Impact of lubricants on processing behaviour of U-PVC

B. Treffler*
The influence of different chemical classes of waxes, used commercially as internal and external lubricants, on the processing behaviour of PVC in profile extrusion is described, drawing on the results of systematic laboratory testing. The present study concentrates on long chain ester waxes, oxidised polyethylene waxes and polyethylene/polypropylene waxes. The last of these three product groups covers the state of the art polyethylene waxes and the new class of metallocene waxes. The influence of the waxes on processing behaviour has been analysed on the basis of extruder pressure and screw torque measurements and extruder energy consumption. The influence of lubricants on the surface quality of profiles is also considered. It is concluded that the effect of PO-waxes and oxidised PE-waxes on the processing behaviour can be correlated with product parameters such as crystallinity, viscosity and acid value. Long chain ester waxes, i.e. montanic waxes, provide additional effects and allow for the adjustment of individual processing parameters.
Keywords: PVC, Profile extrusion, Lubricants, Waxes, Polyethylene waxes, Metallocene waxes

Introduction
The quality characteristics (surface nish etc.) of U-PVC extrusions are critical for customer-sensitive applications such as window frames and other architectural components. These characteristics and the processability of PVC during extrusion and other processing operations can be tailored by the use of lubricants. Systematic laboratory testing with various classes of wax lubricant (long chain ester waxes, oxidised polyethylene waxes and polyethylene/polypropylene waxes (including state of the art polyethylene waxes and metallocene waxes) has been conducted to investigate their effect on the processing behaviour of PVC. It has proved possible to correlate wax properties with product parameters and also, with appropriate formulations, to tailor the processing properties of PVD during extrusion.

processing, just particle ow. Suitable lubricants are able to delay or accelerate this process.

Chemical structure and polarity

The structure and, importantly, the polarity of the lubricants are decisive factors during PVC processing (Fig. 2). External lubricants, which are less compatible with the plastic matrix, act as a lubricating lm between the polymer melt and the hot metal parts of the processing machine. Internal lubricants take effect primarily between the particles (polymer chains). However, very few lubricants can be classied purely in one group or the other.36 Their effects usually

Morphological structure of PVC

The PVC particles used for processing (secondary particle) are made up of so-called primary particles or globules (Fig. 1), which are about 1 mm in size. These globules in turn consist of nodules about 10 nm in size. At processing temperatures up to 190uC, the secondary particles break down into globules, a process normally referred to as plasticisation. Above about 190uC, these in turn break down into nodules, a process referred to as gelation.13 Thus, there is not a pure melt during PVC
Clariant GmbH, Gersthofen, Germany *Corresponding author, email beate.treffler@clariant.com

1 Morphological structure of PVC

2005 Institute of Materials, Minerals and Mining Published by Maney on behalf of the Institute Received 29 April 2005; accepted 19 May 2005 DOI 10.1179/174328905X55506

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4 Lubricants in PVC mode of action 2 Classication of various lubricants by their effect on PVC

overlap and also depend on the concentration (solubility limit).

globules. The characteristics of the nal particles are not affected by the quantities that are normally used. Typical representatives of internal lubricants are glycerol mono-oleate (GMO), glycerol mono-stearate (GMS), and stearyl-stearate.

Model of flow behaviour

Internal lubrication assumes wall adhesion of the polymer melt. The ow velocity in a die (laminar ow) increases from zero at the wall to a maximum at the centre of the die (Fig. 3a). The higher the internal lubrication effect, the higher the rate of ow (constant processing parameters). External lubrication however removes this basic assumption of ideal wall adhesion. These lubricants form the lubricating lm mentioned earlier. The ow front moves equally fast across the die, and it is also referred to as block ow (Fig. 3b).7

Gelation behaviour and release effect

Gelation of PVC is delayed primarily by the reduction in wall adhesion. As the non-polar remnants of the lubricant molecules become longer, they are less able to penetrate the PVC particle, and the external proportion of the lubrication effect increases. The polyolen and parafn waxes represent an extreme case. They do not dissolve in PVC, are displaced from the melt, and are deposited between the metal and the melt. As a result, however, they are also susceptible to incompatibility reactions, such as plate-out. Between the two extremes mentioned, polar/internal and nonpolar/external lubricants (Fig. 4), there is a wide range. Oxidation of polyethylene waxes can produce polar wax oxidates. Ester waxes made up of long-chain non-polar remnants also display an external lubricant effect and form a lubricating lm (Fig. 4). Montanic acid esters are typical examples of such ester waxes. Thanks to their polar groups, they are anchored to the globules adequately enough that no plate-out occurs and no negative effect upon melt strength and Vicat softening point can be observed.3,4,8

Mode of action of lubricants

Viscosity reduction
Lubricants with high polarity and short C-chains have a relatively high ability to penetrate the PVC particle. The extreme case is represented by plasticisers, which permeate the entire particle and thus change not only the viscosity, but also the hardness of the nal product. However, internal lubricants penetrate the particle to only a limited extent and reduce friction between the

3 Inuence of velocity of ow front by a internal and b external lubricating effect

5 Test formulation (based on Ca/Zn-stabilised window prole compound)

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6 Pressure formation/single screw, 60 rev min21 9 Pressure formation/single screw

7 Energy consumption/twin screw, at die

10 Energy consumption/single screw I

8 Gloss of proles/twin screw extrusion

From theory to practice

How do external lubricants inuence the processability of a PVC-window prole compound? This will be discussed now in the context of the experimental results obtained with extruders in the present study.911 Figure 5 lists the basic formulation used for the tests examining the processing properties of various external lubricants; the behaviour observed is correlated with product properties. This will facilitate the choice of lubricant required for optimum production. The structures and properties of the commercial formulations used in the tests are summarised in the Appendix.

11 Energy consumption/single screw II

PE/PP-waxes in PVC extrusion

In these compounds, the non-polar and thus incompatible waxes act as external lubricants which regulate

or delay the gelation process. Furthermore, in the main, they provide a stronger die lubrication and higher gloss. The crystallinity of the waxes plays a decisive role. High crystallinity leads to stronger external lubrication which is visible in low pressure formation (Fig. 6) and lower energy consumption (Fig. 7) (mPP-Wax 6102, PPWax). Less strongly but nevertheless remarkably, the

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12 Gloss/single screw 14 Energy consumption/twin screw, at die

low viscosity of the wax promotes a similar behaviour (mPP-Wax 6102). On the other hand, high pressure formation/energy input can be achieved with waxes having low crystallinity and high viscosity (mPP-Wax 1502) (Figs. 6 and 7). Both metallocene PP-waxes provide positive effects on surface properties (Fig. 8).

Oxidised PE-waxes in PVC extrusion

These polar and therefore partially compatible lubricants increase pressure formation (Fig. 9) and energy input (Figs. 10 and 11) in the extruder leading to earlier gelation. A correlation between grade of oxidisation with respect to viscosity of the wax and extent of inuence on rheology can be found. Also, gloss is positively inuenced (Fig. 12). Within this product group, the rate of oxidation and the viscosity play key roles. The higher the acid value (measurement of oxidation rate), the higher the energy input and pressure formation (ox. PE-Wax 153) (Figs. 9 and 10). Also increasing the viscosity of the wax provides similar behaviour in the extruder. High viscosity leads to higher energy input/pressure formation (ox. PE-Wax 29) (Figs. 9 and 11). With all the tested oxidised PE-waxes, the surface properties were positively inuenced (Fig. 12).

additional effects which differ from those discussed above in the context of polyolen waxes (PO-waxes). The montanic acid ester waxes demonstrate that pressure formation in the extruder can be reduced (Fig. 13), but at the same time the rheology (measured by energy consumption, this time for a twin screw machine) remains at the same level (Fig. 14). This effect is contrary to the behaviour when increasing the dosage of PE-/ox. PE-Wax in order to reduce pressure. In this case, the rheology is noticeably inuenced. As can be seen in Fig. 15, the gloss was signicantly increased by use of the complex ester but little effect was observed for the other compounds.

Summary
1. The impact of PO-waxes and oxidised PE-waxes on the processing behaviour is not a black box but can be correlated with product parameters such as crystallinity, viscosity and acid value. 2. Long chain ester waxes, i.e. montanic waxes, provide additional effects and allow for the adjustment of the individual processing parameters. This knowledge enables the prole producers to select the optimised lubricant combination for the process.

Montanic acid ester waxes in PVC extrusion

Commonly used in high-end, Pb-stabilised proles and in Ca/Zn-stabilised formulations, Montan waxes provide

Acknowledgements
Based on a presentation at the 9th International PVC Conference held in Brighton, UK, in April 2005.

13 Pressure formation/single screw, 50 rev min21

15 Gloss/twin screw, at die

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Appendix

References
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6. H. Zweifel (ed.): Plastics additives handbook, 5th edn, 542; 2001, Munich, Hanser Publishers. 7. H. Zweifel (ed.): Plastics additives handbook, 5th edn, 514; 2001, Munich, Hanser Publishers. 8. H. Zweifel (ed.): Plastics additives handbook, 5th edn, 517; 2001, Munich, Hanser Publishers. 9. G. W. Becker and D. Braun (eds.): Kunststoff handbuch, vol. 2/2, 905936/942950; 1986, Munich, Hanser Publishers. 10. H. Zweifel (ed.): Plastics additives handbook, 5th edn, 532534; 2001, Munich, Hanser Publishers. 11. Plastics extrusion technology, 2nd edn, 7995; 1997, Munich, Hanser Publishers.

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