the most to an increase in
shear rate. Hence, for PP it would be more appropriate to deal with mould filling
problems by increasing the injection speed rather than increasing the melt temperature.
Material with broader MWD is processed more easily during injection moulding since
the low molecular weight chains acts as plasticiser. However, narrow molecular weight
distribution grades are preferred for extrusion applications.
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Figure 25 Viscosity versus shear rate curve for homopolymer and controlled
rheology grades of PP
The rheological requirements from the resin for different processing routes are
different. In injection moulding, the material is sheared between two surfaces, hence,
shear viscosity is more important. Extensional flow and melt strength are useful
requirements during thermoforming, extrusion coating, foaming, blow moulding and
film blowing. As mentioned above, PP has low melt strength, hence, thermoforming,
blow moulding and film blowing of PP are difficult. To improve the acceptance of PP
in these applications, high melt strength grades have been introduced by the resin
manufacturers. High melt strength grades have broader molecular weight distribution
and show greater shear thinning (Figure 26). The long chain branching in high melt
strength grades is similar to that in LDPE. However, it is thought that the branch chains
are significantly longer and can be as long as the main chain itself. The extensional
viscosity of conventional and high melt strength grades of PP is compared in Figure 27
and it shows that conventional grades have low extensional viscosity and melt strength.
High melt strength grades break in elastic manner at high extension rates while
conventional grades break in normal necking mode without significant recoil. High
melt strength grades offer significant advantages over conventional grades for many
processing routes: improved sag resistance and part uniformity for thermoforming,
improved fine cell structure for low density foams, sag resistance and part uniformity
for blow moulding and increased bubble stability for film blowing [23, 24].
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The main use of the viscosity versus shear rate data is during the mould design to
predict the behaviour of the mould during an actual filling cycle. Its use at the moulding
shop floor is, however, limited. Consideration of the rheology of the material at the
moulding floor by comparison of rheological behaviour of similar grades from different
suppliers might reap sufficient economical dividend. For example, the final choice of
the grade for injection moulding from different equivalent grades available from the
resin manufacturers may be made from the injection pressure versus injection time
curve for different grades. The material which offers lowest injection time at minimum
injection pressure could be the final choice of material. Similarly, for blown film
applications, screw speed, power required and head pressure estimation based on
rheological characterisation may be useful.
Injection moulding is a very commonly used technique for producing PP articles and
almost a third of PP is processed by injection moulding. Although the process of
injection moulding is very simple, injection moulding machines and moulds are very
costly due to the high pressure needed for injection of the thermoplastic melt and the
associated complex controls. However, the ability to produce articles at high speed tips
the balance in favour of injection moulding. In injection moulding, the plastics material
is heated until it becomes a viscous melt and it is then forced into a closed mould that
defines the shape of the article to be produced.
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the melt state to the solid state. Higher compression ratio screws (3:1 to 4:1) with
length/diameter (L/D) ratio greater than 20 are required for filled grades and grades
using masterbatches, to achieve good plasticisation and homogeneous melt.
The shot volume for the injection machine is a function of screw diameter and its
maximum retraction during plasticising. Quoted injection weights are usually
referenced for PS. The melt densities of polystyrene and PP are 0.89 and 0.85 g/cm3,
respectively. This means the shot weight for PP on a particular injection moulding
machine will be less than for PS on the same machine. The shot weight for most
plastics on a particular injection moulding machine, with the exception of LDPE and
HDPE, is higher than PP.
Shot volume is limited by the residence time. PP has a tendency to oxidise and is
routinely protected by the inclusion of antioxidants in the polymer production process.
Hence, PP cannot be exposed to very high residence times. Allowable residence time
depends on the material temperature and the nature of heat stabilisation. Longer
residence time is possible at lower temperature. The shot volume may be up to 85% of
the machine maximum shot volume. The minimum shot volume depends on the
residence time and can be as low as 15% of the maximum shot volume of the machine.
PP normally requires no predrying before injection moulding. Exceptions can arise after
storage under unfavourable conditions or when processing filled grades. In the case of
filled plastics or dark coloured plastics, additional enhancement of the surface quality
could be achieved by predrying the compounds at 120 °C for 3 hours in a dried air
circulating oven.
Moulding conditions are quite unique to the article being moulded and depend on the
part configuration, mould design, material properties, choice of the material and
properties required from the finished part. PP can be injection moulded at a melt
temperature of 200–300 °C and a mould temperature of 20–90 °C. However, a melt
temperature of 220–260 °C and mould temperature of 20–40 °C are quite normal.
Lower mould temperature may be used for fast cycling of parts with a high injection
rate. However, high mould temperatures may be required for thick-walled parts where
premature freezing of the walls may lead to the formation of internal voids. The melt
temperature for flame retardant grades of PP should not exceed 220–230 °C. Higher
temperatures can result in discolouration and thermal degradation. In the long run,
higher temperatures can also lead to corrosion of the mould and the machine. It is
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always advisable not to let products stay in the heated machine for lengthy periods and
to flush the barrel with unfilled grades of PP. The melt temperature of the easy flowing
grades should be kept low, as recommended by the material manufacturer.
6.3 Extrusion
Extrusion is the single most popular process for forming PP. Fibre and filament account
for most of the PP extrusion. Sheet and profile extrusion account for only a minor share
of the market.
A large portion of extruded PP goes into the manufacture of fibre and filament. The
various versions of extruded PP fibre and filament are multifilament, continuous
filament, bulk continuous filament, staple fibre and monofilament. The diameter of the
monofilaments (75–5000 denier) is considerable higher than those of the staple fibres
(1–10 denier). The MFR requirements from the resin are quite different and
monofilaments are produced from resins with very low MFR. The main applications for
fibres and filaments are carpet yarns, upholstery fabrics, disposable fabrics, woven
sacks, rope, cord and strapping.
The suitable screws for extrusion of PP should have a high L/D ratio of 24 to 30 and a
high compression ratio of 3 to 4. Attention to the barrel can also improve the material
conveying performance at the inlet, stepping up the output rate. A series of axial
grooves in the barrel wall, extending for at least three screw diameters, is effective for
PP. Normally PP is not likely to contain moisture, volatiles or entrained air so vented
screws are not normally used in its processing. The main methods for manufacturing PP
film are cast and blown film techniques.
Cast film of PP may be produced by using chill roll or water quench techniques. Both
of these processes are characterised by relatively high melt temperatures and rapid rates
of film cooling. This results in films with low haze, good clarity and high gloss. Slit
dies are used to produce the cast film. The film thickness is controlled by the gap
between the die lips but also by the rotational speed of the chill roll. Relatively high
melt temperatures between 240–270 °C are used to optimise the optical properties.
When carefully controlled, the thickness uniformity of chill roll cast film is
substantially superior to blown film. The rapid quenching of the film by direct water
cooling reduces the crystallinity and produces a tough film.
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In the blown film process, internal air pressure is used to produce a relatively thin film.
Normally air is used as the coolant for PE films but it presents greater difficulty when
used with PP due to the slower cooling speed and the greater thermal degradation of
material. The water quench process is generally the preferred method of producing
blown PP film.
Biaxially oriented PP (BOPP) film is a highly transparent, stiff film. The film can be
produced using a blown film or tenter process. Stretching in both the machine direction
and transverse direction is carried out at a temperature below the melting point of the
polymer and results in the partial orientation of molecules in the direction of stretch.
The film produced by the blown process is nearly isotropic in both the directions while
the film produced by the tenter process tends to be more highly oriented in the direction
of machine. The cost of the tenter process equipment is much higher in comparison to
blown film equipment.
Biaxially oriented films are not readily heat sealable. This is a prime requirement for
packaging films so BOPP is normally given a surface coating of a heat sealable
polymer such as a coextruded PP random copolymer.
6.3.3 Coextrusion
Coextruded film may be a very complex structure composed of many layers to provide
different functionalities and of different tie layers which improve the bonding between
adjacent layers. Separate extruders are required for extrusion of the different layers.
Apart from the functionality provided by the resin, the main issues involved with the
selection of different layers for coextrusion are the viscosity of the resin and the
adherence between layers.
Strapping tapes, film tapes, monofilaments, fibres and nonwovens are usually stretched
immediately after extrusion to achieve considerable increase in ultimate tensile strength
in the stretching direction as a result of molecular orientation. The elongation at break
correspondingly decreases. The film for stretched tapes can be produced by a cast film
technique using either the water quench or chill roll process.
The distinction between sheet and film arises from the thickness; sheets are usually
thicker than 0.25 mm. PP sheets can be produced with slit dies in a range of widths and
thicknesses. The width of the sheets may be as high as 2.5 m. Sheets may be used for
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PP pipes can normally be produced on plants which are designed to process HDPE.
However, some special considerations are needed since PP degrades faster and is more
sensitive to oxidation. PP has a similar heat capacity to HDPE with a lower thermal
conductivity. Consequently, the output in the case of PP is 15% lower than that for
HDPE. Applications for PP pipes include potable water supply, domestic waste
systems, under-floor heating circuits, chemical effluent disposal systems and thermal
spring conduits.
The principal advantages of PP for use in pipe extrusion are good heat ageing, high heat
distortion temperature, low frictional losses, light weight and good resistance to attack
by chemicals. Flame retardant grades could be used for construction applications. PP
pipes are very sensitive to degradation by UV radiation. Hence, the material should be
stabilised against UV degradation for above ground piping and where the pipes are
stored in the open for considerable time before installation.
To maintain good weld strength in pipes, a long die length to increase die pressure and
minimise flow variations is required for spider-type dies. During the selection of
suitable pipe size and wall thickness, suitable care should be taken to provide an
adequate safety factor. A safety factor of two based on the long-term strength of the
pipe for the design life of the pipe is recommended. The variation in temperature should
also be considered where the PP pipes are being used for under-floor heating or effluent
waste water pipes; a fatigue situation might occur due to temperature variation.
PP random copolymer has been used for piping systems for domestic hot and cold
water supply [25]. The important issues for consideration are high drinking water
quality, corrosion resistance, ease of installation and cost reduction in installation. The
random copolymer is preferred over the block copolymer since it has better long-term
internal pressure resistance at elevated temperature. The insensitivity of the random
copolymer to the pH of the water, low noise from flowing water, low pressure loss and
good thermal insulation are also contributory factors. Domestic piping systems are
required to fulfil a service life of at least 50 years at a temperature of 60–70 °C at 1
MPa. Welding of the pipes is very crucial and is further discussed in Section 7.1.1.1.
Pipes and fittings should have high impact strength, a homogeneously fine structure
throughout the thickness of the pipe and low frozen-in stresses. Thick-walled pipes
made of conventional PP tend to have coarse morphology in the middle of the wall.
Frozen-in stresses are undesirable because pipes are subjected to internal pressure
stresses in operation. Early failure may result where these are combined with external
stresses.
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The basic difficulty is to reconcile the need for a homogeneous melt which requires
high melt temperatures and shear mixing with the tendency of these conditions to cause
polymer degradation. In order to work at the lowest practical temperatures, very good
temperature control is necessary for all stages of the process and in addition the
machine should be of robust construction. This is because at low temperatures, high
pressures will be developed in the barrel. In particular, the thrust bearings must be well
designed. To minimise wear the extruder barrels should have a continuous hardened
steel liner.
The continuous extrusion blow moulding process is commonly used for PP and
involves a slow extrusion rate, running the risk of thinning as a parison stretches under
its own weight. Hence this technique is not suitable for containers with a capacity of
more than 10 litres. Intermittent extrusion might be the solution for long or heavy
parisons or for thermoplastic materials with low melt viscosity or strength. The
extrusion temperatures for homopolymer and block copolymers are in the range of 210
°C while the melt temperature for random PP is about 190 °C. A melt temperature
greater than 230 °C are not normally used for blow moulding. The screw required for
extrusion of the parison is similar to the screw requirements for the extrusion process in
general. The critical requirements for the screw design are to achieve high production
rates with good plasticisation of the material without degradation. Conventional
extruders with screw lengths greater than or equal to 20 and smooth barrels, or with
barrels with a grooved feed zone can be used for plasticisation. The latter offer
advantage with regard to the output rate and uniformity.
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The amount of PP presently used for thermoforming is very small and the reasons are
similar to those discussed in Section 6.4. The low elasticity of semi-crystalline
polymers at forming temperatures makes vacuum forming of the PP very difficult.
More heat is required to make it formable and the cooling time is longer. Its low melt
strength means that it is prone to excessive sagging when heated above its melting
point. It is difficult to heat PP sheet evenly because it tends to buckle when warmed.
The problem lies in the way the tensile strength of PP varies with temperature, which is
different to the behaviour of amorphous materials. With PP, there is an extremely rapid
change in tensile strength just below the crystalline melting temperature. The
temperature window within which thermoforming is possible lies within this range. The
material must on the one hand be soft enough to be deformed by the air pressure of
about 0.6 MPa but on the other hand, it must retain sufficient strength for
thermoforming. This temperature window is only about 5 °C in the case of PP. In
contrast, the change in the mechanical properties of polystyrene is more gradual and it
remains processible within a window of 50 °C. Increased die swell makes accurate
extrusion profiling of PP difficult.
Despite the inherent difficulties in thermoforming PP, the advances in the material and
the machinery are making this a rapid growth area for PP [5, 27]. The good oxygen
barrier properties of stretched PP, high softening point, good chemical resistance, low
cost, excellent toughness, good stress crack resistance and light weight of the material
are the advantageous properties which could be used to replace thermoformed
polystyrene. PP containers can be hot filled and microwaved [28].
PP can be thermoformed in two distinct phases: in the solid phase below its crystalline
melting point and in the melt phase above its crystalline melting point. Both techniques
have advantages and disadvantages.
Solid phase forming of PP is carried out in the temperature range of 155–165 °C. Under
these conditions, the sheet is relatively strong and resistant to sagging. The
disadvantage is that the vacuum may not be sufficient for forming so plug assistance
will be required. The pressure required for forming is highly dependent on the forming
temperature and a few degrees difference in temperature may make quite a large
difference in pressure required. Solid phase thermoforming of PP requires specialised
machinery. This uses high air pressure to form sheets which have been heated to a
temperature below their melting point. Furthermore, the cut-in-place design is essential
for PP. The part needs excessive cooling and can deform excessively. The cut-in-place
technique separates excess material as soon as possible, thus reducing warpage.
Melt phase forming of PP is carried out in the range of 175–185 °C and requires grades
of PP with high melt strength. Conventional grades have insufficient strength to be
formed successfully by this method. Sag resistance is related to the extensional
viscosity of the material and to the molecular weight of the material. Long chain
branching is preferred to achieve high melt strength. Grades with long chain branching
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(which offers improved sag resistance and drawability) are suitable for thermoforming
of large parts. The residual stress level in melt phase forming of PP is quite low (less
tendency to warp and distort on heating than with solid phase forming) and there is
reduced wall thickness variation. Further, the variation in forming pressure with
temperature is quite low during melt phase forming of PP.
Crystallinity, the orientation of the chains and the clarity depend on the forming
temperature. The shrinkage of PP thermoformed articles is complex and is a function of
sheet crystallinity, orientation, thermoforming conditions and orientation arising from
stretching of the sheet. Hence, a reliable figure for shrinkage is not possible.
The specific heat of PP is very much higher than for the amorphous plastics. This is
because with PP the glass transition temperature of the amorphous region has already
been exceeded at room temperature and at the thermoforming temperature the
crystalline region begins to melt. PP requires 2 to 2.5 times more heat than PS to raise
its temperature from the ambient to the thermoforming temperature. Thermoforming
moulds for PP should be made from material with high thermal conductivity such as
aluminium. Furthermore, the moulds should be efficiently cooled.
PP for thermoforming typically has a MFR in the range of 1.8 to 8.0. Suitable
homopolymers, random and copolymer grades could be used offering their relative
advantages and disadvantages [4]. Nucleated homopolymers are preferred. Higher
stiffness of the homopolymer grades allows reduced wall thickness, thereby, achieving
cost savings.
6.6 Calendering
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7.1 Joining
7.1.1 Welding
Like all other plastics, PP can be welded by application of heat and pressure.
Ultrasonic, heated tool, hot gas, vibration or spin welding techniques can be used with
PP. The choice of the welding technique depends on the area of joint, and the number
and the shape of the parts to be joined. The strength of the welding depends on the
geometry of the component, welding method and welding parameters. The selection of
the welding method and the design of the component should be carefully considered at
the design stage.
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In heated tool welding, a heated platen is used to melt the joining surfaces of two
thermoplastic parts. The two interfaces are then brought into contact and allowed to
cool to provide a hermetic seal. The main variations of heated tool welding are hot
plate, socket, butt fusion and saddle. The technique may be used to weld most
thermoplastics. If the correct procedures are used, the weld strength may be equal to the
tensile strength of the parent material. It is a relatively slow welding process; weld
times can range from 10 seconds for small components to 60 minutes for components
with large weld area. The main welding parameters are the temperature of the hot plate,
the heating time, the welding pressure and the welding time.
For welding PP pipes, socket welding is used where a heated pipe is inserted into a
heated fitting. It is reported to be the preferred method for joining PP pipes for domestic
installations. Electrofusion fittings are used in exceptional circumstances where socket
welding is not possible. Heated element butt fusion is the most common method of
joining PP pipes for industrial applications. The cut surfaces of the pipes are planed,
heated in contact with a heated element, and then joined and cooled under pressure.
Valves and other armatures can be incorporated by flanging, welding or threading.
In hot gas welding, a stream of hot gas, typically air, is directed towards the joint
between the two thermoplastics parts to be joined, where it softens or melts the
polymer. A thermoplastic filler rod may also be used to form a weld. Hot gas welding is
a manual process and the quality of the bond depends on the skills of the operator. The
adjustable parameters are gas type, flow rate and temperature, and the angle of the filler
rod to the parts being welded. The variations of the hot gas welding technique are hand
welding, speed welding and extrusion welding.
In friction welding, the heat needed to melt the thermoplastic material is generated by
pressing one of the parts to be joined against the other and rapidly vibrating it. If the
correct procedures are used, weld strength could be equal to the tensile strength of the
parent material. The heat generated by the friction melts the material at the interface
between 2–3 seconds. Further time is required to align the parts and to hold them
together under pressure until a solid bond is formed. The main welding parameters are
rotational speed, friction pressure, forge pressure, displacement and duration. The main
variations of frictional welding are linear vibration welding, orbital friction welding
(circular movement), spin welding and angular friction welding.
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In ultrasonic welding, the high frequency sound energy is used to soften or melt the
thermoplastic at the joint. Parts to be joined are held together under pressure and are
then subjected to ultrasonic vibrations usually at a frequency of 20 to 40 kHz. It is a
very fast welding process and can be easily automated. The main advantages are fast,
strong, clean and reliable welds. Due to the semi-crystalline nature of PP with a sharp
melting point, PP is not as easily weldable as PS. However, good results may be
obtained by near field ultrasonic welding. PP does not transmit ultrasonic waves well
enough to weld it using far field ultrasonic welding.
In the laser welding technique, a high intensity laser beam is used to increase the
temperature at the joint interface of thermoplastic material to or above the melting
point.
In IR welding, the joining surfaces are heated to the melting temperature using IR
radiation. When melting begins, the parts are brought together under pressure, forming
the weld on cooling. IR joining systems have been tried on PP, and joints with a
welding factor greater than 0.9 (1 represents the ideal) at –40 °C testing temperature
have been reported.
The use of these welding techniques is not yet well established for PP.
The high solvent resistance of PP prevents the solvation of the moulding surface, and,
therefore, solvent bonding is not possible.
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For adhesive gluing, the surfaces to be joined must be adequately treated to improve
adhesion. Flaming, corona discharge and primer are used for surface treatment. The
methods for surface treatment are similar to those used for decorating and printing
(Section 7.3). Adhesives used for bonding of PP are contact adhesives based on
polyurethanes or synthetic rubber, two-pack adhesives based on epoxy resins,
polyurethanes, etc., vinyl acetate copolymer hot melt adhesives, pressure-sensitive
adhesives and polyurethane contact cements.
The strength of a bonded joint is highly dependent on its geometry and the adhesive
used. The factors affecting the choice of adhesive are resistance to various chemicals,
moisture, high temperature and vibrations. Testing of the bonded joint is necessary to
ensure optimum bonding is achieved.
7.1.4 Sealability
7.2.1 Machining
PP is a relatively soft material and is easy to machine. It can be easily machined with
carbide-tipped or high-speed steel tools on conventional metalworking or woodworking
machines. High cutting speed or low feed rates are required for optimal finishes. The
heat generated can be dissipated by cooling with fluids such as water and cutting
emulsions. Using sharp tools, PP can be machined using sawing, turning, milling,
planing, chiseling and drilling. Reaming, grinding, filling and polishing are less suitable
processes.
In snap-fit fastening, two parts are joined through an interlocking configuration that is
moulded into the parts. A protrusion on one part is briefly deflected during joining to
catch in a depression or undercut moulded into the other part. The force required for
joining varies depending on the part design. Depending on the locking angle, these
connections are either easily released or permanent. The high level of elasticity of PP
makes the material suitable for snap-fit joints. Snap-fit joints require more attention to
the engineering design and can fail during assembly or use if not designed properly.
They are commonly used in assembly of tools, housings, electronic components,
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medical devices, etc. The snap-fit joints may be designed to be stress free during use. If
not stress free during use, it will be subjected to creep and stress relaxation.
Two plastic parts may be joined using mechanical fasteners such as screws and bolts,
self-tapping screws or inserts. The fasteners may be reusable, if required, and can be
moulded in metal or plastic. Plastic fasteners are light in weight, corrosion resistant and
impact resistant. Use of fasteners requires that the plastic component can withstand the
stresses generated during insertion and the stresses left in the moulding near the
fasteners. The high stress produced near the fasteners can make the parts more
susceptible to chemical and thermal attack. The design stress, residual stress and
assembly stresses in the component should not exceed the maximum allowable stress
for the plastic. To reduce the stress concentration, inserts with smooth rounded surfaces
produce less stresses than knurled inserts. In addition, knit lines should not be located in
areas of the part that are being inserted.
7.3 Decorating
Surface pretreatment by flaming using a very oxygen rich burner flame or application
of electrical processes is usually required to improve the adhesion of printing inks and
coating to PP [31]. However, use of pretreatment, in some cases, may not be required
when primers are being used. A wide variety of equipment and devices are available for
pretreatment of PP. Corona discharge is preferred in the case of film. Pretreatment of
the film may be required before printing if the film has been stored for a long time.
Chemical pretreatment by dipping in a chromosulphuric acid bath is also possible. UV
irradiation treatment of a UV primer is also possible. It is reported as a reliable,
efficient and economical method for obtaining an improved level of adhesion of paint
on PP, even when the parts have complicated shapes [32]. The coating generally leads
to a reduction in the impact strength.
Printing processes suitable for PP include pad transfer, screen printing, laser printing,
dyeing, and fill and wipe. Due to the non polar nature of PP, the choice of primer or
surface treatment is very crucial for printability and paintability.
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Elastomer-modified grades of PP are more suitable for printing, painting and other
decoration techniques since etching of the rubber particles provides the location for
bonding of the primer to the surface of PP artefact. PP bumpers made with an EniChem
grade of EPR are said [33] to have paint cohesion 20 times higher than unmodified PP
or a reactor-modified PP, and over three times better than PP/EPR grades available
now.
Plastic surfaces can be given a metallic appearance using metallising and electroplating.
In vacuum metallising, the metal is heated in a vacuum chamber to its vaporisation
point, which is lower than the melt temperature of plastics. The metal vapour than
deposits on the cooler plastic surface. In electroplating, an electric current is used to
deposit metals from a metal salt solution onto a plastic rendered conductive by
electroless plating. Other techniques for depositing metal layers on plastic substrates are
flame/arc spraying and sputtering. Metallising requires a clean surface, free from mould
release agents. Primers or pre-cleaners can be used to improve the adhesion of the metal
to the polymer surface. The parts should have uniform walls and mouldings should be
stress free. Normal commercial metallising equipment is suitable for metallising of
plastic parts.
7.3.3 Appliques
The standard requirements for applying surface coverings are a clean surface free of
mould release agents with minimal sink marks and projections. The adhesive backing
must be compatible with the PP and should not cause cracking or crazing.
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8 Causes of Failure
Like other plastics, PP is not free from product failure during service. In a recent study
[34], the main reasons for failure in plastics, in general, are stated in decreasing order of
failures as environmental stress cracking, dynamic fatigue, static notch failure, creep
related failure, chemical attack, UV attack, heat degradation and wear/abrasion.
Environmental stress cracking, which is the largest reason of failure in other plastics, is
not very significant for PP. PP is virtually free from the problems of environmental
stress cracking.
Another major reason for the failure of plastic products is dynamic fatigue. However,
being a semi-crystalline material, PP offers better fatigue resistance than amorphous
thermoplastics. It should be noted that dynamic fatigue strength of PP is lower than that
of engineering plastics.
PP is not greatly used for wear and abrasive applications. Consequently, the examples
of PP with failure related to wear are extremely limited.
UV and heat degradation is another reason for short product life or catastrophic failure
in PP artefacts. Correct choice of the material and proper understanding of the service
environment is necessary. The UV resistance of PP depends on the thickness of the
artefact. Flame retardant grades have poor UV resistance.
Another cause of failure in PP artefacts is the poor quality of the weld lines. Weld lines
are inherent weak positions due to the poor fusion of the material at molecular level.
However, the strength of welds can be maximised by favourable moulding conditions
such as sufficiently high melt temperature, high tool temperature, heated metal inserts
and fast injection times. Similarly to other plastics, more attention should be paid to
filled or reinforced grades of PP.
PP artefacts are prone to severe shrinkage and warpage. Sensible product design and
processing parameters are the solution to the problem. If batch-to-batch variation in the
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shrinkage and warpage is observed at similar moulding conditions, the material should
be characterised for rheological behaviour.
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The issues relating to a PP article during its lifetime can be divided into the following
categories: material selection, design, processing and post assembly, performance in
service and environmental and legislative issues.
Impact properties: Significant cause of in-service failure. High brittle temperature. For
impact demanding applications or sub-ambient applications, consider block
copolymerised or elastomer-modified grades but improvement in impact properties at
the expense of stiffness. Avoid accidental mixing of homopolymer and copolymer
grades.
Wear and friction: Not very suitable for wear and friction applications. Consider PA or
acetals.
9.2 Design
Warpage: Serious problem. May cause high rejection rate during moulding. Consider
warpage at the design stage. Warpage reduced in controlled rheology or metallocene-
catalysed grades. Consider computer-based flow simulation at the mould design level.
Weld lines: Points of inherent weakness and lead to many failure problems. Particularly
important in reinforced grades, particularly with glass fibre. Use process conditions or
mould modification to improve weld strength.
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Thermoforming: Difficult. Narrow processing range, high forming pressure and extra
cooling required. Specialised machinery might be required.
Welding: Suitable welding techniques are friction, vibration, hot gas and hot plate
welding. Ultrasonic welding difficult while radio frequency welding not possible.
Adhesive gluing: Difficult to bond plastic, surface preparation very crucial. Proper
selection of glue necessary. Consider improved design to avoid the need for gluing or
use welding.
Thermal oxidation and heat stability: Poor thermal oxidation and heat stability.
Consider using thermally stabilised grades.
Fire resistance: Poor fire resistance. Fire retarded grades can offer up to V-0 rating.
Heat resistance very critical. Consider materials which are inherently fire retarded, e.g.,
PVC.
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Food applications: Check raw material compliance with various national and
international legislation. Pay special attention to elastomer-modified grades. Fire
retarded grades are not suitable. Consider organoleptic properties which might be a
problem with controlled rheology grades. Consider using metallocene-catalysed grades.
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References
1. M.C. Hough and R. Dolbey, The Plastics Compendium, Volume 1: Key Properties
and Sources, Rapra Technology Limited, UK, 1995.
4. W. Roels and D. Booth, Popular Plastics and Packaging, 1991, 36, 1, 45.
7. C. Paulik, M. Gahleitner and W. Neissl, Kunststoffe Plast Europe, 1996, 86, 8, 16.
8. W. Spaleck, B. Bachmann and A. Winter, Plastics Southern Africa, 1994, 23, 11,
16.
13. J. Sidwell, The Rapra Collection of Infrared Spectra of Rubbers, Plastics and
Thermoplastic Elastomers, Rapra Technology Limited, UK, 1997.
16. J.A. Brydson, Plastics Materials, 7th Edition, Butterworth-Heinmann, 1999, 258.
19. B.M. Lucas, J.P. Samuel and M.T. Thakkar, Engineering Plastics, 1991, 4, 4, 239.
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22. D.V. Rosato, D.V. Rosato and M.G. Rosato, Injection Molding Handbook, Third
Edition, Kluwer Academic Publishers, 2001.
23. H.J. Yoo and D. Done, Proceedings of Antec ’92, Detroit, Michigan, USA, 1992,
569.
24. R.J. Koopmans, Proceedings of Antec ’97, Toronto, Ontario, Canada, 1997, 1006.
28. T.M. Pontiff, Proceedings of Antec ’93, New Orleans, Louisiana, USA, 1993, 3047.
35. D.C. Wright, Failure of Plastics and Rubber Products, Rapra Technology Limited,
Shawbury, UK, 2001.
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Practical Guide to Polypropylene
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Practical Guide to Polypropylene
RM Rockwell M
RR Rockwell R
SAN Styrene-acrylonitrile copolymer
SD Shore Durometer
TGA Thermogravimetric analysis
TPX Polymethylpentene
UL Underwriters’ Laboratories
UPVC Unplasticised PVC
UV Ultraviolet
VOC Volatile organic compound
XRF X-ray fluorescence spectroscopy
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