The process of forming plastics into various shapes typically involves the steps of melting, shaping, and solidifying. As an example, polyethylene pellets can be heated above Tm, placed in a mold under pressure, and cooled to below Tm in order to make the final product dimensionally stable. Thermoplastics in general are solidified by cooling below Tg or Tm. Thermosets are solidified by heating in order to carry out the chemical reactions necessary for network formation.
In extrusion, a melted polymer is forced through an orifice with a particular cross section (the die), and a continuous shape is formed with a constant cross section similar to that of the orifice. Although thermosets can be extruded and cross-linked by heating the extrudate, thermoplastics that are extruded and solidified by cooling are much more common. Among the products that can be produced by extrusion are film, sheet, tubing, pipes, insulation, and home siding. In each case the profile is determined by the die geometry, and solidification is by cooling.
Longitudinal section of a screw extruder of thermoplastic polymers. Plastic pellets are fed from a hopper into the barrel of the extruder, where the pellets are gradually melted by mechanical energy generated by a turning screw and by heaters arranged along the barrel. The molten polymer is forced through a die, which shapes the extrudate into products such as the examples shown.
Most plastic grocery bags and similar items are made by the continuous extrusion of tubing. In blow extrusion, the tube is expanded before being cooled by being made to flow around a massive air bubble. Air is prevented from escaping from the bubble by collapsing the film on the other side of the bubble. For some applications, laminated structures may be made by extruding more than one material at the same time through the same die or through multiple dies. Multilayer films are useful since the outer layers may contribute strength and moisture resistance while an inner layer may control oxygen permeability—an important factor in food packaging. The layered films may be formed through blow extrusion, or extrudates from three machines may be pressed together in a die block to form a three-layer flat sheet that is subsequently cooled by contact with a chilled roll.
The flow through a die in extrusion always results in some orientation of the polymer molecules. Orientation may be increased by drawing—that is, pulling on the extrudate in the direction of polymer flow or in some other direction either before or after partial solidification. In the blow extrusion process, polymer molecules are oriented around the circumference of the bag as well as along its length, resulting in a biaxially oriented structure that often has superior mechanical properties over the unoriented material.
Blow extrusion of thermoplastic polymers. Molten extrudate is forced past a tubing mandrel, expanded into a balloon shape by a stream of air, drawn upward by rollers, and pinched into a collapsed sheet to be cut into a number of products.
In the simplest form of compression molding, a molding powder (or pellets, which are also sometimes called molding powder) is heated and at the same time compressed into a specific shape. In the case of a thermoset, the melting must be rapid, since a network starts to form immediately, and it is essential for the melt to fill the mold completely before solidification progresses to the point where flow stops. The highly cross-linked molded article can be removed without cooling the mold. Adding the next charge to the mold is facilitated by compressing the exact required amount of cold molding powder into a preformed “biscuit.” Also, the biscuit can be preheated by microwave energy to near the reaction temperature before it is placed in the mold cavity. A typical heater, superficially resembling a microwave oven, may apply as much as 10 kilovolts at a frequency of one megahertz. Commercial molding machines use high pressures and temperatures to shorten the cycle time for each molding. The molded article is pushed out of the cavity by the action of ejector pins, which operate automatically when the mold is opened.
In some cases, pushing the resin into the mold before it has liquefied may cause undue stresses on other parts. For example, metal inserts to be molded into a plastic electrical connector may be bent out of position. This problem is solved by transfer molding, in which the resin is liquefied in one chamber and then transferred to the mold cavity.
In one form of compression molding, a layer of reinforcing material may be laid down before the resin is introduced. The heat and pressure not only form the mass into the desired shape but also combine the reinforcement and resin into an intimately bound form. When flat plates are used as the mold, sheets of various materials can be molded together to form a laminated sheet. Ordinary plywood is an example of a thermoset-bound laminate. In plywood, layers of wood are both adhered to one another and impregnated by a thermoset such as urea-formaldehyde, which forms a network on heating.
It is usually slow and inefficient to mold thermoplastics using the compression molding techniques described above. In particular, it is necessary to cool a thermoplastic part before removing it from the mold, and this requires that the mass of metal making up the mold also be cooled and then reheated for each part. Injection molding is a method of overcoming this inefficiency. Injection molding resembles transfer molding in that the liquefying of the resin and the regulating of its flow is carried out in a part of the apparatus that remains hot, while the shaping and cooling is carried out in a part that remains cool. In a reciprocating screw injection molding machine, material flows under gravity from the hopper onto a turning screw. The mechanical energy supplied by the screw, together with auxiliary heaters, converts the resin into a molten state. At the same time the screw retracts toward the hopper end. When a sufficient amount of resin is melted, the screw moves forward, acting as a ram and forcing the polymer melt through a gate into the cooled mold. Once the plastic has solidified in the mold, the mold is unclamped and opened, and the part is pushed from the mold by automatic ejector pins. The mold is then closed and clamped, and the screw turns and retracts again to repeat the cycle of liquefying a new increment of resin. For small parts, cycles can be as rapid as several injections per minute.
Injection molding of thermoplastic polymers. (Left) Plastic pellets are fed from a hopper into a reciprocating screw injection molding machine, where they are melted by the mechanical energy exerted by a turning screw and by heaters arranged along the barrel. (Centre) The screw moves forward, injecting the molten plastic into a mold. (Right) After the plastic has solidified, the mold is opened and the molded piece ejected.
Reaction Injection Molding
One type of network-forming thermoset, polyurethane, is molded into parts such as automobile bumpers and inside panels through a process known as reaction injection molding, or RIM. The two liquid precursors of a polyurethane are a multifunctional isocyanate and a prepolymer, a low-molecular-weight polyether or polyester bearing a multiplicity of reactive end-groups such as hydroxyl, amine, or amide. In the presence of a catalyst such as a tin soap, the two reactants rapidly form a network joined mainly by urethane groups. The reaction takes place so rapidly that the two precursors have to be combined in a special mixing head and immediately introduced into the mold. However, once in the mold, the product requires very little pressure to fill and conform to the mold—especially since a small amount of gas is evolved in the injection process, expanding the polymer volume and reducing resistance to flow. The low molding pressures allow relatively lightweight and inexpensive molds to be used, even when large items such as bumper assemblies or refrigerator doors are formed.
The popularity of thermoplastic containers for products previously marketed in glass is due in no small part to the development of blow molding. In this technique, a thermoplastic hollow tube, the parison, is formed by injection molding or extrusion. In heated form, the tube is sealed at one end and then blown up like a balloon. The expansion is carried out in a split mold with a cold surface; as the thermoplastic encounters the surface, it cools and becomes dimensionally stable. The parison itself can be programmed as it is formed with varying wall thickness along its length, so that, when it is expanded in the mold, the final wall thickness will be controlled at corners and other critical locations. In the process of expansion both in diameter and length (stretch blow molding), the polymer is biaxially oriented, resulting in enhanced strength and, in the case of polyethylene terephthalate (PET) particularly, enhanced crystallinity.
Blow molding has been employed to produce bottles of polyethylene, polypropylene, polystyrene, polycarbonate, PVC, and PET for domestic consumer products. It also has been used to produce fuel tanks for automobiles. In the case of a high-density-polyethylene tank, the blown article may be further treated with sulfur trioxide in order to improve the resistance to swelling or permeation by gasoline.
Blow molding of plastic containers. (Counterclockwise from top) A molten polymer is extruded into a hollow tube-shaped parison. A split mold is closed around the parison, which is expanded against the sides of the mold by a stream of air. Once the plastic has solidified, the mold is opened and the shaped bottle released.
Casting And Dipping
Not every forming process requires high pressures. If the material to be molded is already a stable liquid, simply pouring (casting) the liquid into a mold may suffice. Since the mold need not be massive, even the cyclical heating and cooling for a thermoplastic is efficiently done.
One example of a cast thermoplastic is a suspension of finely divided, low-porosity PVC particles in a plasticizer such as dioctyl phthalate (DOP). This suspension forms a free-flowing liquid (a plastisol) that is stable for months. However, if the suspension (for instance, 60 parts PVC and 40 parts plasticizer) is heated to 180 °C (356 °F) for five minutes, the PVC and plasticizer will form a homogeneous gel that will not separate into its components when cooled back to room temperature. A very realistic insect or fishing worm can be cast from a plastisol using inexpensive molds and a cycle requiring only minutes. In addition, when a mold in the shape of a hand is dipped into a plastisol and then removed, subsequent heating will produce a glove that can be stripped from the mold after cooling.
Thermoset materials can also be cast. For example, a mixture of polymer and multifunctional monomers with initiators can be poured into a heated mold. When polymerization is complete, the article can be removed from the mold. A transparent lens can be formed in this way using a diallyl diglycol carbonate monomer and a free-radical initiator.
In order to make a hollow article, a split mold can be partially filled with a plastisol or a finely divided polymer powder. Rotation of the mold while heating converts the liquid or fuses the powder into a continuous film on the interior surface of the mold. When the mold is cooled and opened, the hollow part can be removed. Among the articles produced in this manner are many toys such as balls and dolls.
Thermoforming And Cold Molding
When a sheet of thermoplastic is heated above its Tg or Tm, it may be capable of forming a free, flexible membrane as long as the molecular weight is high enough to support the stretching. In this heated state, the sheet can be pulled by vacuum into contact with the cold surface of a mold, where it cools to below Tg or Tm and becomes dimensionally stable in the shape of the mold. Cups for cold drinks are formed in this way from polystyrene or PET.
Vacuum forming is only one variation of sheet thermoforming. The blow molding of bottles described above differs from thermoforming only in that a tube rather than a sheet is the starting form.
Even without heating, some thermoplastics can be formed into new shapes by the application of sufficient pressure. This technique, called cold molding, has been used to make margarine cups and other refrigerated food containers from sheets of acrylonitrile-butadiene-styrene copolymer.