MOLDING OF RUBBER FOR HIGH PERFORMANCE M1. May APPLICATIONS* J.G. Sommer GenCore, Research Division, 2990 Gitcut St ROAD, AKKON, Onto 44305 CONTENTS Introduction... Discussion ..... A. Molding methods : 1. Compression molding ..... 2. Transfer molding 3. Injection molding B. Molds . os 1. Materials . 2. Design factors C. Compounding considerations. 1.” Materials and properties 2. Shrinkage ...... D. Additional molding con: 1, Rheology 2. Backrinding 3, Mold fouling . 4. Inserts . 5. Control Highperformance 9 Seals .. 1. O-Rings 2. Lip seals ‘ B. Bearings and mounts. 1, Bridge bearings 2. Engine mounts ...... 3. Nozzle bearings G. Electrical applications . 1. Spark plug boots 2. Electrical connectors Summary . References 1, INTRODUCTION High-performance (HP) rubbers or elastomers are defined by Malcolmson as being substantially more resistant than general purpose elastomers to heat, oil, weather, or a combination of these', Examples of general purpose elastomers “Presented at a Meeting of The Rubber Division, American Chemical Society, Indianapolis, Indiana, 8-11, 1984. B. 662MOLDING 663 are natural rubber (NR) and styrene-butadiene rubber (SBR). NR is considered here as an HP rubber because it forms crystallites when strained. Excellent fatigue resistance and high strength are a consequence of these crystallites. These prop- erties are needed in some molded products for HP applications. ‘As used here, the term “molding” refers to the act or process of shaping millable elastomers in a mold. Discussion is limited to elastomers which are cross- linked in molds, ie., thermoplastic elastomers are not discussed. This paper broadly considers rubbers, molding methods, and some problems associated with molding for HP applications. Molding procedures are then re- viewed for several products used in HP applications. Il. DISCUSSION ‘The elastomers discussed are NR, SBR, chloro-sulfonyl-polyethylene rubber (CSM), silicone rubber, hydrofluoroelastomer (FKM), perfluoelastomer (PFE), chloroprene rubber (CR), and nitrile-butadiene rubber (NBR). Brief mention is made of ethylene/acrylate elastomer and polyphosphazene elastomer. These elas- tomers are molded by compression, transfer, or injection. ‘A. MOLDING METHODS Several advantages and disadvantages are compared below for compression, transfer, and injection molding. 1. Compression molding.—Simplicity of design and use are advantages for compression molding. Mold damage caused by removing compression molds from presses is a disadvantage’. Another disadvantage is poor control of the closure dimension (Figure 1). During mold closing, rubber flows from the mold cavity and partially fills the flash grooves. It is the flash between the cavity and the groove that causes the most variation in closure dimensions. Hence, the vertical or closure dimension for compression molded parts is less well-controlled than comparable dimensions for transfer or injection molded parts. 2. Transfer molding.—By this method (Figure 2), rubber is forced from a tansfer pot, through a sprue, and then into a mold cavity to form a molded rubber part. The flash pad remains in the transfer pot until it is removed after FLASH GROOVE PARTING LINE CLOSURE DIMENSION RUBBER OIMENSION Fic. 1—Compression mold showing fixed and closure dimensions of a molded rubber part.664 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 58 PLUNGER TRANSFER POT FLASH PAD — acess oS Z eZ PART MOLDED RUBBER Fic, 2.—Transfer mold with flash pad and molded rubber part. completion of the molding cycle. An advantage of transfer molding, relative to compression, is better dimensional control’. Control is better because rubber enters a closed mold. Another advantage is that a freshened rubber surface is presented to adhesive- coated inserts; this favors the good adhesion often required of HP rubber parts containing a mold-bonded insert?. A disadvantage of transfer molding is the scrap associated with the flash pad (Figure 2). This scrap can be considerable for high-viscosity rubber compositions required in some HP applications. Both transfer and injection molding share the advantage that preheated rubber enters mold cavities; cure time is shortest for injection molding because hotter rubber enters cavities. 3. Injection molding —The design of injection molding machines evolved from the simple ram type machine to a machine with a combined screw and ram. The best features of both of these are combined in a modern injection machine which is shown schematically in Figure 8. These features include good temperature control in the barrel and a rotating screw which pumps heated rubber into the injection chamber via a 3-way valve®. After the desired amount of rubber is metered into this chamber, the ram advances to push rubber through the valve into the mold. Some machines use a screw which functions as both a screw and ram. An advantage to having a separate ram is that clearance? between ram and chamber wall can be as little as 0.05 mm. With this small clearance, leakage of rubber past the ram is less than for a screw machine in which the screw also functions as a ram. Hence, the ram in Figure 3 can generate extremely high pressure (to about. 200 MPa)’. Pressures like this are sometimes necessary to cause adequate flow of high viscosity rubber required for some HP applications. High pressure forces rubber through the sprue, runners, and gates (Figure 4)'. A gate is the final restrictive pathway into a mold cavity. Restrictions in the gate and nozzle, along with high pressure, cause rubber to flow at extremely high shear rates in these restrictions. Associated with this high flow rate is a substantial increase in rubber tem- perature. As a result, cure times for injection molding are short relative to compression and transfer molding; this difference is even more pronounced for thick parts. The shorter cure times for injection molding are also partly due to the higher temperatures typically used with injection molds.MOLDING 665 BARREL RAM INJECTION CHAMBER VALVE HEATING FLUID HEATING FLUID zy NOZZLE MOLD Fic, 3—Injection molding machine with separate screw and ram. SECONDARY RUNNERS FiG. 4.—Distribution system for an injection mold. After Reference 4666 RUBBER CHEMISTRY AND TECHNOLOGY VoL. 58 B, MOLDS Materials and design factors for molds are briefly reviewed. These can affect the quality of rubber parts used in HP applications. 1. Materials —The choice of materials for molds is influenced by a number of factors. Two important factors are mold hardness and the tendency for some rubber compounds to corrode molds. Demands are especially severe for materials used in injection molds’. These molds must often withstand considerably higher temperatures and pressures than those encountered by compression and transfer molds. For molds used for mak- ing rubber parts with close tolerances, stress-relieved steel might be used?, Cavities can be made from tool steel hardened to Rockwell C60. To favor long mold life, Dym! recommends heat treating mold steel to Rockwell C54—C56; this treatment can be followed by plating with a hard chromium layer. A chromium layer imparts a desirable surface finish required on some HP molded parts. It also protects mold surfaces against corrosion caused by certain rubber compositions. For example, a chromium surface exhibits excellent cor- rosion resistance to CSM (chloro-sulfonyl-polyethylene) rubber’. In the absence of chromium, it is possible for CSM compounds to liberate sulfur dioxide and attack unprotected steel surfaces of molds. This attack can cause mold pitting which in turn affects the appearance of molded parts; pitting can eventually cause parts to stick and tear. For long production runs of CSM compounds, stainless steel molds are recommended. 2. Design factors.—Mold design is an important consideration because it crit- ically affects the accuracy of finished products, whether they be made by compres- sion, transfer, or injection. If compression molded parts are to have accurate dimensions, the mold must be sufficiently rigid to resist distortion, The press used for the mold must be in good condition. The platens on the curing press must be parallel; otherwise, the flash on the compression mold will not be of uniform thickness. This parallelism, while still important, is less critical for transfer molded parts. Some nonparallelism? is accommodated between plunger and transfer pot in a transfer mold (Figure 2). This causes nonparallel faces on the flash pad rather than in the horizontal faces of a compression molded part. Another design factor is the vertical clearance between the plunger and the wall of the transfer pot? which is typically about 0.12 mm. This clearance is large enough to prevent binding between plunger and transfer pot; it is small enough to prevent significant leakage of compound from the transfer pot. Leakage is an important consideration for costly compounds molded for HP applications. For these applications, multicavity transfer molds are often used rather than single-cavity molds. Uniform filling of these cavities is difficult. The high re- sistance to transverse flow of rubber in the transfer pot causes this difficulty. This resistance increases sharply as the transfer pad decreases in thickness. As a result, cavities in a transfer mold fill nonuniformly with time. This can cause unfilled central cavities if a flash pad is too thin. Increased flash pad thickness generally solves this problem; this solution increases the volume of rubber required and, hence, the cost. Nonuniform filling of multicavity injection molds is also a problem. A typical distribution system for a multicavity injection mold? is shown in Figure 4. Instead of the sprue directly entering the mold (Figure 3), the sprue enters primary runners. These then distribute rubber sequentially into drops, secondary runners, gates, and finally into cavities to form molded parts. TheMOLDING 667 symmetry shown in Figure 4 favors uniform filling of cavities in an injection mold. Gate location is important for injection molds, especially when adhesive-coated inserts are bonded to a molded part. If a gate is improperly located in a mold, impinging rubber can remove adhesive from an insert. This could cause a lo- calized nonbonded region (discussed later under inserts). With critical parts like O-rings, the gate should be small; it should be located to provide a desirable molded surface after trimming. It is also important to locate the gate so that rubber knits in a noncritical region of a part. Strength at the knit line may be only 90-95% of the strength in a nonknit area’, Special molds have been designed to prepare tensile specimens for examination of strength in knit lines'®. Ic is also important to vent air so as to prevent air entrapment in moldings and between rubber and mold surface. Vents are especially important in injection molds because rubber is often injected into cavities in only several seconds. This rapid filling compresses air and sharply raises its temperature; this high tem- perature can degrade rubber surfaces. To prevent this, vents must be sized and located to effectively remove air from cavities. As an alternative to vents, a vacuum can be applied to cavities. With either method, the vent or vacuum port should be located at the last part of the cavity to fill. Another important consideration is the type of compound to be molded. C. COMPOUNDING CONSIDERATIONS When a rubber technologist designs a rubber compound for an HP appli- cation, a number of difficult choices are required. These include the type of rubber, as well as the type and level of ingredients, eg., fillers and curatives. These choices affect not only end-use properties, they also affect molding be- havior. The relationship among materials, molding behavior, and end-use prop- erties is discussed, with emphasis placed on NR. 1. Materials and properties Table I shows the effect of the type of crosslinking TapLe I? CROSSLINKING SYSTEMS IN NR’ Crosslinking System Conventional Semi-EV EV Ingredients julfur 25 12 0.33 CBS accelerator® 05 18 3.0 TMTD accelerator’ - - 20 Properties looney scorch time, f, at 120°C, min. 18.5 16 8 Fatigue life’, ke 162 120 50 Compression sev, % 31 18 13 *After Reference 11 ‘RSS| 100; HAF black 50; process oil 4; zinc oxide 3.5; stearic acid 2.5; antioxidant 2. 2 = oe 7 a2 oS ° eu af 20 o= 8 LOG SHEAR RATE, s7! Fic. 6.—Effect of temperature and shear rate on viscosity. After Reference 17. MOLD TEMP. °c) 160 8 OR 180. \ RUBBER TEMP. IN BARREL (°C) 3 8 10 20 30 40 50 FILL TIME (S) Fic. 7—Effect of operating variables on the operable region (OR) for an injection molding process. ‘After Reference 17.MOLDING 671 shows that viscosity of a rubber compound decreases sharply as shear rate increases". Increasing temperature causes a less pronounced decrease in viscosity. In practice, lower viscosity aids flow of a compound during molding. During the injection molding process, considerable viscosity reduction occurs in the high- shear-rate regions, eg., the gate in Figure 4. In these high-rate regions, viscosity during injection is about one hundredfold lower than that for compression (Fig- ure 6). It is this sharp viscosity reduction that allows injection molds to fill in a very short time. While increasing temperature of a compound further reduces viscosity, scorch must be avoided. Figure 7 illustrates the relationship among rubber temperature in the barrel, mold temperature, and fill time for an injection molding process”. This figure shows the combinations of these three factors which produce completely filled parts that are free of scorch. The area in the figure where this occurs is called the operable region (OR) ‘The OR is bounded on one side by the heavy dark line; the crosshatched region to the left of this line is inoperable because injection pressure is too low to fill the mold. The region to the right of the respective mold temperature (160°C or 180°C) is inoperable mainly because of scorch. Computer simulation of the injection molding process requires appropriate scorch data. Scorch data from an oscillating disk rheometer, Mooney viscometer, and capillary rheometer were examined’, Only the capillary rheometer provided reliable data for predicting scorch by computer simulation. Different scorch methods produced different scorch results in our laboratory. Scorch data were obtained on a capillary rheometer and on a Mooney viscometer. ‘Two different sulfur-cured, black-filled, SBR compounds were examined (iden- tified as Compound A and Compound B). For the capillary rheometer test, a Monsanto Processability Tester was used (Conditions: 121°C with a 10 min, warm up, L/D = 20 and 1.51 mm dia. capillary). Results are shown in Table III. The data in Table III show a relatively small difference in scorch times measured by the capillary rheometer; a large difference is noted for Mooney scorch values. These scorch results show that the measurement method strongly affects the scorch values, consistent with the differences mentioned above'’, Scorch sometimes causes flow problems during injection molding at the high temperatures associated with high production rates. Process aids added to a compound might reduce scorch problems; these aids tend to reduce temperature increase in the nozzle and gates during injection. Wheelans® suggests that this temperature increase be maintained by incorporating the needed scorch safety in the compound without using process aids. Sufficient scorch time is needed after mold filling to allow relaxation of rubber molecules to their random coil configuration"®. Relaxation times that are too short may cause anisotropic properties. ‘Tape UL ScoRCH VALUES DETERMINED BY TWO DIFFERENT METHODS. Scorch method ‘Compound A B Mooney Scorch* >30 15.6 Capillary rheometer’ 14.1 124 “Time (min.) to a5 point rise at 250°F with the small rotor. ‘Time (min.) to a 0.35 MPa increase in pressure.672 RUBBER CHEMISTRY AND TECHNOLOGY VoL. 58 2. Backrinding.—This term describes the torn or gouged appearance of some vulcanizates at the mold parting line. Backrinding is caused by the continuing thermal expansion of rubber in a mold after crosslinking occurs at the parting line. This expansion forces crosslinked rubber into the opening at the parting line and causes it to rupture. Both molded part geometry and rubber composition affect backrinding. It becomes more severe as the mass/surface area ratio increases for a molded part. Hence, backrinding is most severe for a sphere or ball, where this ratio is max- imum. The occurrence of backrinding was demonstrated by curing a ball in a compression mold (43 mm diameter) with the parting line at the equator of the ball. An unfilled NR compound, designated 1A by ASTM D 3184-75, was molded; twice the designated level of TBBS accelerator was used. Doubling the TBBS (N-tert-butyl-2-benzothiazole sulfenamide) level in the compound reduces scorch time and aggavates backrinding. This compound was cured at 120°C or 160°C. The 160°C temperature caused a severely gouged or torn appearance about 4.5 mm wide at the parting line. For the ball cured at 120°C, the parting line was only about 0.5 mm wide and relatively smooth. Hence, at the reduced temperature of 120°C, scorch time was sufficiently long to avert backrinding. Other techniques to reduce backrinding include preheating a compound before placing it in a mold cavity, e.g., by microwave, or placing the minimum weight of compound in the mold that is required for a given molded part. Backrinding can occur with any crosslinkable composition; itis a special prob- lem with some HP elastomers like perfluoroelastomer (PFE). To reduce or elim- inate backrinding in O-rings made from PFE, special compression molds have been designed (Figure 8)” The major difference between a conventional compression mold (Figure 1) and the one in Figure 8 is the enlarged section between the mold parting line and the O-ring cavity. Although the effect of the enlarged section is not com- pletely understood, it is claimed to reduce or eliminate backrinding. The thicker rubber in the enlarged section can be trimmed, e.g., by a die cutter. 3. Mold fouling.—This is the process by which undesirable material is de- posited on a mold surface". It is especially undesirable on molds used to produce ENLARGED SECTION FLASH GROOVE O-RING CAVITY FiG, 8—Cross section of left half of a special mold for curing O-rings from perfluoroelastomer. After Reference 20.MOLDING 673 rubber parts for HP applications. For example, with fluoroelastomer, fouling impairs flow in a mold; it also causes surface imperfections as well as causing parts to stick to a mold surface’. Another problem is that the film on dirty molds can alter heat transfer to rubber during molding”. With the wide range of different elastomers and compounding ingredients in use, there are many causes for fouling. For example, CSM rubber can foul the surface of an ordinary steel mold’; ingredients like TMTD and whiting can be problems”. Fouling by TMTD is associated with its decomposition to the carbamate. Whiting (calcium carbonate) is a problem if itis used to dust pelletized rubber which is subsequently injection molded. Whiting can severely foul runner systems and significantly reduce their crosssectional area’. The reduced area, combined with the high viscosity compositions required for some HP applications, can cause underfilled rubber parts. To minimize problems with fouling, a number of mold cleaning methods are used?!, These include blasting the fouled surface with particulates, acid and alkaline treatments, and ultrasonic treatments. These methods are a disadvantage because a mold must be removed from a press for treatment. Removal can be avoided by using an in-place cleaning method". A special rubber compound containing an aminohydroxy additive is cured in a fouled mold. The additive permeates the film of fouled material and releases it from the mold; the film is then removed along with cured cleaning compound. Another source for mold fouling is the adhesive used to bond rubber to inserts during molding. Adhesive might be displaced from a coated insert to a mold face. 4. Inserls.—Many rubber parts for HP applications contain inserts. During molding, it is best to firmly position inserts by contact with the mold; if they are completely imbedded in rubber, removable support pins are necessary to position them. Vertical molding presses (these have horizontal platens) are recommended so that inserts are held in position by gravity. If necessary, permanent magnets may be used to hold steel inserts in place. It may be desirable to preheat adhesive-coated steel inserts before molding, especially if the insert is thicker" than about 2 mm. While preheating might be done with hot air, this method may cause the adhesive to crosslink before metal reaches the desired temperature. To avoid this, induction heating may be used; by induction, the metal is heated selectively and rapidly with less effect on the hesive. While complete precure of the adhesive must be avoided, a partial cure is sometimes useful. A partial cure can reduce the scouring or wiping of adhesive by rubber during molding. Wiping can be a special problem with injection mold- ing where extremely high pressures cause rubber to enter a mold rapidly. If this rapidly flowing rubber impinges directly upon an adhesive-coated insert, it might displace the adhesive and cause a nonbonded region. This can be quite critical for a rubber part that must perform in an HP application. To prevent nonbonded regions, injected rubber must not impinge directly upon adhesive-coated inserts”. Figure 9 shows a preferred sprue location for a mold for an engine mount®. Rubber enters the mold remote to the adhesive- coated plates, and therefore does not scour adhesive from them. Hence, good bonding should result. ‘The need for a post cure is a problem with some elastomers containing a bonded insert, such as silicone and fluoroelastomer. Post-cure temperature is generally much higher than molding temperature. This higher temperature might decompose the adhesive, corrode the metal insert, and weaken the bond.674 RUBBER CHEMISTRY AND TECHNOLOGY Vou. 58 NC SPRUE MOLD RUBBER ADHESIVE-COATED PLATES Fic. 9.—Cross section of an injection mold for an engine mount with adhesive-coated metal plates in place. After Reference 25. It is recommended that post-cure temperature be gradually increased, rather than to immediately expose a bonded part to the final (highest) post-cure temperature, A graduated temperature increase permits volatile materials to diffuse. While metal inserts are typically used in rubber, plastic inserts might also be. A rubber impeller with a plastic insert is representative of an HP application”. The impeller is used in the water pump of an outboard motor; it is tested under severe conditions, namely 2,000 hours at 82°C and 6,000 revolutions per min. After this test, the impeller survived but the die cast aluminum housings con- taining the impeller were literally destroyed. The use of aplastic insert in rubber requires additional consideration relative to a metal one”. The plastic insert must have a softening temperature that is high enough to resist distortion at molding temperature. Plasticizer must not migrate from the rubber composition to the plastic insert, as happened with polycarbonate plastic. 5. Control. Microprocessors are finding increased use in controlling rubber molding operations. A microprocessor can simultaneously control a number of important molding factors. For example in injection molding, a microprocessor might control temperature, injection speed and back pressure™. Microprocessor control is also used in transfer molding operations®. A single microprocessor-based system controls 42 presses for transfer molding electrical connectors. This system holds mold temperatures within +1.7°G, a significant improvement over former control methods. In another approach, thermocouples in production press platens, and an oscillating disc rheometer (ODR), provide data to a computer”. Using the ODR data, the computer compensates production cure schedules for batch-to-batch variations. The computer also compares thermocouple readings with set point data stored in it. This information is then used to control the temperature of molds used for curing rubber seals.MOLDING 675 Il, HIGH-PERFORMANCE APPLICATIONS In this section emphasis is placed on rubber seals, bearings, and mounts used in selected HP applications; then rubber use in electrical applications is briefly discussed. A. SEALS Seals are devices used to prevent or reduce passage or flow of a fluid (gas or liquid) between two surfaces. There are many types of molded rubber seals used in HP applications, but only O-rings and lip seals are considered here. 1. O-rings.—A special mold (Figure 8) for making O-rings from perfluoro- elastomer (PFE) was described in the section on backrinding. This special mold is needed because of the very poor processability of PFE". Other aspects of this elastomer are also unusual. O-rings from PFE may require a stepwise post cure over a 5-day period to a final temperature of 550°C, preferably under nitrogen or some other inert gas”. Also unusual is the availability of PFE. It is not available as an uncrosslinked elastomer; instead, it is available only in the form of finished parts, e.g. O-rings" In the form of finished parts, it cost about $4/gram in 1977; this cost is no doubt justified by the outstanding performance of PFE. PFE has a continuous service temperature of 260°C or above; it resists hot jet fuels, hydraulic fluids, as well as virtually all organic fluids and amines that rapidly swell or attack hydrofluoroelastomers*'. For example, O-rings from PFE are resistant to fluids like acrylonitrile, methyl methacrylate and m-phenylene diamine. Compression set values for PFE and FKM O-rings are shown in Table While set values of PFE are inferior to FKM at lower temperatures, set for PFE is lower at an extreme temperature of 288°C. Because of outstanding tem- perature and fluid resistance, PFE O-rings seal against aggressive fluids like dinitrogen tetroxide in missile applications". Molding very small O-rings by compression causes scrap losses of 50% or more“. These O-rings had an inner diameter of 7.7 mm with a maximum cross- section of 1.8 mm; typically, molds contain 200-400 cavities. ‘A comparison was made between compression molding and injection molding FKM O-rings by computer simulation, It was concluded that O-rings could be injection molded from FKM at scrap and production rates comparable to compression molding. The only justification for injection molding was the elim- ination of certain necessary processing steps in O-ring manufacture by compres- sion molding. ‘Taste IV Compression SET OF O-RINGS Set, % after 70 hours at Temperature, °C indicated temperature PFE FKM 24 20 9 232 70 32 288 18 100676 RUBBER CHEMISTRY AND TECHNOLOGY VoL. 58 (a) (b) Fic. 10.—Round-shaped preform (a) tends to trap air when molded; elliptical-shaped preform (b) forces air out during mold closing. When molding O-rings by compression, shape of the preform is important. Improperly shaped preforms may trap air and cause imperfections on the surface of O-rings (Figure 10). A round preform (Figure 10a) tends to trap air at the 6 and 12 o'clock positions. An elliptical shaped preform contacts these positions first (Figure 10b); contact between rubber and mold progresses as the mold closes. This action moves air to the parting line where it is expelled, providing O-rings with a good surface finish. 2. Lip seals.—Like O-rings, lip seals are widely used in sealing applications requiring high performance. These are annular shaped seals generally formed by in-mold bonding of elastomers to steel". Often, a concentric steel spring provides additional radial force to improve and maintain sealing. This spring is inserted in the semicircular groove to the left of the seal lip (Figure 11). STEEL GATE (L) LIP Fic. 11.—Gross section of an NBR lip seal with the gate located either by the lip (L) or by the heel (H) of the seal. After Reference 35,MOLDING 677 This figure shows a crosssection of an NBR lip seal which was injection molded with two different gate locations. The gate in the mold was located either by the lip of the seal or by the heel of the seal. Following mold filling, the NBR com- pound bonded to the steel insert and cured. Cured seals were then tested for leakage. It was found that heel-gated seals consistently leaked after testing for only about 15-18 minutes. Lip-gated seals did not leak even when tested for periods as long as 300 hours. Then the lip-gated injection mold for these seals was made into a compression mold. Preforms were loaded into this compression mold so that they flowed in either of two directions. When flow was from heel to lip, nearly all seals leaked. No leakage occurred for seals where flow was from lip to heel. Hence, similar leak test results were obtained on seals molded by either compression or injection. Other tests on the seals established that dimensions, radial forces and overall physical and chemical properties were all within normal limits. Hence, direction of flow in the molds determined the tendency for these seals to leak*®, This points out the subtleties associated with molding rubber parts for some HP applications. Lip seals molded from FKM rubber meet severe conditions when installed as crankshaft oil seals; conditions include temperature (— 40°C to 150°C), dry run- ning capability, and resistance to the effects of dirt and contamination during operation®. Dirt entry into the sal is limited by a dust lip molded onto it. Hence, this seal contains two molded lips, an oil lip like that in Figure 11, as well as a dust lip. B. BEARINGS AND MOUNTS Rubber bearings and mounts are used in many demanding HP applications. One reason for this is that they provide an extremely wide range of useful properties when rubber type and design are appropriately matched. HP appli- cation examples include rotor bearings for helicopters, structural mounts to protect buildings from vibration, bridge bearings, engine mounts and nozzle bearings for the space shuttle. Only the last three applications are discussed further; in these applications emphasis is placed on NR 1. Bridge bearings.—Figure 12 shows a cut section from a bridge bearing. Bearings like this support the considerable weight of a bridge but deflect only slightly in the vertical direction. The steel plates, bonded to rubber, provide extremely high stiffness in this direction. There is movement of the bridge in the horizontal direction caused by its thermal contraction and expansion. The bearing effectively accommodates this horizontal movement in shear. Because bearing stiffness in shear is low, only low forces are transferred to the support structure of a bridge. NR is a preferred rubber for bridge bearings, particularly in cold climates; it keeps horizontal forces low and relatively constant throughout the year’”. Bridge bearings have unusual shrinkage characteristics, Shrinkage or con- traction is considerably higher in the vertical direction (Figure 12) than in the horizontal direction. This difference is caused by the high coefficient of expan- sion of rubber relative to steel. Because rubber in bridge bearings is bonded to steel, rubber contracts much like steel in the horizontal direction, Most of the volume contraction is accommodated by linear contraction in the vertical direc- tion. Hence, molded bridge bearings will have the proper dimensions only if these differences are considered in designing molds for them. 2. Engine mounts.—Fibers, incorporated in engine mounts, cause a higher stiffness in one horizontal direction than in a transverse horizontal direction®.678 RUBBER CHEMISTRY AND TECHNOLOGY VoL. 58 Fic. 12—Section cut from a bridge bearing showing steel plates bonded to rubber. 1.0 SHRINKAGE (%) oO 0 4 8 12 FIBER LEVEL (PHR) Fic. 13.—Effect of oriented fibers on the shrinkage of an NR compound along (A) the fiber axis, and perpendicular (P) to the fiber axis. After Reference 15,MOLDING 679 Fic. 14.—Nozzle bearing for the solid rockets used with the space shuttle". Courtesy Malaysian Rub- ber Producers Research Association. For example, oriented fibers cause mount stiffness opposing forward engine displacement to be 1.5 times that opposing transverse displacement. Typically, differences in shrinkage are associated with different fiber orientations. Figure 13 shows the effect of bonded and oriented fibers on the shrinkage of an NR compound". The fibers were oriented by a two-roll mill; they are embedded in an NR compound containing 20 parts by volume of HAF carbon black. In Figure 13, shrinkage, measured perpendicular to the fiber axis, is virtually unchanged by the level of fiber. When measured along the fiber axis, increased fiber level progressively reduces shrinkage. Thus the oriented fibers affect shrinkage in a manner similar to the steel plates in the bridge bearing. Again, this must be taken into account in designing molds if critical part dimensions are to be met. 3. Nozzle bearings.—A laminated NR/steel bearing (Figure 14), used in the space shuttle Columbia, represents an extremely demanding application for a molded rubber product®. One face of the bearing is attached to the rocket base, the other to the nozzle. In service, the bearing must resist compressive forces of 13 MN. While doing this, it must permit the nozzle to vector =8°. Figure 15 shows a cross section of the bearing in its 18 Mg mold. Split rings on the inside diameter (I.D.) control spacing of the annular steel elements in the laminate. The column of vertical circles in the mold represents electric heaters; strip heaters are also used. Eight individually-controlled heat zones provide suf- ficient heat to cure a bearing in 12 hours. During cure, over 100 thermocouples monitor temperature. During molding of subscale bearings, rubber flowed together from adjacent layers of NR and caused surface flaws. The split rings on the outside diameter680 RUBBER CHEMISTRY AND TECHNOLOGY VoL. 58 SPLIT RINGS ON 0.0. ELECTRIC OF MOLD HEATERS: ‘SPLIT RINGS ON 1.0. OF MOLD NR LAYERS Fic. 15.—Cross section of a nozzle bearing in its mold. After Reference 39. (O.D,) in Figure 16 eliminated this problem; they allowed excess rubber to ex- trude directly from the mold. ‘Another problem was associated with local nonbonding; a cold area in the mold and a minor upward shift in the activation threshold for the adhesive system were later found to cause this problem. Resolution of these molding problems has provided bearings which peform satisfactorily in this demanding HP appli- cation. ©. ELEGTRICAL APPLICATIONS Molding of spark plug boots and electrical connectors are briefly considered in this section. 1. Spark plug boots. —Spark plug boots must meet stringent specifications. For example, some need excellent dielectric properties and must resist temperatures of 232°C", Large quantities of spark plug boots are molded from silicone rubber by transfer and injection. With injection molding, production rates are extremely high“®. Four molds, each with 96 cavities, are used in a four-station injection machine. Because of the high cost of the silicone rubber, runners are mixed with virgin silicone rubber. This mixture, as pellets, is fed into the injection machine at high rates. Thus, spark plug boots represent an HP application where parts are made in extremely large quantities. 2. Electrical connectors. —Flash in molded electrical connectors is a consider- able problem. The flash might get between pin and socket in a connector; this could cause an open circuit. A special compression mold prevents flash fromMOLDING 681 PINS TOP PLATE UNCURED RUBBER BOTTOM CAVITY FOR PLATE EXCESS Fic. 16.—Mold design to prevent flash in holes of electrical connectors. After Reference 41 SLEEVES forming in molded holes in connectors. In the mold (Figure 16), uncured rubber is shown in the mold cavity between the bottom and top mold plates‘, When the mold closes, the rubber is squeezed into the cavity in the center plate; pins in the top plate enter the sleeves in the bottom plate. This action forms a flash-free hole in the connector. Excess rubber flows through the sleeves into the cavity provided in the bottom plate. Flash is also a problem in transfer-molded electrical connectors”. During molding, pins are bonded to silicone rubber. If enough molding pressure was used to fill all cavities, flashing occurred on the pins; if pressure was reduced to stop flashing, unfilled parts resulted. This dilemma was resolved by incorporating a processing additive that improved rubber flow. Hence, reduced molding pressure was adequate to fill the 64-cavity mold; flash on the pins was greatly reduced. Where flash did occur, it was mainly caused by undersized pins. IV. SUMMARY This paper broadly considers rubbers (elastomers), molding methods, and some problems associated with molding for high-performance (HP) applications. Molding procedures are then reviewed for several products used in HP appli- cations. The elastomers mainly discussed are NR, SBR, CR, NBR, chloro-sulfonyl- polyethylene rubber, silicone rubber, hydrofluoroelastomer and perfluorelas- tomer. NR is used in HP applications because it possesses desirable properties such as excellent fatigue resistance and high strength. Other rubbers or elasto- mers, such as silicone or perfluoroelastomer, are used in HP applications because they resist high temperatures and aggressive fluids. When molding these elastomers by compression, transfer, and injection, spe- cial procedures are sometimes necessary. These are discussed along with factors682 RUBBER CHEMISTRY AND TECHNOLOGY VoL. 58 that affect molding behavior and the quality of molded products. These factors include: rheology, rubber shrinkage, inserts in moldings, mold fouling, mold materials, and design factors for molds. ‘A special design is used for a compression mold for O-rings made from perfluoroelastomer. These are used to seal against aggressive fluids like dinitro- gen tetroxide. In other HP sealing applications, NBR lip seals are used; molding factors are discussed which significantly affect their sealing capability. Also discussed are laminates, where NR is bonded to metal. These are used as bridge bearings and the steel plates in them cause nonuniform shrinkage. 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Colbert, Plast. and Rubber Process. Appl. 2, 309 (1982), A. S. Berens and J. H. Born, presented at the Fourth European Conference for Plastics and Rubber, Paris, France, June 1974.MOLDING 683, *8 Elastomers Notebook, E. 1. duPont, No. 228, Winter 85/84, p. 14 2”, A. Meyer and J. A. Welch, RuBBER Citem, TECHNOL. 50, 145 (1977). SC. D. Moore (to Ford Motor Co,), U.S. 4,262,889 (April 21, 1981). °° Rubber Dev. 38, 84 (1982), “W. Lynch, in “Handbook of Silicone Rubber Fabrication", Van Nostrand~Reinhold Company, New York, 1978, ch. 6, “1G. J. Daubenberger (to Daco Rubber, Inc.), U.S. 3,145,422 (August 25, 1964). °° Chem, Process. (Chicago) 46, 120 (1983),