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Lubricants are added to most polymers at low levels to increase the overall rate of processing or improve surface parameters. They have been used in the past to facilitate extrusion, injection, compression etc. of many polymers

Most used lubricants; Ca and Zn stearates 45% Waxes 23,5% Fatty acid amines 19% Fatty acid esters12%
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Lubricants often improve the properties of the products; Brightness Heat stability in the course of a processing operation Light stability Resistance to degradation by corrosive agents and to water absorption Better dispersion of additivies Improved electrical optical and mechanical properties etc. Stearic acid and its Ca, Li, Ba, Al, Pb etc., salts, Natural waxes Microcrystalline paraffins with high melting point Mineral and vegetable oils Whale fat
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Some examples;

A main function of lubricants is to prevent polymers that have a tendency toward tackiness from sticking on metallic parts of processing machinery; this is external lubrication. Another important function is to provide internal lubrication to the polymer under processing to improve the free flow of the melt bulk polymer by reducing friction between chain segments.

These two combined functions give a better outform the processing equipment and also they facilitate mold release.

The lubricant acts exactly as an oil in the case of bearing lubrication and the spherical agglomerates slide directly on a lubricant layer. With a melt polymer a melt lubricant may form either a homogeneous phase or a mixture of the two separate liquids according to their mutual miscibility. This is the reason that melt PVC and a lubricant may form a two phase system at least , made of spherical PVC agglomerates dispersed in a liquid solution of PVC single molecules and the melt lubricant or in the melt lubricant alone if it is not miscible with PVC

The effect of lubrication on the processibility for three thpes of differently polymerized PVC; c1: the emulsion polymerized polymer contains emulsifiers that act as lubricant. Only this type of PVC with low molecular weight can be processed without lubricant.

Other important consideration in selection 1- mutual interaction between lubricants and other additivies 2- the way and conditions of processing polymer compounds

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To be effective lubricant should be slightly soluble in the polymer and should have some cohesion with polymer molecules in order to exude too easily It should be a long chain hydrocarbon ended by a polar group Its melting point should be such that the film produced at the surface of the polymer particles is strong enough

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According to their action 1-external 2-internal External Lubricant; very low solubility in the polymer; they exude partially from the bulk,creating a separating layer between the polymer and the metal surface of the processing machine.

Polar end of the lubricant molecules is strongly adsorbed to the metal surface. The strength of the bond between a lubricant and the metal surface depends on the nature of the metal surface so as to form a stationary layer of lubricant molecules that then initiates the formation of multimolecular layer as shown in fig. 2.6 ; The strength of the bond between a lubricant molecule and the metal surface depends on the nature of the metal surface ; it determines whether the adsorption is physical or chemical in nature. If the lubricant is an acid such as lauric acid it reacts with metals such as Cd and Zn but not with Ag,Al,Ni,Cr etc..
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Internal lubricants; which have a good affinity to the polymer and reduce its viscosity in the melt state. They reduce the heat produced by the action of the friction forces. They also affect elastic behaviour in the course of succesive processing steps (swelling-melt fracture etc.) It has also been observed that external lubr. extend the plastication time of PVC comp.s and that internals reduce it.

The limit of the affinity between a polymer and a lubricant is criterion for the diffrentiation A lubricant begin to act as an external above a given concentration in the polymer. If the affinity to the polymer is limited mechanical properties vary with its concentration before the limited affinity is attained. In such cases that substance functions as a plasticizer.
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Saturated hydrocarbons, lubrication efficiency increases with the chain length. Solid paraffins(polyethylene waxes Mw: 2000-10000) are more effective than parraffin oils or low-melting paraffins (Mw:200-400) Fatty acids;mainly as external lubricants. The higher molecular weight acids have a greater affinity to PVC. Stearic acid is the one most used (low priceavailability). Commercial materials used as lubricants usually contain from 40% to 97% stearic acid and the rest is made of palmitic, myristic and oleic acids.

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High molecular weight alcohols;differ from fatty acids in their actions. They have more affinity to PVC and do not exude at concentrations used in practice(~2%). They are considered internal lubricants. ie: cetylstearyl alcohol. Metal soaps: external lubricants and are among best mold release. In some cases they improve heat and light stability of PVC( ie: Li,Sr, Ca, AL,Ba, Pb) Waxes: esters of fatty acid and high molecularweight monofunctional alcohols. The two long chains attached to the polar group produce very good lubrications ie: wax from partially saponified montanic acid,ester with C28 and C32 chains,stearyl stearate.

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Fatty acid monoesters; good molding properties and act as secondary plasticizers, affecting the mech. properties. ie: butyl and octyl stearates Partially esterified polyfunctional alcohols by fatty acids; 3 different types 1-Hydrogenated tallow glycerides (HTG) CH3(CH2)16COOCH2 CH3(CH2)16COOCH CH3(CH2)16COOCH2 2- Glyceryl monostearates (GMS) or glyceryl monoricinoleates 3- Esters of sorbitol, ethylene glycol,propylene glycol, pentaerythritol and high molecular weight alcohols. Act as internal lubri. Fatty acid bisamides; have outstanding external lubrcation properties

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Some commercial products improves rheological properties of the melt bulk polymer and brilliance of the surface of finished products without affecting machenial properties. Some of them also act as antistatic agent. Polyethylene (PE) Mw:2000 is recomended Fatty acid amide,calcium stearate, sodium stearate are some examples

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Normal rules for selection; Metal soaps, mainly stearates, function as external lubricants, since they have low affinity to all polymers Long-chain fatty acids, alcohol and amides act as internal lubr. for polar polymers such as PVC, pA etc. But have low aff. to non polar polymers (polyolefins) Long chain dialkyl esters have med. aff. to most polymers and can act both int. and ext lub., they often used to obtain a balanced lubrication High-Mw paraffin waxes function as external lubr. For polar polymers,(low aff.) but they have high aff. to polyolefins then they used as int.lubr.
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Table 2.1; most used lubricants

Different lubr. are used together to obtain special properties for plastic materials. Total quantity used vary 1%-2% They can be added during preparation of compounds, to the extruders or in the course of polymerization react.
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Mold release is facilitated by a better design of molds by keeping walls of the molds clean and polished, and by reducing the friction coefficient between plastic materials and molds The use of mold release agents increases the productivity of molding process such as compression molding, injection molding, production of plastic bottles by extrusion blowing, or injection blowing.
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Waxes, soaps, and silicones are used. Paraffin waxes are not very convenient Soaps offer a better adhesion to metals because of the polar part of their molecules. However they also can be removed by plastic materials, since they have a long and bulky nonpolar chain that is weakly attached to the metals surface by only one point.

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Silicones, mainly polydimethylsiloxane, are excellent mold-release agents. Their chain contains numerous polar groups that adhere strongly to the metal surface and their methyl groups pointing away from the surface facilitate the flow of the melt plastic material. Silicones function thus as a permanent separation layer. Their heat stability is relatively high (~300C) and no C film is formed when they decompose. However their presence creates some problems when impression or metallization is to be done afterward on the surface of the products. Mold-release agents are used in the form of powders, oils or jellies, solutions, sheets or films. As sheets, cellophane, PV AL, CA and so on, are used.

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