Specialty Polyphenylene Sulfide (PPS) Compound for
Transcription
Specialty Polyphenylene Sulfide (PPS) Compound for
Specialty Polyphenylene Sulfide (PPS) Compound for New Generations of Fiberoptic Connectors J. R. Dole, Celanese, 8040 Dixie Highway, Florence, KY 41042 USA Presented at the 33rd Annual IICIT Symposium October 23-25, 2000 at Orlando, Florida Introduction A new linear polyphenylene sulfide (PPS) compound has been introduced to meet the expanding needs of businesses and individual consumers as they convert to rapid transmission fiberoptic technology from traditional copper wiring. Developed in conjunction with end-users, cable manufacturers and custom molders, this material is uniquely positioned to satisfy the most stringent existing and anticipated market requirements. Working closely with fiberoptic product manufacturers and end-users, a number of formulations were developed and trialed, of which Fortron 8670A61 had the optimum balance of properties as noted in Table 1. Table 1. Short Term Properties Fortron 8670A61 Fiberoptic Connector Grade 1 Test Fortron® 8670A61 linear PPS has excellent melt flow and can easily fill the extremely thin sections and features of the new smaller, denser connectors. That low viscosity and its faster crystallization behavior also benefit the processor via lower mold maintenance and faster cycle times for increased productivity. Additionally, smaller runner systems are possible to significantly reduce material consumption, scrap and thus “all-up” part costs. The new product exhibits low, uniform shrinkage and thermal expansion/ contraction and minimal moisture uptake, so precise tolerances can be molded-in and maintained over a wide variety of end-use service conditions. This compound is targeted to compete favorably with ceramics, zirconia, and thermosetting resins, as well as high performance precision engineering plastics in use in today’s fiberoptic products. It is ideal for new generations of small form factor (SFF) connectors, which have twice the density of the current popular fiberoptic connectors. Discussion The key targets for development of this new grade were: Method Units Value Specific Gravity ISO1183 g/cc 1.81 Water Absorption ASTM D570 % 0.015 Melting Point – °C 283 Tensile Strength ISO 527 MPa 65 Tensile Weld Line Strength ISO 527 MPa 34 Tensile Elongation ISO 527 % 0.5 Flex Strength ISO 178 MPa 100 Flex Modulus ISO 178 MPa 16,500 Compressive Strength ISO 604 MPa 140 Compressive Modulus ISO 605 MPa 17,500 Notched/Unnotched Izod ISO 180/1A KJ/m2 3/10 Rockwell “M” Hardness Deflection Temp Under Load: @ 1.8 MPa @ 8.0 MPa Coefficient of Thermal Expansion: Flow Transverse ASTM D785 – 102 ISO 75 ISO 75 °C °C 275 215 ISO 11359-2 ISO 11359-2 1x10 -5/°C 1x10 -5/°C 1.6 1.6 Flammability UL94 – V-0 Key among the “short term” properties is low moisture absorption, so molded connectors could maintain the tightest possible tolerances in end use. As can be seen from Table 2, the new grade has 25% lower moisture uptake versus popular PPS grades already used in fiberoptic connector manufacture. Versus out-of-kind thermoplastics and thermosets compared, that advantage grows to 42-62%. 1. High melt flow to fill intricate parts easily and reduce material consumption and costs (via smaller runners) 2. Fast crystallinity to maximize productivity and minimize tooling and machinery investment Table 2. Relative Moisture Absorption Fortron Fiberoptic Connector Grades versus Competition per ASTM D570 3. Lowest possible, most uniform shrinkage and thermal expansion characteristics, plus low environmental effects from post-molding stress relief and moisture uptake Grade Moisture Gain (wt%) after 24 Hrs Immersion Fortron® 8670A61 0.015 Fortron® 6165A6, 6850L6 0.020 Amorphous PES/PEI 0.260-0.400 Ease of machining/polishing for optimum surface characteristic Thermosetting Resins 0.350-0.400 4. 1 See www.celanese.com for latest datasheet. Page | 1 Specialty Polyphenylene Sulfide (PPS) Compound for New Generations of Fiberoptic Connectors (continued) A second critical element is a low, controlled, isotropic as possible coefficient of thermal expansion. Test conditions commonly span 140ºC, and it is most desirable to have a minimal dimensional change or distortion over this range. As can be seen in Table 3, the new grade exhibits better isotropic dimensional control performance. Its CTE may not be absolutely the lowest against competing materials in all “directions”, but its uniformity is most impressive. Table 3. Relative Coefficients of Thermal Expansion (CTE) Fortron Fiberoptic Connector Grades versus Competition as per ISO 11359-2 and ASTM D696 CTE (x10 /°C) from -50 to +90 °C Table 5 depicts the isotropic and very low shrinkage of the new product, and how shrinkage is reduced dramatically in thinner wall sections. Versus the best previous grades, the new compound offers an improvement in average shrinkage and is perfectly isotropic versus the more anisotropic competing products. TABLE 5. Relative Mold Shrinkage Performance Fortron Connector Grades versus Competition Grade Shrinkage (mils/inch) Grade Part Thickness 8670A61 3.0mm 5 Grade Flow Transverse Fortron® 8670A61 1.6 1.6 Fortron® 6165A6 1.9 2.4 Fortron® 6850L6 1.5 1.7 Amorphous PES/PEI 1.4 2.3 Thermosetting Resins 1.1 2.0 Next, it is quite important that any material be easy to handle, possess a broad molding window for flexibility in processing, and be able to exactly reproduce fine features in intricate connectors. Isotropy in shrinkage assists the designer, moldmaker, and molder in the task of producing devices to the desired tolerance range – in this case typically 1-3 microns. Table 4 describes the material preparation, equipment, and set up requirements for the new grade, which are similar to those for other PPS compounds. Table 4. Recommended Molding Conditions for Fortron 8670A61 Fiberoptic Connector Grade Drying Conditions 6165A6 6850L6 200-220ºC Center Zone 280-300ºC Front Zone 290-310ºC Measured Melt Temperature 290-315ºC Transverse 4 4 1.5mm 3 3 0.75mm 1.5 1.5 3.0mm 4 6 1.5mm 3 5 0.75mm 3 4 3.0mm 4 6 1.5mm 3 5 0.75mm 3 4 Competing PEI/PES 3.0mm 3-7 5-7 Competing Thermoset 3.0mm 1 3 Additionally, with the processor in mind, this new compound also exhibits significantly better flash performance, as can be seen in Table 6. Previous grades, commonly used in less demanding applications, were improved upon by 40-50% in retarding the tendency to flash. 3-4 hours @ 140º-150ºC dehumidifying hopper dryer Machine Settings Feed Zone Flow TABLE 6. Relative Flash Performance Fortron Fiberoptic Connector Grades Trials Conducted in Summit Laboratories With Celanese Flash Tool (see Figure 1) Grade 8670A61 Flash Length Index 5 Screw Speed 40-100 rpm 6165A6 9 Cushion 3-9 mm 6850L6 10 Back Pressure 0 - 10 MPa Injection Speed Medium Fast (up to 120mm/sec) Screw Design L/D 16:1 to 28:1 3:1 - 4:1 compression Even distribution of feed, transition, metering zones Nozzle Small orifice reverse tapered or positive shutoff Mold Temp. 140-160ºC Page | 2 Specialty Polyphenylene Sulfide (PPS) Compound for New Generations of Fiberoptic Connectors (continued) the typical fiberoptic connector, is the dominant factor in the molding cycle time to crystallize and solidify the shot prior to ejection. And, if it is not possible to use the reground runners as feedstock to mold parts, then the runner weight is the pre-eminent fraction of molding scrap. With lower-flow materials (both other PPS grades and “out-of-kind” thermoplastics and thermo-sets), large runner diameters (2.5 - 4.5mm) were neces sary, accounting for 90-95% of the shot weight in 2 and 4 cavity tools – all going to scrap, and effectively multiplying the real cost per part. Figure 1. Schematic of 70 x 70 x 4.5mm Celanese Flash Tool vent 1 4 vent vent 2 3 vent vent 3 2 vent vent 4 1 vent 19 mm 12.7 mm Center Gate 75 microns vs. 6.4 mm width 60 microns vs. 6.4 mm width 3 45 microns vs. 6.4 mm width 4 1 mm vs. 6.4 mm width 1 2 The new grade also offers excellent flow in thin sections, as noted in Table 7. TABLE 7. Mold Flow vs. Wall Thickness/Pressure Fortron PPS 8670A61 Fiberoptic Connector Grade Wall Thickness (mm) 1.5 3.0 Injection Pressure (MPA) Flow Length (mm) 20 40 40 55 80 65 20 4. Another tangible benefit of the new compound is its relatively good weld line performance - key to improved part performance in multi-gated, “hollow” or cored parts, as shown in Table 8. Even though it is more highly reinforced than any other commercial Fortron® grade, the new compound has excellent weld strength. TABLE 8. Weld Line Tensile Strength Retention Fortron PPS 8670A61, 6165A6, 6850L6 Fiberoptic Connector Grades as per Test Method ISO 527 Grade Weld Line Strength (MPa) Retention (%) Single Gated Bar Double End Gated Bar 8670A61 65 34 52 200 6165A6 130 36 28 40 265 6850L6 125 28 22 80 330 This can have several demonstrated benefits: 1. By filling at lower pressures, parts will contain much less molded-in-stress. Trials indicated mold ed-in-stress can yield dimensional changes of 0.0009-0.0010 inches (23-25 microns), or about 10 to 20X the typical tolerance for fiberoptic connectors. Low molded-in- stress levels in parts made from the new product offer a significant improvement in control of dimensions in end-use versus previously available grades. Table 9 shows a comparison of molding cycles with the new Fortron grade, established PPS grades commonly used in fiberoptic interconnects, and out-of-kind competition, showing relative molding cost and productivity impact. Fortron 8670A61 fills easier and crystallizes faster than any other PPS we produce, offering a 20% improvement versus our other commercial PPS compounds. Cycle times in trials were nearly 30% faster versus amorphous family products and 40% quicker versus thermosets. Translating to commercial volumes, the new PPS compound shows the potential to save in the range of $7-15M per million pieces molded. 2. The high flow of the new grade makes ever-moreintricate designs possible. Small features as fine as 5 mils (125 microns) are capable of being produced. 3. This same flow advantage translates to substantially smaller runners being necessary to feed multi-cavity molds. The runner, being far greater in thickness than Page | 3 Specialty Polyphenylene Sulfide (PPS) Compound for New Generations of Fiberoptic Connectors (continued) TABLE 9 Molding Performance Cycle Time/Cost Per Piece Fortron ® PPS 8670A61 vs. Other Products Grade Avg. Cycle Time (secs) “Molding Time Value” Cost/1000 pcs. Fortron 8670A61 11.0 $36.67 Fortron 6165A6, 6850L6 13.2 $44.00 Competing PES/PEI 14.1 $47.00 Competing Thermoset Epoxy 15.4 $51.33 *Basis = 1,2,4 cavity molds average = 3.0 cavities Part weights = 0.097 to 0.312 gm Shot weights including runner 3.2 to 15.6 gm Fortron 8670A61 cycle time range 10.0 - 14.8 secs Machine hour cost = U.S. $36.00 A typical ferrule and multi-fiber connector is shown in Figure 2. Figure 2 (a) Top View Machining and polishing of connectors molded from the new grade is improved versus previous Fortron compounds. The higher flow and unique combination of polymers and fillers make for a superior as-molded surface finish. Additionally, the higher hardness of the new grade improves machinability, reducing or eliminating problems with “chip clearance” and surface “smearing”. As Fortron 8670A61 is very highly reinforced, we recommend molds and injection molding machine barrels and screws be made of specialty wear resistant materials for longest life. Molds: • • • • • • D-2 tool steel, hardened to Rockwell C 57 minimum Bohler-Uddeholm Elmax® (same hardness) Thyssen Stahl Ferro-Titanit ® @ Rockwell C 66 minimum Crucible CPM 9V ® @ Rockwell C 57 minimum Hitachi H-503® @ Rockwell C 50 minimum Toyo Kohan V-50® @ Rockwell C 57 minimum Screws: Stellite® 6 or Toyo Kohan TH® Barrels: Xaloy® 800 or Toyo Kohan TH® Summary Fortron 8670A61 – specially developed for new, more complex, higher density fiberoptic connector products offers a multiplicity of benefits to the end-user, cable assembler, and molder: Figure 2 (b) End View Page | 4 • • • Reduced raw material consumption and cost Lower molding and finishing expenses Improved dimensional stability for enhanced performance. 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